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Eduard Meijer
Charge transport in disordered
organic field-effect transistors
PROEFSCHRIFT
door
Samenstelling promotiecommissie:
Rector Magnificus, voorzitter
Prof.dr.ir. T.M. Klapwijk, Technische Universiteit Delft, promotor
Prof.dr. P.W.M. Blom, Rijksuniversiteit Groningen
Prof.dr. L.D.A. Siebbeles, Technische Universiteit Delft
Prof.dr. G.G. Malliaras, Cornell University, Ithaca, New York, USA
Prof.dr. H. Bässler, Philipps Universität, Marburg, Deutschland
Prof.dr. D. Emin, University of New Mexico, Albuquerque, USA
Dr. D.M. de Leeuw, Philips Research Laboratories, Eindhoven
Prof.dr. S.W. de Leeuw, Technische Universiteit Delft, reservelid
This work is part of the research programme of the Stichting voor Fundamenteel Onderzoek der Materie
(FOM), which is financially supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek
(NWO).
The work described in this thesis has primarily been carried out at the Philips Research Laboratories,
Eindhoven, The Netherlands, as part of the Philips Research Programme.
1 General Introduction 1
1.1 Historical perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Charge transport in polymeric semiconductors . . . . . . . . . . . . . . . 3
1.2.1 Hopping transport . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.2 Multiple trapping and release model . . . . . . . . . . . . . . . . 7
1.2.3 Polarons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.3 Scope of this work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.3.1 The field-effect transistor . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Outline of this thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2 The switch-on voltage and the field-effect mobility in disordered organic field-
effect transistors 15
2.1 The switch-on voltage . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.3 The classical threshold voltage . . . . . . . . . . . . . . . . . . . 17
2.1.4 Definition of the switch-on voltage . . . . . . . . . . . . . . . . . 18
2.1.5 Modeling and discussion . . . . . . . . . . . . . . . . . . . . . . 18
2.1.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2 The field-effect mobility . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.2 Calculation of the charge distribution . . . . . . . . . . . . . . . 23
2.2.3 Modeling the mobility variation . . . . . . . . . . . . . . . . . . 24
2.2.4 Discussion of the field-effect mobility . . . . . . . . . . . . . . . 26
2.2.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3 Unifying the charge transport in polymeric FETs with PLEDs . . . . . . 26
2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.2 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.3 The mobility - charge density relation . . . . . . . . . . . . . . . 28
2.3.4 Unification of the LED and FET models . . . . . . . . . . . . . . 29
2.3.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
viii Contents
Summary 119
Samenvatting 123
Dankwoord 131
Chapter 1
General Introduction
area displays as well as for high-volume production of integrated circuits [11]. Also,
the mechanical toughness of polymers and the flexibility of polymeric thin films allow
their use in flexible displays and flexible electronics (see Fig.1.1). Furthermore, polymers
are usually associated with low-processing costs, allowing them to be used in disposable
products.
The properties of polymers can be tuned by adding functionalizing sidegroups, or
by building in elements such as sulfur or nitrogen. A lot of effort is being put in the
synthesis of new materials, with improved performance and novel properties. These ad-
vantages make them interesting candidates for low-cost, flexible industrial applications.
Understanding the optical and electronic properties of these materials on a microscopic
level has turned out to be an intriguing challenge that merges the fields of physics and
chemistry.
For the operation and performance of all these devices the charge transport through
the polymer layer is the dominant factor. It is therefore crucial to gain insight into their
charge transport mechanisms. In the following section the most widely used descriptions
of charge transport in disordered organic semiconductors are presented. Emphasis is put
on the presence of disorder. In the context of charge transport, the scope of this thesis
is in the physical description of field-effect transistors based on disordered organic semi-
conductors.
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Figure 1.2: (a) The moleculare structure of polyacetylene, for clarity, hydrogen
atoms are not shown. The alternating double and single bonds in-
dicate that the polymer is conjugated. (b) Schematic representation
of the electronic bonds in polyacetylene. The pz -orbitals overlap to
form π-bonds.
molecule. These delocalized π-electrons are largely responsible for the opto-electronic
behavior of conjugated polymers.
There are large differences between the three-dimensional crystal lattice of most in-
organic semiconductors and the amorphous structure of conjugated polymers. Inorganic
semiconductor crystalline lattices, such as silicon and germanium, are characterized by
long range order and strongly coupled atoms. For silicon and germanium this results in
the formation of long-range delocalized energy bands separated by a forbidden energy
gap [12]. Charge carriers added to the semiconductor can move in these energy bands
with a relatively large mean free path. The limiting factor for this band transport is scat-
tering of the carriers at thermal lattice vibrations, i.e. phonons [10, 12]. This is depicted
schematically in Fig.1.3a. As the number of lattice vibrations decreases with decreasing
temperature, the mobility of the charge carriers increases with decreasing temperature.
In conjugated polymers the polymer chains are weakly bound by van der Waals
forces5. These polymers typically have narrow energy bands, the highest occupied molec-
ular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which can
easily be disrupted by disorder. Although electric charge is delocalized along the π-
conjugated segments of the polymer backbone, the length of such perfectly conjugated
segments is typically limited to length scales of around 5 nm, separated by chemical de-
fects, such as a nonconjugated sp3 -hybridized carbon atom on the polymer backbone, or
by structural defects, such as chain kinks or twists out of coplanarity. Due to the disorder
the semiconductor can not be regarded simply as having two delocalized energy bands
separated by an energy gap. Instead, the charge transporting sites, which are the seg-
ments of the main chain polymer, are subject to a Gaussian distribution of energies (see
Fig.1.4b), implying that all states are localized [13]. The shape of the density of states
(DOS) is suggested to be Gaussian, because of the observed Gaussian shape of the optical
spectra [13].
5 We note that the carbon atoms in a polymer chain are strongly coupled.
1.2 Charge transport in polymeric semiconductors 5
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Figure 1.4: (a) Schematic view of polymer chains broken up in conjugated seg-
ments, which are represented as charge transport sites, between
which the charge carriers hop. (b) A representation is given of the
smeared out density of states, which is often approximated by a
Gaussian distribution for the HOMO and LUMO levels.
the hopping rate between an occupied site i and an adjacent unoccupied site j , which are
separated in energy by E i − E j and in distance by Rij , is described by:
E −E
exp − ki B T j Ei > E j ,
νi j = ν0 exp −2γ Ri j (1.1)
1 Ei < E j ,
where γ −1 quantifies the wavefunction overlap between the sites, ν0 is a prefactor, and k B
is Boltzmanns constant. The Miller-Abrahams model addresses hopping rates at low tem-
peratures between shallow three-dimensional impurity states, assuming that the electron-
lattice coupling is weak. When the Miller-Abrahams model is applied to polymeric semi-
conductors, it is assumed that the conjugated segments of the polymers play the role of
nearly isolated impurity states, and that Eq.1.1 is still valid at high temperatures [16].
Depending on the structural and energetic disorder of the system it can be energet-
ically favorable to hop over a longer distance with a low activation energy (energy dif-
ference between sites), than over a shorter distance with a higher activation energy. This
extension to the Miller-Abrahams model is called variable range hopping [17]. Monroe
developed a model describing hopping transport around the Fermi level in an exponential
density of states [18]. He found that this hopping description is analytically very simi-
lar to a model in which charge carriers are thermally activated to a transport level. For
the description of the temperature and gate voltage dependencies of organic field-effect
transistors Vissenberg and Matters [19] developed a percolation model based on variable
range hopping in an exponential density of states, which will be used throughout this
thesis.
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1.2.3 Polarons
Next to the disorder-induced localization of charge, the strong electron-phonon coupling
in organic materials results in localization of charge. An excess charge carrier on a conju-
gated polymer chain can minimize its energy by a local lattice deformation. This quasipar-
ticle consisting of charge and a lattice deformation, or phonon cloud, is called a polaron.
As polarons represent a local distortion of the lattice, the associated energy levels must
split off from the HOMO level and the LUMO level. These energy levels, which reside
in the energy gap, have often been observed in optical absorption experiments on charged
conjugated polymer films [22–24].
In polaronic charge transport, not only the charge moves under an applied electric
field but the lattice deformation moves with it. Typically, for hopping transport of po-
larons, a description in terms of Miller-Abrahams hopping [16] is insufficient, as multi-
phonon hopping rates need to be considered [25, 26].
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As a follow-up to the previous chapter the field dependence of the in-plane conduc-
tivity is investigated in PTV and P3HT in Chapter 4. Using an empirical relation for
this field-dependence we find an isokinetic temperature that is comparable to the values
obtained from the Meyer-Neldel experiments of Chapter 3. Implications of these findings
are addressed.
function of bias voltage, measurement frequency and temperature. We find that simple
Mott-Schottky analysis can only be applied here if the relaxation time of the semicon-
ducting polymer is taken into account. The long relaxation times are a direct result of the
disorder in the semiconducting polymer layer.
An alternative method for the determination and monitoring of the dopant density
is given in Chapter 8, where the dopant density is extracted directly from the transfer
characteristics of transistors based on PTV and P3HT. It is demonstrated that, due to the
fact that in disordered semiconductors the charge carrier mobility depends on the charge
density, the bulk current can be separated from the field-effect current in the total current
density. It is found that the morphology of the polymer film is crucial for the stability of
transistors that are prone to oxygen doping effects.
In the first 5 chapters we have looked at unipolar p-type organic field-effect tran-
sistors. In Chapter 9 we use a blend of hole-conducting OC1 C10 -PPV and electron-
conducting PCBM to construct a solution-processed ambipolar organic field-effect tran-
sistor. The characteristics of this kind of transistor are measured and analyzed and CMOS-
like inverter operation is demonstrated, paving the way for solution-processable CMOS-
like logic circuitry.
As was demonstrated in the previous chapter a suitable choice of electrode and semi-
conductor can result in ambipolar FETs. In Chapter 10 we show that even a single
solution-processed organic semiconductor can be used in ambipolar transistors, demon-
strating that in principle an intrinsic organic semiconductor can transport both polarities
of charge. Important parameters for experimental observation of this ambipolar behavior
are extrinsic effects such as workfunction mismatch and material purity.
References
[1] http://www.nobel.se/physics/laureates/1956/press.html
[3] http://www.nobel.se/physics/laureates/2000/press.html
[4] D.M. Pai and B.E. Spingett, Rev. Mod. Phys. 65, 163 (1993).
[5] http://www.nobel.se/chemistry/laureates/2000/press.html
[6] C.K. Chiang, C.R. Fincher, Y.W. Park, A.J. Heeger, H. Shirakawa, E.J. Louis, S.C.
Gan, A.G. MacDiarmid, Phys. Rev. Lett. 39, 1098 (1977).
[7] C.K. Chiang, M.A. Druy, S.C. Gau, A.J. Heeger, E.J. Louis, A.G. McDiarmid, Y.W.
Park and H. Shirakawa, J. Am. Chem. Soc. 100, 1013 (1977).
[9] R.E. Peierls, Quantum theory of solids, Oxford University Press, London (1955).
[10] M. Pope and C.E. Swenberg, Electronic Processes in Organic Crystals and Poly-
mers, Oxford University Press (1999).
[11] A.R. Brown, C.P. Jarrett, D.M. de Leeuw and M. Matters, Synth. Met. 88, 37 (1997).
[12] C. Kittel, Introduction to solid state physics, 6th edition (John Wiley & Sons, Inc
1986).
[17] N.F. Mott and E.A. Davies, Electronic processes in non-crystalline materials, 2nd
Edition, Oxford University Press, London (1979).
[19] M.C.J.M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998).
[20] G. Horowitz, R. Hajlaoui and P. Delannoy, J. Phys. III 5, 355 (1995).
[21] D. Emin, private communication, D. Emin, Phys. Today 35, 34 (1982).
[22] K.E. Ziemelis, A.T. Hussain, D.D.C. Bradley and R.H. Friend, Phys. Rev. Lett. 66,
2231 (1991).
[23] P.A. Lane, X. Wei and Z.V. Vardeny, Phys. Rev. Lett. 77, 1544 (1996).
[24] R. Österbacka, C.P. An, X.M. Jiang and Z.V. Vardeny, Science 287, 839 (2000).
[25] T. Holstein, Ann. Phys. 8, 325 (1959).
[26] D. Emin, Adv. Phys. 24, 305 (1975).
[27] S.M. Sze, Physics of semiconductor devices, 2nd edition, John Wiley & Sons, (New
York, 1981).
Chapter 2
Abstract
In this chapter we critically evaluate two characterization parameters of disordered or-
ganic field-effect transistors.
• The switch-on voltage is defined as the flat-band voltage, and is used as character-
ization parameter. The transfer characteristics of the solution processed organic
semiconductors pentacene, poly(2,5-thienylene vinylene) and poly(3-hexyl thio-
phene) are modeled as a function of temperature and gate voltage with a hopping
model in an exponential density of states. The data can be described with reason-
able values for the switch-on voltage, which is independent of temperature. This
result also demonstrates that the large threshold voltage shifts as a function of tem-
perature reported in the literature constitute a fit-parameter without a clear physical
basis.
In the last section of this chapter the transistor description is compared to the models used
for polymeric light-emitting diodes and it is demonstrated that the two device descriptions
can be unified, when the large differences in charge densities in the two device geometries
are taken into account.
16 The switch-on voltage and the field-effect mobility
2.1.2 Experimental
In the experiments we used heavily doped Si wafers as the gate electrode, with a 200 nm
thick layer of thermally oxidized SiO2 as the gate-insulating layer. Using conventional
lithography, gold source and drain contacts are defined with an interdigitated geometry.
The SiO2 layer is treated with the primer hexamethyldisilazane (HMDS) to make the
surface hydrophobic. The samples are measured under high vacuum (10−7 mbar) in an
Oxford optistat CF-V flow cryostat, using a Hewlett-Packard 4156A semiconductor pa-
rameter analyzer. The films of PTV are truly amorphous whereas the pentacene films are
polycrystalline. The P3HT films can be considered nanocrystalline, as ordered regions
of this regioregular polymer alternate with disordered regions [1]. We do not observe
any hysteresis in the current-voltage characteristics and the curves are stable with time
(in vacuum). The field-effect mobilities in the devices have been estimated from the
transconductance [7] at a gate voltage, Vg = −19 V at room temperature and are given
in Table 2.1. For the P3HT transistor described here the processing conditions were not
optimized to give the high mobilities reported in literature [1].
2.1 The switch-on voltage 17
Table 2.1: Values obtained by using Eq.2.6 to model the transfer characteris-
tics of solution-processed pentacene, PTV and P3HT. TD O S repre-
sents the width of the exponential density of states, σ0 is the conduc-
tivity prefactor, α −1 the effective overlap parameter, Vso the switch-
on voltage, and µ RT the field-effect mobility at Vg = −19 V and
room temperature.
Using a percolation model of variable range hopping, an expression for the conductivity
as a function of the charge carrier occupation δ and the temperature T is derived [8]:
TD O S
T
δ Nt (TD O S /T )4 sin π TDTO S
σ (δ, T ) = σ0 (2.4)
(2α)3 Bc
2.1 The switch-on voltage 19
where σ0 is a prefactor of the conductivity, Bc is a critical number for the onset of percola-
tion, which is 2.8 for three-dimensional amorphous systems [17], and α −1 is an effective
overlap parameter between localized states. To calculate the field-effect current we have
to take into account that in a field-effect transistor the charge density is not uniform. Using
the gradual channel approximation (|Vg | |Vds |, where Vds is the source-drain voltage),
we neglect the potential drop from source to drain electrode. To take into account that
the charge-density decreases from the semiconductor-insulator interface to the bulk, we
integrate over the accumulation channel:
W Vds t
Ids = d xσ [δ(x), T ] , (2.5)
L 0
where L, W , and t are the length, width and thickness of the channel, respectively. From
Eqs. 2.4 and 2.5 we obtain the following expression for the field-effect current:
W Vds semi 0 σ0 T 2k B TD O S
Ids =
Lq 2TD O S − T semi 0
4 TDTO S
TD O S
sin π TD O S
T
T
×
(2α) Bc
3
2TDTO S −1
semi 0 Ci Vg − Vso
× (2.6)
2k B TD O S semi 0
where q is the elementary charge, 0 is the permittivity of vacuum, semi the relative di-
electric constant of the semiconductor, and Ci is the insulator capacitance per unit area.
Eq.2.6 is used to model the transfer characteristics of solution processed PTV, pentacene,
and P3HT as a function of Vg and T . The four parameters σ0 , α −1 , TD O S , and Vso were
used to model all the curves, with a value of Bc =2.8. After this initial fit, each curve was
individually modeled with only Vso as variable parameter, with the other parameters fixed.
From this modeling, no temperature dependence of Vso was observed. The results of the
modeling are shown in Figs.2.1, 2.2, and 2.3. The fit parameters are given in Table 2.1.
Good agreement is obtained for all three semiconductors. The single constant Vso for
all temperatures accounts for any fixed charge in the oxide and/or at the semiconductor-
insulator interface. Also, the low values obtained for Vso are realistic numbers. Because
the measurement resolution in the low current regime is limited to 1-10 pA, the onset of
the experimental curves in Figs.2.1, 2.2, and 2.3, seems to be shifting to more negative
gate voltages with decreasing temperature. This is due to current decrease as a function
of temperature, as a result of the thermally activated field-effect mobility (see Chapter
3) [18]. This effect does not translate in a temperature dependence of Vso . Analysis of
the data with the square root technique yields an apparent threshold voltage shift with
temperature of 15 V for the PTV. Eq. 2.1 gives similar results. The values obtained for
the prefactor of the conductivity σ0 seem to be too high with respect to theoretical con-
siderations [15]. The conductivity prefactor is discussed further in Chapters 3 and 4.
20 The switch-on voltage and the field-effect mobility
.
.
.
.
.
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Figure 2.1: Ids versus Vg of a PTV thin-film field-effect transistor for several
temperatures. The solid lines are modeled using Eq.2.6. W=2 cm,
L=10 µm, Vds = −2 V . The inset shows the structure formula of
PTV.
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Figure 2.3: Ids versus Vg of a P3HT thin-film field-effect transistor for several
temperatures. The solid lines are modeled using Eq.2.6. W=2.5
mm, L=10 µm, Vds = −2 V . The inset shows the structure formula
of P3HT.
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We note that, the Fermi level shifting with decreasing temperature [10] has no effect
on Vso . The Fermi level shift, which results from the Fermi-Dirac distribution of the
charge carriers in the exponential density of states, is calculated from Eq.2.3 and is found
to be 0.04 eV over a temperature range of 200 K (see Fig.2.4). This displacement does
not result in a shift of Vso with temperature.
2.1.6 Conclusion
It was argued that the threshold voltage extracted from the transfer characteristics of dis-
ordered organic transistors, using MOSFET theory or Eq.2.1, is only a fit parameter if
the strong inversion regime is not observed in the transfer characteristics. The use of this
parameter in the physical description of organic field-effect transistors is therefore incor-
rect. Instead, we have defined a switch-on voltage for unintentionally doped disordered
organic field-effect transistors as the gate voltage that has to be applied to reach the flat-
band condition. Using a disorder model of hopping in an exponential density of states,
the experimental data of solution-processed PTV, pentacene and P3HT could be described
with reasonable values for the switch-on voltage, which is temperature independent. The
use of Vso as characterization parameter of disordered organic field-effect transistors is
not limited to the model described here, but is generally applicable.
amount of induced charge Ci Vg in Eq.2.7 is only valid when all charge carriers have the
same mobility. In that case, the field-effect mobility is calculated from [7]:
L ∂ Ids
µF E = . (2.8)
W Ci Vds ∂ Vg Vds →0
To check the validity of this equation for disordered organic FETs, we calculate the
charge distribution in the device from Poisson’s equation. Then we use the hopping model
described in the previous section to calculate a local mobility, and compare the results with
the values obtained from Eq.2.8 for both P3HT and PTV field-effect transistors.
where V
is the local potential, which varies from zero far away in the semiconductor bulk
to V in the accumulation channel. The potential distribution as a function of the distance
from the S/I interface, x, follows from the relation:
V0 dV
x= (2.10)
V Fx (V
)
where V0 is the surface potential of the S/I interface. From the variation of the gate-
induced potential V (x) as a function of distance x the density of holes δ Nt (x) can be
calculated. The induced charge per unit area Q ind is related to the gate voltage as follows:
9J 9
9J 9
δ1 >FP @
W
[>QP@
In order to take into account the charge carrier dependent mobility we use again the hop-
ping model described in the previous section. From Eq.2.4 an expression for the local
mobility is derived:
TD O S
T
σ (δ, T ) (T
σ0 D O S /T ) 4
sin π T
TD O S
µl = = (δ Nt )TD O S /T −1 (2.12)
qδ Nt q (2α)3 Bc
Using the parameters from Table 2.1 the local mobility is calculated as a function
of distance from the S/I interface and is plotted in Fig.2.6 for Vg = −19 V at room
temperature for PTV and P3HT. For PTV the modeled local mobility varies from 2.1·10−3
cm2 /Vs at the S/I interface to 8.4·10−4 cm2 /Vs at a distance of 5·10−10 m from the S/I
interface. For P3HT the local mobility varies from 6.6·10−4 cm2 /Vs at the interface to
1.2·10−4 cm2 /Vs at a distance of 5·10−10 m from the interface. The calculations show
that in a polymeric FET even for moderate gate voltages, variations in the local mobility
are considerable. Thus, due to the inhomogeneous charge carrier density in a disordered
FET the local mobility demonstrates a strong variation in the active channel.
2.2 The field-effect mobility 25
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Figure 2.6: The local charge carrier mobility as function of position in the
accumulation layer for (a) a PTV FET and (b) a P3HT FET at
Vg = −19 V . The extracted field-effect mobility as determined
from Eq.2.8 is given as the solid symbol in both figures.
26 The switch-on voltage and the field-effect mobility
2.2.5 Conclusion
In disordered organic field-effect transistors the dependence of the mobility with gate
voltage is determined by the charge carrier dependence of the local mobility. Taking into
account the distribution of the charge carrier density in the active channel perpendicular
to the insulator the local mobility has been calculated as a function of position in the
accumulation layer. It is demonstrated that for disordered organic FETs, in spite of the
strong variations in the local mobility in the active channel, the experimentally determined
field-effect mobility (Eq.2.8) is a reasonable estimate for the local mobility of the charge
carriers at the semiconductor-insulator interface.
.
.
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interest the exponential density of states, which consistently describes the FET measure-
ments at high carrier densities, is a good approximation for the Gaussian density of states,
which consistently describes the PLED measurements at low carrier densities.
with µ∞ the mobility in the limit T → ∞, σ D O S the width of the Gaussian DOS, a the
intersite spacing, and F the applied electric field. The J − V characteristics of a P3HT
28 The switch-on voltage and the field-effect mobility
PLED can also accurately be modeled with space-charge limited currents in combination
with Eq.2.13, as is demonstrated in Fig.2.7. The modeled parameters from Eq.2.13 are
given in Table 2.2. We find at low electric fields hole mobility values for P3HT and
OC1 C10 -PPV of respectively 3×10−5 cm2 /Vs and 5×10−7 cm2 /Vs. These values are
upto three orders of magnitude lower as compared to the mobility values obtained from
the FETs.
where q is the elementary charge, and l is the semiconductor layer thickness. For the
FET, the experimental field-effect mobility is determined as a function of gate bias using
Eq.2.8 and we calculate the volume charge carrier density, p = δ Nt , at the semiconduc-
tor/insulator interface as a function of gate voltage, as outlined in section 2.2.
2.3 Unifying the charge transport in polymeric FETs with PLEDs 29
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µ >FP 9V@
7'26 .
S>FP @
Figure 2.8: Charge carrier mobility as a function of the hole density for
P3HT and OC1 C10 -PPV determined in a hole-only diode ( p <
1017 cm −3 ) and in a field-effect transistor ( p > 1017 cm −3 ). The
dashed lines are a guide to the eye.
The hole mobility versus the volume charge density for P3HT and OC1 C10 -PPV are
given in Fig.2.8, where the values at low charge density ( p < 1017 cm −3 ) are derived
from the PLED data and the values at high charge density ( p > 1017 cm −3 ) are derived
from FET data. From Fig.2.8 we see that the mobility starts to increase rapidly with
charge carrier density when the charge density is larger than a certain minimum value.
Fig.2.8 shows that when measured at the same high values of volume charge carrier den-
sity the field-effect mobility of OC1 C10 -PPV is nearly equal to the field-effect mobility of
P3HT. Furthermore, the dependence of the field-effect mobility on charge carrier density
is stronger for OC1 C10 -PPV, which is likely due to the presence of stronger energetic dis-
order in the OC1 C10 -PPV as compared to P3HT, as reflected by the larger value of TD O S
for OC1 C10 -PPV. The strong energetic disorder explains the low mobility values reported
for OC1 C10 -PPV based light-emitting diodes [19], which operate at relatively low carrier
densities as compared to field-effect transistors. The large differences in mobility values
obtained from diodes and FETs, based on a single semiconducting polymer, are direct
results of the large difference in charge densities in these devices.
7 .
'26
'26>FP H9@
S [ FP
9 9
S [ FP
9 9
(QHUJ\>H9@
Figure 2.9: The Gaussian DOS (dashed line), as obtained from the hole-only
diode analysis and the exponential DOS (solid line), as obtained
from the field-effect transistors as a function of energy for P3HT.
The exponential DOS is found to be a good approximation of the
Gaussian DOS.
roughly corresponds to 1/a 3 (a=1.5 nm). Additionally, the exponential DOS of P3HT as
obtained from the FET characteristics is shown, which is described by the characteristic
temperature TD O S . For the charge carrier density range in which the P3HT FET operates,
we find that the exponential distribution with TD O S =425 K is a good approximation of the
Gaussian DOS with σ D O S =0.098 eV. This same analysis holds for the obtained OC1 C10 -
PPV data [24]. This demonstrates that the two theoretical descriptions are consistent. The
mobility description at high carrier densities, which employs an exponential DOS, is an
accurate representation of the mobility description at low carrier densities, which uses a
Gaussian DOS.
2.3.5 Conclusion
In conclusion, the large mobility differences reported for conjugated polymers used in
PLEDs and FETs have been shown to originate from the strong dependence of the mo-
bility on the charge carrier density. The exponential density of states, which consistently
describes the field-effect measurements, is shown to be a good approximation of the tail
states of the Gaussian density of states used in the description of PLEDs.
References
[1] H. Sirringhaus, P.J. Brown, R.H. Friend, M.M. Nielsen, K. Bechgaard, B.M.W.
Langeveld-Voss, A.J.H. Spiering, R.A.J. Janssen, E.W. Meijer, P.T. Herwig and D.M.
de Leeuw, Nature (London) 401, 685 (1999).
[2] S.F. Nelson, Y.-Y. Lin, D.J. Gundlach and T.N. Jackson, Appl. Phys. Lett. 72, 1854
(1998).
[3] M. Pope and C.E. Swenberg, Electronic Processes in Organic Crystals and Polymers,
Oxford University Press (1999).
[4] S.M. Sze, Physics of Semiconductor Devices (Wiley, New York, 1981)
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Lett. 73, 108, (1998).
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[10] G. Horowitz, M.E. Hajlaoui and R. Hajlaoui, J. Appl. Phys. 87, 4456 (2000).
[12] M. Shur, M. Hack and J.G. Shaw, J. Appl. Phys. 66, 3371 (1989).
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[17] G.E. Pike and C.H. Seager, Phys. Rev. B 10, 1421 (1974).
32 References
[18] E.J. Meijer, M. Matters, P.T. Herwig, D.M. de Leeuw and T.M. Klapwijk, Appl.
Phys. Lett. 76, 3433 (2000).
[19] P.W.M. Blom, M.J.M. de Jong and J.J.M. Vleggaar, Appl. Phys. Lett. 68, 3308
(1996).
[20] P.W.M. Blom, M.J.M. de Jong and M.G. van Munster, Phys. Rev. B 55, R656 (1997).
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[22] S.V. Novikov, D.H. Dunlap, V.M. Kenkre, P.E. Parris and A.V. Vannikov, Phys. Rev.
Lett. 81, 4472 (1998).
[23] M.A. Lampert and P. Mark, Current Injection in Solids (Academic, New York,
1970).
[24] C. Tanase, E.J. Meijer, P.W.M. Blom and D.M. de Leeuw, submitted.
Chapter 3
Abstract
We have measured and analyzed the temperature and gate voltage dependencies of the
field-effect mobility in organic field-effect transistors. We find that the mobility prefactor
increases exponentially with the activation energy in agreement with the Meyer-Neldel
rule. This behavior is demonstrated in the mobility data of solution-processed pentacene
and poly(2,5-thienylene vinylene) and in mobility data reported in literature. Surprisingly,
the characteristic Meyer-Neldel energy for all analyzed materials is close to 40 meV.
Possible implications for the charge transport mechanism in these materials are discussed.
34 The Meyer-Neldel rule
3.1 Introduction
The temperature and gate voltage dependence of the charge carrier mobility, µ F E , of
organic-based field-effect transistors (FET) have been the subject of research for some
years now [1–7]. However, the charge transport mechanisms in these organic devices
are still not fully understood. Reports vary from thermally activated behavior [2, 3, 5]
to temperature independent transport [4]. Moreover, large variations in the experimental
data on even nominally the same samples make it difficult to obtain an accurate picture of
the transport mechanism [4, 6]. Band-like transport in extended states has been reported
in the past for high-purity single crystals [1]. It should be noted that in contrast to this
highly orderded system the carrier transport in disordered or partially ordered systems
is governed by localized states, which results in a different transport mechanism. The
temperature and gate voltage dependencies of µ F E in organic FETs have been described
in terms of multiple trapping [3], hopping [7] and Coulomb blockade [5]. A common
factor in all these models is the gate voltage dependence of the activation energy, E a .
Whenever a property, say X, has a thermally activated behavior,
−E a
X = X 0 exp , (3.1)
kB T
and E a is a variable, it is empirically found [8] that the prefactor, X 0 , increases exponen-
tially with the activation energy:
Ea
X 0 = X 00 exp . (3.2)
EMN
This relation between the prefactor X 0 and E a is known as the Meyer-Neldel rule (MNR) [8].
Here k B is the Boltzman constant, T the absolute temperature, X 00 is a constant prefactor
and E M N is the so-called Meyer-Neldel energy. A combination of Eqs. 3.1 and 3.2 gives
the general form:
1 1
X = X 00 exp −E a − , (3.3)
kB T EMN
which implies a single crossing point for different activation energies at an isokinetic
temperature determined by the Meyer-Neldel energy: T0 = E M N /k B . The MNR has been
observed in a wide variety of physical, chemical and biological processes [9]. However,
the microscopic origin of the MNR and therefore, the physical meaning of E M N , are still
a topic of discussion in literature [9].
In this work we demonstrate that the MNR applies to the field-effect mobility data
of solution-processed pentacene and poly(2,5-thienylene vinylene) (PTV) FETs, as well
as to mobility data reported in literature. We discuss the relation between the transport
mechanism in organic FETs and the possible origin of the MNR.
3.2 Experimental
In the experiments we used heavily doped Si wafers as the gate electrode, with a 200
nm thick layer of thermally oxidized SiO2 as the gate-insulating layer. Using conven-
tional lithography, gold source and drain contacts were defined with a channel width
3.3 Demonstration of the MNR 35
, >$@
VG
Figure 3.1: Ids vs. Vg for pentacene (Vds =-2 V (open squares) and -20 V (filled
squares)) and PTV (Vds =-2 V (open circles) and -40 V (filled cir-
cles)) at 290 K in vacuum (10−7 mbar). Vg was swept from +2 to
-30 V and back to +2 V.
W =2 cm and length L=10 µm. The SiO2 layer was treated with the primer hexamethyl-
disilazane (HMDS) to make the surface hydrophobic. The films of both pentacene and
PTV were deposited using a precursor-route process [2, 10, 11]. The obtained PTV films
are truly amorphous [12]. The pentacene films are polycrystalline with a planar spacing
of 14.3 ± 0.1 Å [12], which corresponds to the bulk triclinic phase of pentacene [13, 14].
The samples were measured under high vacuum (10−7 mbar) in an Oxford optistat CF-V
flow cryostat, using a Hewlett-Packard 4156A semiconductor parameter analyzer.
The source-drain current, Ids , is plotted as a function of gate voltage, Vg , in Fig. 3.1
for both the pentacene and PTV transistors at 290 K. We do not observe any hysteresis in
the measurements and the curves are stable in time (in vacuum).
( >H9@
m >FP 9V@
9J>9@
) 9J 9
9J 9
9J 9
9J 9
9J 9
7>. @
( >H9@
D
m >FP 9V@
9J>9@
9J 9
( 9J 9
)
9J 9
9J 9
9J 9
9J 9
7>. @
Figure 3.3: Temperature dependence of the field-effect mobility of PTV. The in-
set shows the dependence of the activation energy on the gate volt-
age.
3.4 Implications for the charge transport 37
We can fit the data [22] in Figs. 3.2 and 3.3 with
−E a
µ F E = µ0 exp (3.5)
kB T
and upon extrapolation to high T we clearly find a common crossing point of the curves.
Plotting the prefactor, µ0 , logarithmically as a function of E a for both pentacene and
PTV (see Fig. 3.4), results in a straight line. This demonstrates that the experimental
results are in agreement with the MNR. From Fig. 3.4 we find E M N ≈ 38 meV and
E M N ≈ 42 meV for pentacene and PTV respectively. When this analysis is also used
on the gate voltage dependent mobility data reported in literature, we find that the MNR
also holds for the mobility data on dihexyl-sexithiophene measured by Horowitz et al. [3]
(E M N ≈ 43 meV) and for the previous studies of pentacene (E M N ≈ 34 meV) and
PTV (E M N ≈ 35 meV) [2]. Furthermore, for C60 FETs it was found that E M N ≈
36 meV [23,24]. Surprisingly, for all these materials the value of E M N is close to 40 meV.
1028 s−1 [27–31]. Furthermore, Yelon et al. [29, 30] have argued that the MNR can not
be solely due to an exponential DOS, as the MNR is much more generally applicable.
They attribute the difficulty of interpreting the prefactor values in the DOS model to the
assumption that the excitation process involves only one phonon [32,33]. If the activation
energy is large compared to the typical phonon energies available, multiple excitations are
required for a hopping event to occur. They show that a multiphonon process can explain
the MNR and that the large spread in values of the prefactor can be accounted for with
reasonable values for the attempt frequencies [29, 30].
In organic FETs, the interpretation of the MNR in terms of a Fermi level shift would
be consistent with the hopping [7] and multiple trapping models [3]. In that case E M N is
equal to the width of the DOS [27] (the TD O S parameter from Chapter 2) and no physical
meaning is attributed to the prefactor µ0 . We argue that the ubiquitous value of E M N
is more likely due to a characteristic transport mechanism in organic materials rather
than to one general DOS. Whether the interpretation given by Yelon et al. [29, 30, 34] is
applicable to our results on organic FETs hinges on the question whether it is justified
to describe the hopping of a charge carrier from one conjugated segment (or molecule)
to the next, as a multiphonon process. We note, that if the charge carrier is a localized
polaron [35, 36], Emin argued that the transport should be a multiphonon process, even if
the phonon energies are comparable to E a [37, 38]. This interpretation would imply that
the observed MNR is a direct consequence of the polaronic nature of the charge carriers.
3.5 Conclusions
In summary, we have shown the validity of the MNR in organic-based FETs. The ubiqui-
tous value of E M N ≈ 40 meV is an indication of a common origin of the MNR in organic
FETs. We have argued that the MNR is directly linked to the charge transport mechanism
and possibly even to polaronic carriers.
References
[1] M. Pope and C. E. Swenberg, “Electronic processes in organic crystals”, Oxford Uni-
versity Press, New York, (1982).
[2] A. R. Brown, C. P. Jarrett, D. M. de Leeuw and M. Matters, Synth. Metals 88, 37
(1997).
[3] G. Horowitz, R. Hajlaoui and P. Delannoy, J. Phys III France 5, 355 (1995).
[4] S. F. Nelson, Y.-Y. Lin, D. J. Gundlach and T. N. Jackson, Appl. Phys. Lett. 72, 1854
(1998).
[5] W. A. Schoonveld, J. Wildeman, D. Fichou, P. A. Bobbert, B. J. van Wees and T. M.
Klapwijk, to be published in Nature.
[6] L. Torsi, A. Dodabalapur, L. J. Rothberg, A. W. P. Fung and H. E. Katz, Phys. Rev. B
57, 2271 (1998).
[7] M. C. J. M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998).
[8] W. Meyer and H. Neldel, Z. Tech. Phys. 18, 588 (1937).
[9] For examples see references in [29, 30]
[10] A. R. Brown, A. Pomp, D. M. de Leeuw, D. B. M. Klaassen, E. E. Havinga, P. T.
Herwig, K. Müllen, J. Appl. Phys. 79, 2136 (1996).
[11] P. T. Herwig and K. Müllen, Adv. Mater. 11, 480 (1999).
[12] A. R. Schlatmann, E. J. Meijer and D. M. de Leeuw, unpublished X-ray diffraction
results.
[13] R. B. Campbell and J. M. Robertson, Acta Cryst. 14, 705 (1961).
[14] I. P. M. Bouchoms, W. A. Schoonveld, J. Vrijmoeth and T. M. Klapwijk, Synth. Met.
104, 177 (1999).
[15] We note that the MNR in inorganic FETs is sometimes evaluated by analyzing the
sheet conductance of the channel [16,17]. However, the extraction of E M N , using the
sheet conductance, may be inaccurate due to a decrease of the effective accumulation
channel thickness with increasing Vg [18, 19]. We therefore look at µ F E instead, as
suggested by Fortunato and co-workers [20, 21].
40 References
[16] R. Schumacher, P. Thomas, K. Weber and W. Fuhs, Sol. State. Comm. 62, 15 (1987).
[17] R. Schumacher, P. Thomas, K. Weber, W. Fuhs, F. Djamdji, P. G. Le Comber and R.
E. I. Schropp, Phil. Mag. B 58, 389 (1988).
[18] M. Yamaguchi and H. Fritsche, J. Appl. Phys. 56, 2303 (1984).
[19] A. P. Gnädinger and H. E. Talley, Proc. IEEE, 916 (1970).
[20] G. Fortunato, L. Mariucci and C. Reita in “Amorphous and Microcrystalline Semi-
conductor Devices” Volume 2, 355, Editor: J. Kanicki, Artech House, Norwood
(1992).
[21] G. Fortunato, D. B. Meakin, P. Migliorato and P. G. Le Comber, Phil. Mag. B, 57,
573 (1988).
[22] We note that the mobility curves of the PTV show a deviation from simple Arrhenius
behavior at low temperatures. This behavior has thus far been modelled with a specific
distribution of traps [3] and hopping in an exponential density of states [7].
[23] J. Paloheimo and H. Isotalo, Synth. Met. 55, 3185 (1993).
[24] J. C. Wang and Y. F. Chen, Appl. Phys. Let. 73, 948 (1998).
[25] H. Overhof, J. Non-Cryst. Sol. 97/98, 539 (1987).
[26] M. Ortuno and M. Pollak, Phil. Mag. B 47, L93 (1983).
[27] P. Irsigler, D. Wagner and D.J. Dunstan, J. Phys. C 16, 6605 (1983).
[28] B. Movaghar, J. Phys. Coll. C4, 73 (1981).
[29] A. Yelon and B. Movaghar, Phys. Rev. Lett. 65, 618 (1990).
[30] A. Yelon, B. Movaghar and H. M. Branz, Phys. Rev. B 46, 12244 (1992).
[31] A. M. Szpilka and P. Visc̆or, Phil. Mag. B 45, 485 (1982).
[32] A. Miller and E. Abrahams, Phys. Rev. 120, 745 (1960).
[33] N. F. Mott and E. A. Davis “Electronic Processes in Non-Crystalline Materials”,
second edition, Clarendon Press Oxford (1979).
[34] H. M. Branz, A. Yelon and B. Movaghar, MRS Symp. Proc. 336, 159 (1994).
[35] T. Holstein, Ann. Phys. 8, 325 (1959).
[36] A. J. Heeger, S. Kivelson, J. R. Schrieffer and W.-P. Su, Rev. Mod. Phys. 60, 781
(1988).
[37] D. Emin, Phys. Rev. Lett. 32, 303 (1974).
[38] D. Emin, Adv. Phys. 24, 305 (1975).
Chapter 4
Abstract
We have investigated the field dependence of the in-plane conductivity in poly(2,5- thieny-
lene vinylene) and poly(3-hexyl thiophene) thin films. The conductivity is found to have a
square root dependence on the lateral electric field. The values for the characteristic tem-
perature, obtained from the empirical field-dependent mobility relation are very similar to
the values found for the isokinetic temperature in Meyer-Neldel experiments on poly(2,5-
thienylene vinylene) and poly(3-hexyl thiophene) field-effect transistors. The possible
relation between the field-dependent mobility and the Meyer-Neldel rule is discussed in
the context of charge transport in disordered organic semiconductors.
42 The isokinetic temperature
4.1 Introduction
Due to possible industrial applications, opto-electronic devices based on disordered or-
ganic semiconducting layers are receiving much attention [1–4]. The disorder in the or-
ganic films dominates the charge transport. Typically, low mobilities with a thermally
activated behavior are observed. Transport is mostly described by hopping. Several inter-
esting physical features are associated with transport through disordered materials, such
as the Meyer-Neldel rule (MNR) [5], which we demonstrated in the previous chapter.
This rule states that the prefactor of the thermally activated mobility increases exponen-
tially with the activation energy. For a number of materials we found the characteristic
isokinetic temperature associated with the MNR to be in the range of 440-510 K [6]. At
high electric fields in disordered systems the mobility becomes field dependent, which
can be described by the empirical relation [7, 8]:
− √
µ = µ0 exp +γ F (4.1)
kB T
with,
1 1
γ =B − , (4.2)
kB T k B T0
where k B is Boltzmann’s constant, T the absolute temperature, F the applied electric
field and the low field activation energy. The field dependence as given in Eq.4.1 is
observed in a wide range of disordered materials, with typical values for the parameters
of =0.5 eV, T0 ∼500-600 K and B=3·10−5eV(m/V)1/2 [9–11]. It has been suggested
that the Meyer-Neldel rule and the field dependent mobility are related effects [11,12]. To
investigate this hypothesis we have studied both effects in two organic semiconductors,
poly(2,5-thienylene vinylene) (PTV), and poly(3-hexyl thiophene) (P3HT).
4.2 Results
The in-plane conductivity, σ , was measured using interdigitated gold contacts on glass
and the MNR using regular MISFET structures, as described in Chapter 2. X-ray ex-
periments on the PTV films did not yield reflections [6], indicating that the PTV films
are amorphous. The P3HT films are nanocrystalline. In Figs.4.1 and 4.2 σ is plotted
as a function of F 1/2 for various temperatures. We do not observe space-charge limited
currents in the range of electric fields shown in Figs.4.1 and 4.2. At low fields ohmic
behavior is observed in Fig.4.2.
Figs.4.3 and 4.2 show the temperature dependence of σ for different electric fields.
The data are well described by Eq.4.1 [13] and the values of , B, and T0 fitted for both
PTV and P3HT are given in Table.4.1. The obtained values are in agreement with data
published for other materials [9–11]. Fig.3.3 shows the field-effect mobility for a PTV
transistor as a function of T −1 for different gate voltages. The same is plotted for P3HT
in Fig.4.5. The curves are fitted to Arrhenius behavior with a gate voltage dependent
prefactor and activation energy, as was outlined in the previous chapter.
4.2 Results 43
.
.
6
.
Q .
.
.
.
s>6FP@
.
) >9mP @
Figure 4.1: In-plane conductivity of PTV as a function of F 1/2 for various tem-
peratures. L=2 µm, W =2 cm. The lines are fits to Eq.4.1. The
inset shows the structure formula of PTV.
.
.
.
.
.
.
s>6FP@
.
.
.
&+
6
Q
) >9mP @
9mP
9mP
9mP
9mP
s>6FP@
7>. @
The intersection of the fitted curves at high temperatures demonstrates the MNR
[5, 6] with a characteristic isokinetic temperature of 4.9·102 K for PTV and 4.6·102 K for
P3HT. Interestingly, the characteristic temperature of the MNR in PTV and P3HT is close
to these values. This indicates that the origin of the T0 in the field dependence (Figs.4.3
and Fig.4.4) could be the same as the isokinetic temperature observed in the Meyer-Neldel
rule (Fig.3.3 and Fig.4.5) [11, 12].
Table 4.1: Values obtained by fitting the field dependence of the conductivity
σ with Eq.4.1 for PTV and P3HT. is the low field activation en-
ergy, B is the field dependent coefficient as given in Eq. 4.2, T0,σ
is the isokinetic temperature determined from the field-dependence
data of Figs.4.3 and 4.4, and T0,F E is the isokinetic temperature
determined from the field-effect experiments of Figs.3.3 and 4.5.
9mP
9mP
9mP
9mP
s>6FP@
7>. @
@
9
H
>
D
(
m >FP 9V@
9 >9@
J
(
) 9J 9
9J 9
9J 9
9J 9
9J 9
7>. @
with µ∞ the mobility in the limit T → ∞, σ D O S the width of the Gaussian DOS, and
a the intersite spacing. Various physical mechanisms for the origin of these correlations
in the Gaussian model have been suggested. Yu et al. considered molecular geometry
fluctuations such as phenylene-ring torsion out of the plane of the molecule, which will
influence the steric energy of neighbouring molecules, and results in long-range energy
correlations between molecular sites [17]. Rakhmanova and Conwell considered struc-
tural disorder, where the morphology of the polymer is crucial, and the long-range cor-
relations between sites arise due to local variations in order. Sites in ordered regions are
suggested to have lower site energies than those in amorphous regions [18], which again
will result in long-range energy correlations. Similar modeling based on the argument
of structural disorder was given by Vissenberg [19]. In principle any model of Gaussian
disorder
√ that incorporates long-range energy correlations between sites will give rise to a
F dependence of ln(µ).
In addition to the different physical interpretations of the field-dependent mobility,
the Gaussian disorder model and the empirical relation of Eq.4.1 also predict that the
temperature dependence of the mobility should be distinct from each other. The zero field
mobility is expected to vary as µ = µ0 exp(−/k B T ) from Eq.4.1, whereas it should
follow a much stronger variation as µ = µ0 exp(−[2σ D O S /(3k B T )]2 ) from Eq.4.3. An
evaluation of the µ F =0 as a function of temperature should therefore allow the applica-
bility of the two models to be tested. Unfortunately, in polymer systems typically only a
4.4 Conclusions 47
small temperature range can be scanned experimentally, and therefore a clear distinction
between ln(µ) ∼ T −1 and ln(µ) ∼ T −2 cannot be made.
4.4 Conclusions
The fact that polarons are the charge carrying species in these polymeric systems and
that disorder is tantamount for the description of charge transport, would suggest that
a combination of the two interpretations arising from the discussion of the isokinetic
temperature would give a more complete description of charge transport. This then results
in a charge transport picture of polaronic charge carriers, that move with a multi-phonon
transfer rate between localized states, which have a Gaussian energy distribution and long-
range energy correlations.
References
[1] C.J. Drury, C.M.J. Mutsaers, C.M. Hart, M. Matters and D.M. de Leeuw, Appl. Phys.
Lett. 73, 108 (1998).
[2] A.R. Brown, C.P. Jarrett, D.M. de Leeuw and M. Matters, Synth. Met. 88, 37 (1998).
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[5] W. Meyer and H. Neldel, Z. Techn. Phys. (Leipzig), 18, 588 (1937).
[6] E.J. Meijer, M. Matters, P.T. Herwig, D.M. de Leeuw and T.M. Klapwijk, Appl. Phys.
Lett. 76, 3433 (2000).
[9] P.W.M. Blom and M.C.J.M. Vissenberg, Mater. Scie and Engin. R27, 53 (2000) and
references therein.
[10] P.W.M. Blom, M.J.M. de Jong and M.G. van Munster, Phys. Rev. B 55, R656 (1997).
[11] D.B.A. Rep, B.-H. Huisman, E.J. Meijer, P. Prins and T.M. Klapwijk, Mat. Res. Soc.
Symp. Proc. 660 (2001).
[13] We assume that the field and temperature dependence of σ are due to the mobility
and not the charge density.
[15] M. Abkowitz, H. Bässler and M. Stolka, Phil. Mag. B 63, 201 (1991).
[16] S.V. Novikov, D.H. Dunlap, V. Kenkre, P. Parris and A. Vannikov, Phys. Rev. Lett.
81, 4472 (1998).
50 References
[17] Z.G. Yu, D.L. Smith, A. Saxena, R.L. Martin and A.R. Bishop, Phys. Rev. Lett. 84,
721 (2000).
[18] S. V. Rakhmanova and E.M. Conwell, Appl. Phys. Lett. 76, 3822 (2000).
[19] P.W.M. Blom and M.C.J.M. Vissenberg, Mater. Scie. Eng. R27, 53 (2000).
[20] A. Yelon and B. Movaghar, Phys. Rev. Lett. 65, 618 (1990).
[21] D. Emin, Phys. Rev. B 61, 14543 (2000).
[22] A. Miller and E. Abrahams, Phys. Rev. 120, 745 (1960).
[23] T. Holstein, Ann. Phys. 8, 325 (1959).
Chapter 5
Abstract
The scaling behavior of the transfer characteristics of solution-processed disordered or-
ganic field-effect transistors with channel length is investigated. This is done for a variety
of organic semiconductors in combination with gold injecting electrodes. From the chan-
nel length dependence of the transistor resistance in the conducting ON-state we deter-
mine the field-effect mobility and the parasitic series resistance. The extracted parasitic
resistance, typically in the M-range, depends on the applied gate voltage, and we find
experimentally that the parasitic resistance decreases with increasing field-effect mobility.
52 Scaling behavior and parasitic series resistance
5.1 Introduction
The interest in organic field-effect transistors has grown rapidly due to envisaged ap-
plications such as integrated circuits [1] and active-matrix displays [2]. Research has
mainly been focused on improving the field-effect mobility, µ F E [3–7], which is known
to depend on material purity and processing conditions. For transistors based on solution-
processed organic semiconductors µ F E typically ranges between 10−4 and 10−1 cm2 /Vs.
The switching speed of organic integrated circuits can be estimated from the performance
of the individual transistors and is roughly proportional to ∼ µ F E /L 2 [8], where L is the
channel length of the transistor. To reach higher switching speeds, the search for higher
mobility materials is therefore important, but it is also of great interest to downsize the
transistor geometries. In this work the scaling behavior of the transfer characteristics
with transistor channel length is investigated for a variety of solution-processable organic
field-effect transistors.
5.2 Experimental
In the experiments we use heavily doped Si wafers as the gate electrode, with a 200-nm-
thick layer of thermally oxidized SiO2 as the gate-insulating layer. Using conventional
lithography, gold source and drain contacts of 100 nm thick are defined with channel
widths ranging from 1 mm to 1 cm and channel lengths between 0.75 and 40 µm. The
structures typically have an underetch of 0.5 µm, which we neglect in the following anal-
ysis. A 10 nm layer of titanium acts as an adhesion layer for the gold on the SiO2 .
The SiO2 layer is treated with the primer hexamethyldisilazane to make the surface hy-
drophobic. No special care is taken to clean the gold surface prior to deposition of the
semiconductor. Poly(2,5-thienylene vinylene) (PTV) films as semiconductor layer are
deposited using a precursor-route process [8]. We systematically varied the processing
conditions for the conversion from precursor to PTV and we determined the average de-
gree of conversion using the method described by Fuchigami et al. [9]. This enabled us
to systematically study PTV transistors at various degrees of conversion ranging from
60% to 100%, and consequently over a range of field-effect mobilities, between 10−4
and 10−3 cm2 /Vs. Poly(3-hexyl thiophene) (P3HT) is spincoated from a 1 wt% chlo-
roform solution [7]. Films of poly([2-methoxy-5-(3’,7’-dimethyloctyloxy)]-p-phenylene
vinylene) (OC1 C10 -PPV) and poly([2,5-di-(3’,7’-dimethyloctyloxy)]-p-phenylene viny-
lene) (OC10 C10 -PPV), are spun from a 0.5 wt% toluene solution. Pentacene thin films
are deposited using a precursor-route process [4, 8]. The measurements are performed
on freshly prepared samples in order to minimize external doping and degradation ef-
fects [10]. The PTV, OC1 C10 -PPV, OC10 C10 -PPV and pentacene samples are measured
in air, whereas the P3HT samples are measured in vacuum and dark after a thermal dedope
procedure [11]. The electrical characteristics are recorded using an HP4155B semicon-
ductor parameter analyzer.
5.3 Scaling behavior 53
D 379 /
µP
µP
µP
, >$@
µP
VG
µP
µ > FP 9V@
P µ
µ
P
P µ
P µ
P µ
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(
)
9J>9@
E 3+7/
µP
µP
µP
, >$@
µP
µ > FP 9V@
P µ
VG
µ
P
µ
P
P µ
( µ)(FRUUHFWHGIRU5S
)
9J>9@
Figure 5.1: Ids vs Vg at Vds = −2 V , for different channel lengths for (a) PTV,
converted at 80oC under 150 mbar of HCl partial pressure [8]. The
characteristics are measured in air at room temperature, W=1 mm.
(b) P3HT, W=1 mm, in vacuum at room temperature after a thermal
dedoping treatment [11]. The insets show the corresponding µ F E -
values derived from the gatesweeps by using Eq.5.1.
5.4 Parasitic series resistance determination 55
/ mP
/ mP
9J 9
,
/>m$
mP@
VG 9J 9
9J 9
9J 9 9J 9
Figure 5.2: The normalized output characteristics for two P3HT transistors
with L=0.75 µm (closed circles) and L=40 µm (open squares).
Clearly the current in the short transistor is more dominated by the
parasitic series resistance as compared to the long transistor.
The experimental data are, in first order, well described by this equation, with R O N de-
pending linearly on L (see Fig.5.3).
From the slopes of the plots in Fig.5.3 we find the channel resistance, Rch , the inverse
of which, [R O N /L]−1 , is the channel conductivity. From the derivative of the channel
conductivity, the field-effect mobility, corrected for R p can be obtained:
−1
R O N
∂ L
= µ F E Vg W Ci (5.3)
∂ Vg
The resulting corrected mobilities are plotted in the insets of figure 5.1. The corrected
curve yields a higher overall µ F E Vg . From the insets of Fig.5.1b it is clear that for the
40 µm-channel, the influence of R p is small, as µ F E obtained from Eq.5.1 is close to the
corrected mobility. We note that any non-linearity of µ F E with Vg in our samples cannot
a priori be attributed to the presence of an R p [18], but is more probably the result of
a specific density of states in the semiconductor at the semiconductor/insulator interface
(see Chapter 2). From the analysis with Eq.5.2 we find R p in Fig.5.3 as the intercept
56 Scaling behavior and parasitic series resistance
9
9
J
9
9
D
J
9 9
J
9 9
5 >*Ω @
J
9 9
J
1
2
/>µ P@
9
J
9
E
9 9
J
9 9
J
9 9
5 >*Ω @
J
9 9
J
1
2
/>µ P@
Figure 5.3: Total device resistance R O N , calculated with Eq.5.2 from the data
in Fig.5.1, as a function of the mask channel length for various gate
voltages, for (a) PTV, (b) P3HT.
5.4 Parasitic series resistance determination 57
379PEDU+&O
FRQYHUVLRQGHJUHHYDULHG
EHWZHHQDQG
379PEDU+&O
FRQYHUVLRQGHJUHHYDULHG
EHWZHHQDQG
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379PEDU+&O
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EHWZHHQDQG
3+7
3+7IURPUHI>@
SUHFXUVRUSHQWDFHQH
m)(>FP 9V@
Figure 5.4: The parasitic resistance times the channel width as a function of
the effective field-effect mobility for a number of polymeric semi-
conductors and pentacene.
5.5 Conclusions
In conclusion, we have used channel length dependent measurements to experimentally
determine the effective field-effect mobility, corrected for parasitic series resistance, in
a variety of spin-coated organic field-effect transistors. The understanding and reduc-
tion of parasitic series resistances is important for downsizing of the organic transistor
geometries, to be able to reach higher switching speeds for integrated circuits. For the
investigated transistors we extract a parasitic series resistance which depends on Vg . This
parasitic resistance is attributed to an injection barrier with a height in the order of a
few times k B T , which results in an ohmic parasitic series resistance. Experimentally, we
find that the parasitic resistance decreases with increasing charge carrier mobility for the
investigated polymeric field-effect transistors.
References
[1] G.H. Gelinck, T.C.T. Geuns, D.M. de Leeuw, Appl. Phys. Lett. 77, 1487 (2000).
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414, 599 (2001)
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de Leeuw, Nature (London) 401, 685 (1999).
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(1999).
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Soc. Symp. Proc. 660 JJ7.9.
[12] E.J. Meijer, C. Tanase, P.W.M. Blom, E. van Veenendaal, B.-H. Huisman, D.M. de
Leeuw, and T.M. Klapwijk, Appl. Phys. Lett. 80, 3838 (2002).
[13] L. Bürgi, H. Sirringhaus, and R.H. Friend, Appl. Phys. Lett 80, 2913 (2002).
Abstract
Metal-insulator-semiconductor diodes with poly(3-hexyl thiophene) as the semiconductor
were characterized with impedance spectroscopy as a function of bias, frequency, and
temperature. We show that the standard Mott-Schottky analysis gives unrealistic values
for the dopant density in the semiconductor. From modeling of the data, we find that
this is caused by the relaxation time of the semiconductor, which increases rapidly with
decreasing temperature due to the thermally activated conductivity of the poly(3-hexyl
thiophene).
62 Frequency behavior and the Mott-Schottky analysis
6.1 Introduction
Low-cost organic integrated circuits are being more and more recognised as a poten-
tially interesting industrial application. This has increased the efforts to develop high-
performance devices. The development of solution-processable high-mobility polymers
[1, 2] and of technology for all-polymer integrated circuits [3, 4] is promising. However,
from the application point of view the lifetime of the devices is an important issue. The
limited lifetime of current devices is mainly determined by the increase in conductivity,
σ , of the semiconductor upon doping in air and light [4, 5].
To study the doping effects in high-mobility polymeric semiconductors we used
metal-insulator-semiconductor (MIS) diodes with poly(3-hexyl thiophene) (P3HT) as the
semiconductor. We measured the temperature and modulation frequency dependence in
these devices. The standard Mott-Schottky analysis to extract the dopant density, N A ,
yields erroneous results for large frequency and temperature ranges. Analysis of the data
will show that this is due to the temperature dependence of the relaxation time of the
P3HT. We model the data with a simple equivalent circuit and argue that the temperature
dependence of the semiconductor relaxation time is due to thermally activated conductiv-
ity of P3HT.
6.2 Experimental
The MIS diodes were fabricated on glass, using patterned Indium-Tin-Oxide (ITO) con-
tacts as gate electrode. A 300 nm insulating layer of novolak R photoresist was spin-
coated on top of the gate. Over the insulator a 200 nm thick P3HT film was spun from
a 1 weight % chloroform solution. Finally, a 10 nm gold layer was evaporated through a
shadowmask to form an ohmic contact with the P3HT layer. A cross-section of the de-
vice is given in the inset of Fig.6.1. The capacitance, C, of the diode can be changed by
depleting or accumulating charge in the semiconductor at the interface with the insulator.
The thickness of the insulator layer, dins , determines the maximum value of C:
ins 0 A
Cins = , (6.1)
dins
where ins is the relative dielectric constant of the insulator, 0 the permittivity of vacuum
and A the area of the device. The minimum value of C is determined by the relative di-
electric constants of the insulator, ins , and the semiconductor, semi , and the total distance
between the conductive layers. When the semiconductor layer is partially depleted, the
depletion layer acts as a capacitance in series with the insulator capacitance. We calculate
the total diode capacitance from the modulus of the impedance, Z , and its phase angle, ,
using: C = − sin /(ω|Z |), with ω=2π f mod , where f mod is the modulation frequency.
The capacitances of the MIS diodes scaled with the area of the devices, ranging from 9 to
36 mm2 , in the entire biasing regime. The results presented in this work represent typical
data measured on more than 10 MIS diodes. All impedance measurements were done
with a Schlumberger 1260 Impedance Gain-Phase Analyzer in vacuum (<10−5 mbar) in
an Oxford CV-flowcryostat.
6.3 The Mott-Schottky analysis 63
*R OG
. 3+7
. 5HVLVW
. *OD VV
,72
&>Q)@
.
.
.
.
.
.
+]
+]
+]
+]
+]
1 >FP @ +]
$
7>.@
From the equivalent circuit analysis we find that Rc is small and can be neglected. The
6.4 Equivalent circuit modelling 65
D
@
]
+
>
D [
IP
& >Q)@
7>. @
$
+]
+]
+]
+]
+]
E
+]
+]
+]
Q >GHJUHHV@
$
7>.@
Figure 6.3: (a) Capacitance of the P3HT MIS diode at Vg = −20 V as a func-
tion of temperature for different frequencies. The inset shows the
frequency at which the phase angle, A , is at its maximum vs re-
ciprocal temperature (b) A of the MIS diode at Vg = −20 V for
different frequencies.
66 Frequency behavior and the Mott-Schottky analysis
. &V
. & LQV 5F
.
.
5V
Q >GHJUHHV@
$
IPRG>+]@
1 1
ωmax = 2π f max = √ , (6.4)
Rs Cs (Cins + Cs )
1/ω τ. (6.6)
is no longer satisfied, the charge carriers can not follow the AC voltage anymore. As a
result, one measures a smaller capacitance of the MIS diode with increasing frequency,
as shown in Fig.6.3a. As Rs increases with decreasing temperature, this restricts the
frequency region over which Eq.6.6 is fulfilled even further for lower temperatures. This
is why we observe an apparent temperature dependent capacitance as shown in Fig.6.1.
We use our understanding of the temperature and frequency behavior to apply Eq.6.2
in a frequency range where these effects are negligible. In this case the lower limit was
taken 25 Hz, and we took the upper limit in frequency one decade lower than the inverse
of τ , for each temperature. For the present device, we extract a dopant density of 5.4·1015
cm−3 , comparable to the value of 1·1016 obtained on P3HT by Brown et al [12].
6.6 Conclusions
In summary, we have fabricated and analyzed MIS diodes based on P3HT. We find that
the Mott-Schottky analysis may not be used for extraction of the dopant density, N A , over
the entire range of temperature and frequency. This is due to the relaxation time of the
68 Frequency behavior and the Mott-Schottky analysis
[1] Z. Bao, A. Dodabalapur, A.J. Lovinger, Appl. Phys. Lett. 69, 4108 (1996).
[2] H. Sirringhaus, P.J. Brown, R.H. Friend, M.M. Nielsen, K. Bechgaard, B.M.W.
Langeveld-Voss, A.J.H. Spiering, R.A.J. Janssen, E.W. Meijer, P.T. Herwig and D.M.
de Leeuw, Nature 401, 685 (1999).
[3] C.J. Drury, C.M.J. Mutsaers, C.M. Hart, M. Matters and D.M. de Leeuw, Appl. Phys.
Lett. 73, 108 (1998).
[4] G.H. Gelinck, T.C.T. Geuns and D.M. de Leeuw, Appl. Phys. Lett. 77, 1489 (2000).
[5] M.S.A. Abdou, F. P. Orfino, Y. Son, S. Holdcroft, J. Am. Chem. Soc. 119, 4518
(1997).
[6] E.H. Nicollian and J.R. Brews, “MOS (Metal Oxide Semiconductor) Physics and
Technology”, Wiley, New York (1982).
[7] S.M. Sze, “Physics of semiconductor devices”, Wiley, New York (1981).
[8] P. Stallinga, H.L. Gomes, H. Rost, A.B. Holmes, M.G. Harrison and R.H. Friend, J.
Appl. Phys. 89, 1713 (2001).
[9] D.B.A. Rep, B.-H. Huisman, E.J. Meijer, P. Prins and T.M. Klapwijk, Mat. Res. Soc
Symp. Proc., 660 (2001).
[10] A.V. Gelatos and J. Kanicki, Appl. Phys. Lett. 56, 940 (1990).
[11] M.C.J.M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998).
[12] P.J.Brown, Charge Modulation Spectroscopy of Poly(3-alkylthiophene), PhD thesis,
Cambridge (2000).
Chapter 7
Photoimpedance spectroscopy of
poly(3-hexyl thiophene)
metal-insulator-semiconductor diodes
Abstract
Capacitance-voltage characteristics of metal-insulator-semiconductor diodes with poly(3-
hexylthiophene) (P3HT) as p-type semiconductor were investigated as function of time,
ambient, and illumination. P3HT is rapidly doped upon exposure to both oxygen and
light. Changes of the acceptor density profiles with time were determined by using Mott-
Schottky analysis of the capacitance-voltage characteristics. The profiles were determined
to be constant over the P3HT film thickness. Wavelength dependent photoimpedance
measurements show that the acceptor creation efficiency peaks upon excitation of the
molecular oxygen-polythiophene contact charge transfer complex at (1.9±0.1) eV.
72 Photoimpedance spectroscopy of P3HT MIS diodes
7.1 Introduction
Thin-film field-effect transistors based on p-type organic thiophene-based semiconductors
usually are unstable under ambient conditions. The conductivity of the organic semicon-
ductor often increases under exposure of oxygen, light, or a combination thereof [1,2]. As
a result, the current modulation, or on-off current ratio, of discrete transistors decreases
with time, the gain of logic gates gets less than unity and, consequently, logic circuits
stop functioning. As is described in Chapter 8, the acceptor density can be estimated
from the pinch-off voltage of discrete ring-type transistors, where the pinch-off voltage
is the applied gate voltage at which the depletion region in the semiconductor becomes
equal to the thickness of the semiconductor layer [3]. This reported analysis implicitly
assumes that the acceptor density is constant over the semiconductor layer thickness. In
this work we determine the acceptor profile in the polymeric semiconductor layer, us-
ing the Mott-Schottky analysis on measured capacitance-voltage (C − Vg ) characteristics
of polymer-based metal-insulator-semiconductor (MIS) diodes. Because we used semi-
transparent MIS diodes, changes in the impedance could be investigated as a function of
time upon exposure to oxygen and/or light. As a typical example we investigated poly(3-
hexyl thiophene) (P3HT) MIS diodes. In order to elucidate the doping mechanism, we
compared the wavelength dependent changes in the photoimpedance measurements with
the absorption spectra of molecular oxygen-polythiophene contact charge transfer com-
plexes as reported by Abdou et al. [2].
7.2 Experimental
The MIS diodes are fabricated on glass, using patterned transparent indium-tin-oxide gate
electrodes. A 300 nm layer of novolak R photoresist is spincoated on top of the contacts
and subsequently cross-linked upon baking at 150 o C. On top of this insulator a 200 nm
thick film of P3HT is spun from a 1 wt% chloroform solution. Finally, a semi-transparant
10 nm gold electrode is evaporated through a shadow mask. The area of the diodes ranges
from 9 to 36 mm2. A schematic cross-section of the MIS diode is given in the inset of
Fig.7.1. After processing, the sample is inserted in an Oxford CF1204 optical flowcryo-
stat, with a vacuum better than 10−5 mbar. Impedance measurements are done using a
Schlumberger 1260 impedance gain-phase analyzer, with a modulation frequency, f mod
of 137 Hz. This frequency is low enough to prevent artifacts in the impedance data due to
the low bulk charge carrier mobility of P3HT, as described in the previous chapter [4]. The
diode capacitance, C, then follows from the modulus of the impedance, Z , and the phase
angle, , by C = −si n/(2π f mod |Z |). For the wavelength dependent photoimpedance
measurements the light of an Oriel 66058 tungsten-filament lamp is fed into a Jobin Yvon
H25 PLE monochromator. The resulting light beam is focused on the sample in the cryo-
stat. The wavelength of the light is varied between 400 nm and 1100 nm. The power
profile of the light incident on the MIS diode is measured. The number of incident pho-
tons is calculated from the calibrated power profile of the lamp in combination with the
monochromator. The absorption spectrum of a thin film of P3HT is measured and taken
equal to the absorption of the P3HT layer in the diode. In the analysis we have assumed
7.3 Flat-band shift under oxygen exposure 73
λ
LQOLJKW QPYDFXXP
∆9 >9@
)%
LQGDUN
PEDU2 PEDU2
V PEDU2 PEDU2
Q
L
&&
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*ROG
3+7
5HVLVW
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,72
9J>9@
Figure 7.1: Normalized C − Vg curves of a P3HT MIS diode in vacuum and af-
ter 82 minutes exposure to a 230 mbar dry oxygen atmosphere. The
arrow indicates the direction of the shift of the curve upon oxygen
exposure. The inset on the left shows a schematic cross section of
the MIS diode. The inset on the right shows the flat-band voltage
shift as a function of time, for different oxygen pressures, as well as
a measurement in vacuum where the MIS diode is exposed to light
(wavelength of 700 nm).
that any dispersion in the absorption of the semi-transparant gold electrode can be disre-
garded. After exposure to oxygen and/or light in the cryostat, the P3HT MIS diodes are
dedoped by annealing the diodes for several hours in vacuum at 150 o C. This process can
be repeated, without apparent degradation of the P3HT [5]. Due to this dedoping proce-
dure there are some variations in the dopant density at the beginning of each experiment.
partially depleted. The depletion layer then acts as a capacitance in series with the insu-
lator capacitance. The minimum capacitance is obtained when the whole film is depleted
and is determined by the dielectric constants of the insulator and the semiconductor, semi ,
and by the total distance between the electrodes. The steepness of the C − Vg character-
istics of an MIS diode, when biased in the gate voltage range where the semiconductor
layer is partially depleted, is the result of the ease with which the semiconductor can be
depleted and is related to the acceptor density and its profile as a function of the depth
inside the film. The C − Vg characteristics of Fig.7.1 are measured in the dark and in
vacuum. The measurements do not change with time in vacuum and dark. The acceptor
density and depth profile therefore do not change; P3HT is stable in vacuum and dark.
Subsequently, the diodes are measured in dark upon exposure to dry oxygen. The
partial oxygen pressure is varied between 0.8 and 230 mbar. The capacitance-voltage
characteristics are recorded every four minutes. The final measurement is included in
Fig.7.1. These two measurements can be shifted over the voltage axis on top of each other.
Apparently, the dominant effect is a shift of the flat-band voltage, VF B , the applied voltage
at which there is no band bending in the semiconductor at the semiconductor/insulator
interface. The flat-band voltage shift is indicated in the insert of Fig.7.1. The increase
of VF B with time is dependent on partial oxygen pressure. Upon exposure to light in
vacuum the MIS diode C − Vg characteristics also show a flat-band shift (see the inset of
Fig.7.1.), which slowly decreases again when the light is turned off. The flat-band voltage
shift is likely due to electrostatic charging of the semiconductor/insulator interface. This
interpretation agrees with reported shifts of the transfer characteristics of P3HT field-
effect transistors (see Chapter 8) [3].
Eq.7.2 holds when the contribution to the capacitance of interface states and minority
carriers can be disregarded [6]. The acceptor density, N A , at a certain depletion depth can
7.4 Photoimpedance spectroscopy 75
V
Q
L
&&
LQYDFXXPDQGGDUN
R[\JHQPEDU
DQGOLJKWλ QP
PLQXWHV
PLQXWHV
PLQXWHV
PLQXWHV
9J>9@
Figure 7.2: Normalized C −Vg curves as a function of time in 230 mbar oxygen
under illumination of light with a wavelength of 700 nm.
GDUNDQGYDFXXP
OLJKWλ QPDIWHUPLQXWHVLQPEDU2
1 >FP @
$
GGHSO>QP@
Figure 7.3: Acceptor density profile extracted from the C − Vg data of Fig.7.2,
using Eqs.7.2 and 7.3, for an undoped P3HT MIS diode in vacuum
and dark (filled squares) and after 60 minutes of exposure to 230
mbar dry oxygen and illumination with λ=700 nm (filled circles).
the insulator [6, 8]. A typical acceptor density of about 1016 cm−3 results in a Debije
length of about 20 nm at room temperature. The acceptor profile information can then
reliably be determined starting from a depletion depth of about 60 nm from the semicon-
ductor/insulator interface.
Acceptor densities in the dark and after illumination at a wavelength of 700 nm
in 230 mbar O2 are presented in Fig.7.3 as a function of depletion depth. In the dark
N A is constant over the P3HT film thickness and amounts to about 3·1015 cm−3 . Upon
illumination N A increases, but in first order is constant over the layer thickness. There is
only a slight increase in acceptor density at the top contact. Similar profiles were obtained
for illuminations at other wavelengths.
The profiles with time can now be calculated from the temporal C−Vg characteristics
of Fig.7.2. We take the values of N A at a depletion depth of 100 nm and plot them in
Fig.7.4 as a function of time on a double logarithmic scale. The acceptor density roughly
follows a power law dependence under light exposure of 700 nm and O2 exposure of
230 mbar with an exponent of about 0.3. We note that typically, the conductivity of a
variety of oligo- and polythiophenes increases with time as t α with α between 0.2 and
0.5, under ambient conditions [9]. This suggests that the increase of the conductivity on
the timescale of the measurements is dominated by an increase in acceptor density.
A clue for the doping mechanism can be obtained from the wavelength dependent
photoimpedance measurements, which are given in Fig.7.5. In these photoimpedance
experiments the MIS diode is exposed for two minutes to light of a certain wavelength in
230 mbar O2 . Then the C − Vg characteristics were recorded in the dark, with the oxygen
7.4 Photoimpedance spectroscopy 77
[
GGHSO QP
PEDUGDUN
YDFXXPQPOLJKW
[ PEDUQPOLJKW
1 >FP @
[
$
[
W>V@
V
Q
L
&&
ZDYHOHQJWKλ >QP@
DFFHSWRUFUHDWLRQHIILFLHQF\>DX@
$EVRUEDQFHQRUPDOL]HG>2'@
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Figure 7.6: Relative acceptor density creation efficiency as a function of the in-
cident illumination, for P3HT in 230 mbar O2 at room temperature.
The absorption spectrum of P3HT is given for comparison.
pressure constant at 230 mbar O2 . This procedure was repeated at several wavelengths
of light going from λ=1000 nm to λ=600 nm, in a consecutive measurement. Due to the
low absorption in the P3HT layer from λ=1000 nm up to λ=700 nm, we assume that the
light is uniformly absorbed in the film. For shorter wavelengths the absorption profile
of the P3HT film will not be homogeneous anymore, but will result in a depth profile of
absorption. We neglect this absorption profile in the measurements up to 600 nm.
The acceptor density is determined from Fig.7.5 at a depletion depth of 100 nm as
a function of the photon energy. The derivative yields the change in acceptor density
with photon energy, where we have assumed that absolute value of N A at the beginning
of each measurement has no influence on the increase of N A . This number is corrected
for the power profile of the light, by dividing with the incident photon flux. The relative
acceptor creation efficiency as a function of photon energy is then obtained by dividing
with the absorbance, and is plotted in Fig.7.6. This efficiency, or cross section, indicates
the ease with which acceptors are formed in P3HT under illumination in an oxygen at-
mosphere. The efficiency peaks at (1.9 ± 0.1) eV. This value corresponds roughly to the
reported absorption of the contact charge transfer complex between molecular oxygen
and polythiophene at 1.97 eV [2].
7.5 Conclusions
In summary, we have investigated the instability of P3HT using semitransparent MIS
diodes. We have measured and analyzed the capacitance-voltage characteristics of these
7.5 Conclusions 79
MIS diodes as function of time, ambient and illumination. On the time scale of the mea-
surements in vacuum and light, and in oxygen in the dark, the P3HT MIS diodes only
show a flat-band voltage shift. However, upon exposure of the P3HT to both oxygen
and light, the capacitance-voltage data show a clear increase of the acceptor density, as
is demonstrated using Mott-Schottky analysis. The acceptor density profile is in first ap-
proximation constant over the semiconductor film thickness. The wavelength dependent
photoimpedance measurements show that the acceptor creation efficiency peaks upon ex-
citation of the molecular oxygen-polythiophene contact charge transfer complex.
References
[1] G.H. Gelinck, T.C.T. Geuns and D.M. de Leeuw, Appl. Phys. Lett. 77, 1489 (2000).
[2] M.S.A. Abdou, F. P. Orfino, Y. Son and S. Holdcroft, J. Am. Chem. Soc. 119, 4518
(1997).
[3] E.J. Meijer, C. Detcheverry, P.J. Baesjou, E. van Veenendaal, D.M. de Leeuw and
T.M. Klapwijk, J. Appl. Phys. 93, 4831 (2003).
[4] E.J. Meijer, A.V.G. Mangnus, C.M. Hart, D.M. de Leeuw, T.M. Klapwijk, Appl. Phys.
Lett. 78, 3902 (2001).
[5] D.B.A. Rep, B.-H. Huisman, E.J. Meijer, P. Prins and T.M. Klapwijk, Mat. Res. Soc.
Symp. Proc., 660, JJ7.9.1 (2001).
[6] E.H. Nicollian and J.R. Brews, “MOS (Metal Oxide Semiconductor) Physics and
Technology”, Wiley, New York (1982).
[7] S.M. Sze, “Physics of semiconductor devices”, Wiley, New York (1981).
[8] D.K. Schroder, “Semiconductor Material and Device Characterization”, Wiley
(1990).
[9] L. Luer, H.-J. Egelhaaf and D. Oelkrug, Optical Materials 9, 454 (1998).
Chapter 8
Abstract
We demonstrate that, by using a concentric device geometry, the dopant density and the
bulk charge carrier mobility can simultaneously be estimated from the transfer charac-
teristics of a single disordered organic transistor. The technique has been applied to de-
termine the relation between the mobility and the charge density in solution-processed
poly(2,5-thienylene vinylene) and poly(3-hexyl thiophene) thin-film field-effect transis-
tors. The observation that doping due to air exposure takes place already in the dark,
demonstrates that photo induced oxygen doping is not the complete picture.
84 Dopant density determination in organic transistors
8.1 Introduction
For the development of polymeric integrated circuits the stability of the characteristics of
the organic semiconductor layer is an important issue. One of the limiting mechanisms
is an increase in p-type doping due to a charge-transfer reaction with ambient molecular
oxygen (see chapter 7) [1]. An increase of doping leads to an increase of the conductivity
of the bulk semiconductor, which reduces the current modulation, or on-off ratio, of the
transistor [2, 3]. Here we will demonstrate that, by using a ring-type transistor geometry,
we can directly estimate the dopant density and the bulk mobility from the transfer char-
acteristics of a single disordered organic field-effect transistor (FET). This allows moni-
toring of the dopant density change in time. The disentanglement of the dopant density
and bulk mobility in the bulk conductivity will be crucial to understand and counteract
the instabilities observed in polymeric transistors. As an example we discuss the dopant
density increase under the influence of oxygen exposure in poly(2,5-thienylene vinylene)
(PTV) and poly(3-hexyl thiophene) (P3HT) field-effect transistors.
379
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L, varying between 10 and 20 µm, and channel widths, W , of 1 mm and 2.5 mm. As a
last step a 200 nm thick semiconductor layer is spincoated over the contacts. The semi-
conductors used, are poly(2,5-thienylene vinylene), which is applied as precursor from
a 0.5 wt% chloroform solution and subsequently formed in-situ by conversion at 150o C
in vacuum [12], and poly(3-hexyl thiophene) which was spun from a 1 wt% chloroform
solution. All transfer characteristics in this study were measured in the linear operating
regime of the transistor, at source-drain voltage, Vds = −2 V , at room temperature, in the
dark.
Fig.8.1 shows the transfer characteristics of a PTV thin-film field-effect transistor,
with a ring-geometry. The initial curve is measured in vacuum after a thermal dedoping
procedure [13]. After this measurement 10 mbar of air is let into the chamber. The time at
which the valve is opened to admit the air is denoted as t = 0. Subsequently, the evolution
of the transfer characteristics in air is monitored as a function of time.
The initial curve shows a characteristic p-type semiconducting behavior. At nega-
tive gate voltages, Vg , holes are accumulated in the semiconductor at the semiconductor-
insulator interface. These accumulated charges move under the influence of the lateral
source to drain field, resulting in the source-drain current, Ids . At positive Vg the holes are
depleted from the semiconductor layer and no mobile charges are left to carry the current.
Upon prolonged exposure to air, in dark, we observe two changes in the transfer char-
acteristics. Firstly, in the depletion regime of the transistor (at positive gate voltages) an
additional current appears, which increases with oxygen-exposure and time. This feature
86 Dopant density determination in organic transistors
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Figure 8.3: dopant density, extracted using Eq.8.4, vs time for several air pres-
sures, in dark.
where 0 is the permittivity of vacuum, semi the relative dielectric constant of the semi-
conductor, q the elementary charge and A the active transistor area (length times the
width). By using the insulator capacitance per unit area,
0 ins
Ci = , (8.2)
dins
and the semiconductor layer capacitance,
0 semi A
Csemi = , (8.3)
dsemi
we can recalculate Eq.8.1 for the pinchoff condition, Vg − Vso = V pinch , at which the
depletion layer width is equal to the semiconductor layer thickness, dsemi , to:
2V pinch 0
NA = , (8.4)
2
dsemi 2dsemi dins
q semi + ins
where dins is the film thickness of the insulator layer, and ins is the relative dielectric
constant of the insulator.
The dopant density, derived using Eq.8.4, as a function of time at different air pres-
sures, is plotted in Fig.8.3. We observe that the initial increase of N A upon exposure to
oxygen is the biggest difference between the measurements at different pressures. In PTV
this initial increase occurs within two minutes after exposure, in the dark. For the P3HT
this is a much slower process in the dark, as can be seen from Fig.8.3. In most models
8.4 Results for PTV and P3HT 89
the charge-transfer reaction with molecular oxygen, requires exposure to light [1]. The
measurements in the dark presented here, demonstrate that further analysis into the dop-
ing mechanisms is required, and that the mechanisms differ quantitatively for different
materials.
Knowing N A from Eq.8.4, we can determine µbulk using Eq.8.5. We remark that the
shape of the curves in depletion can be described by modeling the curves with
W Vds N A qµbulk
Ids = dsemi − Wdepl , (8.6)
L
using the values obtained from Eq.8.4 and Eq.8.5.
are also given. The charge accumulated at the semiconductor-insulator interface is cal-
culated using Poisson’s equation, and the charge distribution in the semiconductor is ne-
glected [19].
We find that the dependence of mobility on charge density is not the same for the
bulk and the field-effect [20]. The µbulk − N A relation obtained here was also found
in studies at dopant densities of 1019 -1020 cm−3 [2]. These observations suggest that
chemical doping of the film not only influences the relative position of the Fermi level
in the DOS. In fact, the presence of the dopant counterions will alter the DOS itself, a
phenomenon well known from studies on amorphous silicon [21].
The bulk mobility of P3HT is found to be much higher than the bulk mobility of PTV
(see Fig.8.4). We argue that this is due to a more ordered film in the case of P3HT [22],
90 Dopant density determination in organic transistors
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Figure 8.4: The bulk charge carrier mobility in PTV and P3HT estimated using
Eq.8.5 vs the dopant density for several air pressures, in dark. For
comparison also the field-effect mobility as a function of induced
charge at the semiconductor-insulator interface of a transistor in
vacuum, is given for both materials.
which can result in a higher bulk mobility. From studies of PTV deposited using a dif-
ferent precursor-route [2], we initially did not find the bulk features in the dark and air
as described above. Only after additional thermal treatment, which did not change the
field-effect behavior, the bulk feature appeared. As the polymer did not degenerate due to
this thermal treatment, we conclude that a morphology change in the bulk of the polymer
results in an increased bulk mobility, and therefore in an added bulk contribution to the
current. Morphological differences between the semiconductor bulk and the semiconduc-
tor/insulator interface will result in different relative contributions of the bulk current and
the field-effect current to the total source-drain current. The bulk current increases with
time due to the doping with oxygen. For a system with a low mobility in the bulk in
combination with a high field-effect mobility, the influence of this bulk current increase
on the total transistor current can be neglected for a longer period of time than in a system
with a high bulk mobility. Study of the bulk morphological aspects of disordered organic
semiconductors, and their influence on the stability of devices is therefore of importance.
We remark that reducing the thickness of the semiconductor layer will also significantly
reduce the bulk current, which we observed experimentally by preparing semiconductor
layers with a thickness in the order of 10 nm. The results in Fig.8.4 demonstrate the power
of our experimental technique, which allows the disentanglement of the dopant density
and the bulk mobility in the bulk conductivity.
8.5 Shift of the switch-on voltage 91
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Figure 8.5: The transfer characteristics of Fig.8.1 are shifted over the voltage
axis, such that the field-effect behavior of the curves coincide. The
insets shows (a) the data of Fig.8.1 on a linear scale and (b) the
same data shifted over the voltage axis on a linear scale.
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Figure 8.6: (a) P3HT FET transfer characteristics in 1 bar air, after some light
exposures from a lamp, L = 20 µm, W = 1 mm. The inset shows
the same data on a linear scale (b) The data are shifted over the
voltage axis in such a way that the field-effect part of the curves
coincide. The inset shows the same data on a linear scale.
8.5 Shift of the switch-on voltage 93
3+7PEDU
379PEDU
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Figure 8.7: Switch-on voltage shift vs time for several air pressures, in dark.
For P3HT this clearly is a large effect.
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quality thermally grown SiO2 in the FETs, which is unlikely to incorporate charge upon
oxygen exposure at room temperature [10, 18, 23]. A dopant profile in the semiconductor
layer can not explain the Vso shift in these organic devices in contrast to standard silicon
devices [8], because here we are not dealing with the formation of an inversion layer
[17]. We suggest that the observed shifts of Vso are due to interfacial charging at the
semiconductor-insulator interface [10]. This is supported by the fact that we observed
these shifts with the same magnitude also in the characteristics of transistors with very
thin semiconductor layers. The origin and nature of these charges are unclear at present.
8.6 Conclusions
In conclusion, we have shown that the dopant density as well as the bulk charge carrier
mobility in disordered organic semiconductors can be simultaneously determined from
the transfer characteristics of a single transistor. This is possible due to a concentric device
geometry, which excludes parasitic currents outside the transistor area and a mobility
dependence on the charge density in the polymer. For two organic semiconductors, P3HT
and PTV, it was demonstrated that field-effect and bulk influences could be separated
because of a clear crossover from an accumulation transistor to a bulk depletion mode
transistor. These polymers already exhibit a dopant density increase upon air exposure in
the dark, which requires a re-evaluation of the doping mechanism in terms of a charge-
transfer reaction with oxygen under light exposure. We have argued that the morphology
of the polymeric semiconductor is of importance for the stability of the transistors. The
ability to analyse dopant influences directly from transistor measurements is crucial to
study instabilities and lifetime issues of polymeric transistors.
References
[1] M.S.A. Abdou, F. P. Orfino, Y. Son, and S. Holdcroft, J. Am. Chem. Soc. 119, 4518
(1997).
[2] A.R. Brown, C.P. Jarrett, D.M. de Leeuw, and M. Matters, Synth. Met. 88, 37 (1997).
[3] G.H. Gelinck, T.C.T. Geuns, and D.M. de Leeuw, Appl. Phys. Lett. 77, 1489 (2000).
[4] M. C. J. M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998).
[5] G. Horowitz, R. Hajlaoui, H. Bouchriha, R. Bourguiga, and M. Hajlaoui, Adv. Mater.
10, 923 (1998).
[6] B. Maennig, M. Pfeiffer, A. Nollau, X. Zhou, K. Leo, and P. Simon Phys. Rev. B 64,
195208 (2001).
[7] H.C.F. Martens, PhD thesis, Charge transport in conjugated polymers and polymer
devices, Leiden University (2000).
[8] S.M. Sze, Physics of Semiconductor Devices Wiley, New York, (1981).
[9] For band transport, where the mobility does not depend on the charge density, this
crossover is not expected to occur in the transfer characteristics [18], in which case
the analysis given here can not be applied.
[10] Y.-Y. Lin, D. J. Gundlach, S.F. Nelson, and T.N. Jackson, IEEE Trans. Elec. Dev.
44, 1325 (1997).
[11] We expect that patterning of the semiconductor layer will give similar results as the
ring-geometry.
[12] A.J.J.M. van Breemen, J.J.A.M. Bastiaansen, B.M.W. Langeveld, J. Sweelssen,
J.A.E.H. van Haare, P.T. Herwig, K.T. Hoekerd, and H.F.M. Schoo, Int. Display Re-
search Conf. Palm Beach, U.S.A. SID 20, 327 (2000).
[13] D.B.A. Rep, B.-H. Huisman, E.J. Meijer, P. Prins, and T.M. Klapwijk, Mat. Res.
Soc. Symp. Proc., 660, JJ7.9.1 (2001).
[14] G. Horowitz, F. Garnier, A. Yassar, R. Hajlaoui, and F. Kouki, Adv. Mater. 8, 52
(1996).
96 References
[17] E.J. Meijer, C. Tanase, P.W.M. Blom, E. van Veenendaal, B.-H. Huisman, D.M. de
Leeuw, and T.M. Klapwijk, Appl. Phys. Lett. 80, 3838 (2002).
[18] S. Scheinert, G. Paasch, M Schrödner, H.-K. Roth, S. Sensfuß, and Th. Doll, J. Appl.
Phys. 92, 330 (2002).
[19] C. Tanase, E.J. Meijer, P.W.M. Blom, and D.M. de Leeuw, submitted.
[20] H. Sirringhaus, N. Tessler, D.S. Thomas, P.J. Brown, and R.H. Friend, Adv. Solid
State. Phys. 39, 101 (1999).
[21] R.A. Street, Hydrogenated amorphous silicon, Cambridge University Press (1991).
[22] H. Sirringhaus, P.J. Brown, R.H. Friend, M.M. Nielsen, K. Bechgaard, B.M.W.
Langeveld-Voss, A.J.H. Spiering, R.A.J. Janssen, E.W. Meijer, P.T. Herwig, and D.M.
de Leeuw, Nature (London) 401, 685 (1999).
[23] S.J. Zilker, C. Detcheverry, E. Cantatore, and D.M. de Leeuw, Appl. Phys. Lett. 79,
1124 (2001).
Chapter 9
Abstract
Progress towards electronics based on organic semiconductors is strongly dependent on
the successful interplay between functional chemical units and the development of well-
performing electronic components. There is ample evidence that organic field-effect tran-
sistors analogous to standard metal-oxide-semiconductor (MOS) transistors have reached
a stage that they can be industrialized [1–3]. Currently organic semiconductors are di-
vided into two classes, electron-transporters and hole-transporters, or n-type and p-type
materials. This distinction is important for the design of light-emitting diodes [4] and
solar cells [5] where both type of carriers are needed. Monocrystalline Si technology is
largely based on complementary MOS (CMOS) structures which use both n-type and p-
type transistor channels. This complementary technology has enabled the construction of
digital circuits which operate with high robustness, a low power dissipation and a good
noise margin. For organic integrated circuits, there is an urgent need to find ways to-
wards organic semiconductors which can be ambipolar, i.e. are capable of transporting
both types of carriers, while maintaining the attractiveness of easy solution-processing.
We report on the fabrication of solution-processed ambipolar field-effect transistors and
inverters based on a blend of two suitable organic semiconductors.
98 Ambipolar organic field-effect transistors
9.1 Introduction
Charge transport through amorphous, or poly-crystalline organic semiconductors is not
fully understood, but a number of aspects are clear. It is possible to blend an active com-
pound with a non-active medium without spoiling the conductive properties, indicative of
the role of percolating conducting paths [6]. Secondly, depending on the electrode work-
functions and the nature of the organic semiconductors, the contacts play a crucial role.
The electrodes need to have a workfunction that allows injection of holes into the highest
occupied molecular orbital (HOMO) of the semiconductor and/or injection of electrons
in the lowest unoccupied molecular orbital (LUMO). Therefore usually other contact ma-
terials are chosen for electron-transporters and hole-transporters [7]. Concomitantly, one
electrode material can be used in combination with two organic semiconductors, when
one has its HOMO level and the other has its LUMO level aligned with the metal work-
function. In the past, this concept was used to construct heterostructure devices by evap-
orating an n-type semiconductor layer on top of a p-type semiconductor layer, which
resulted in both n-type and p-type transistor operation [8, 9]. In this stacked geometry,
the gate field needs to deplete the lower layer first to achieve accumulation in the top
layer. Also separate n-type and p-type transistors have been evaporated, which could be
combined to CMOS integrated circuits [10]. Instead of evaporating the organic semicon-
ductors sequentially, one would like to deposit both semiconductors in one easy process-
ing step, as was demonstrated by Tada et al. [11]. The fact that two active compounds
can be mixed together in solution, opens up the possibility to deposit simultaneously two
strongly interpenetrating networks of percolating conducting paths, with both hole- and
electron-transporting capabilities.
The interpenetrating networks used in this work, are composed of hole- transport-
ing poly[2-methoxy-5-(3’,7’- dimethyloctyloxy)]-p-phenylene vinylene (OC1 C10 -PPV)
and electron-transporting [6,6]-phenyl C61 -butyric acid methyl ester (PCBM). This mix-
ture is typically used for organic photovoltaic cells research [5]. The molecular struc-
tures of these materials are given in Fig.9.1. Gold electrodes were used as injecting
contacts. The choice of the semiconducting materials in combination with the injecting
electrodes is crucial. The energy levels that come into play are schematically represented
in Fig.9.2. For simplicity, the energy levels are drawn as straight lines, but band bending
occurs at the semiconductor-insulator interface upon an applied gate bias. This shifts the
Fermi level in the semiconductor, which in turn can result in band bending at the elec-
trode/semiconductor interface. The HOMO level of OC1 C10 -PPV, at 5.0 eV, is aligned
with the workfunction of gold, at 5.1 eV, which will result in an ohmic contact for hole
injection from gold into the OC1 C10 -PPV-network. Due to the large bandgap of OC1 C10 -
PPV gold is a blocking contact for electrons into OC1 C10 -PPV [7]. The alignment of the
gold workfunction with the LUMO level of the electron-transporter PCBM is not as good,
and the mismatch in energy levels results in an injection barrier, φB , of 1.4 eV for electron
injection into the PCBM network. However, this injection barrier is significantly reduced
to 0.76 eV, due to the formation of a strong interface dipole layer at the Au/PCBM in-
terface [12]. Similar behavior has been observed for the Au/C60 interface by ultraviolet
photoemission spectroscopy [13].
In general, the width of an injection barrier can be narrowed application of a large
9.1 Introduction 99
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Figure 9.2: Device band diagram of interpenetrating networks of OC1 C10 -PPV
and PCBM in contact with Au electrodes, when no biases are ap-
plied to the transistor. For simplicity the energy levels are drawn
as straight lines. It should be noted that band bending due to an
applied gate voltage can reduce the barrier for electron injection
into the PCBM network.
9.2 Experimental 101
9.2 Experimental
In the experiments we used heavily doped Si wafers as the gate electrode, with a 200
nm SiO2 , grown via thermal oxidation, as the gate-insulating layer. Using conventional
lithography, gold source and drain contacts were defined with a channel width W of 1 mm
and length L of 40 µm. The SiO2 layer was treated with the primer hexamethyldisilazane,
which makes the surface hydrophobic. The transistors were completed by spinning a
solution of PCBM and OC1 C10 -PPV (4:1 by weight), with a 0.5% weight content in
chlorobenzene. Prior to spincoating, the solution was stirred for one hour at 80oC. The
completed devices were annealed in vacuum for 15 hours at 90oC. The films were inves-
tigated with atomic force microscopy, showing the same surface morphology as reported
by Shaheen et al. [15] for the same mixture. This indicates that the constituents are uni-
formly mixed. The electrical measurements were performed at room temperature in a
vacuum of 10−5 mbar. A schematic cross-section of the transistors is given in Fig.9.1.
The semiconductor layer of transistors with PCBM only was spincoated from a 1 wt%
PCBM solution in chlorobenzene, while the semiconductor layer of OC1 C10 -PPV was
spun from a 0.4 wt% OC1 C10 -PPV solution in toluene or chlorobenzene. We note that
the wetting behavior of the PCBM and the OC1 C10 -PPV on the substrates was very differ-
ent, with the OC1 C10 -PPV solutions forming uniform films, whereas the PCBM solutions
where difficult to deposit in a uniform film. The transfer characteristics of a transistor
with gold electrodes and PCBM as the semiconductor show good electrical performance,
and a field-effect mobility was determined of 10−2 cm2 /Vs at a gate voltage, Vg = 20 V ,
demonstrating that the energy level mismatch between gold and PCBM can be overcome
with the field-effect.
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sistor operating in (a) hole-enhancement, and in (b) electron-
enhancement mode.
electron injection from gold into PCBM, which is much more pronounced than in a unipo-
lar PCBM transistor, where the output characteristics look qualitatively similar to those of
Fig.9.3a1. At low gate voltages and high drain voltages, we again observe a pronounced
increase in current, typical of an ambipolar transistor, and which is not observed in the
unipolar PCBM transistor.
The current increase can readily be understood, when considering that under certain
biasing conditions both holes and electrons are accumulated in the transistor channel,
forming a pn-junction [16].
1 The super-linear output characteristics at low V observed in the blend transistor, indicate an injection
ds
problem from the Au into the PCBM, which is probably due to the selective wetting of PCBM and OC1 C10 -
PPV on gold, which can also account for the low electron mobility in the blend transistor as compared to the
PCBM-only transistor.
9.3 Ambipolar transistor operation 103
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Figure 9.4: The transfer characteristics of the OC1 C10 -PPV:PCBM ambipolar
transistor. (a) For Vg < 0 V only the hole contribution is ob-
served in the current, whereas for Vg > 0 V the electron current
is seen.(b) For Vg > 20 V only the electron contribution to the
current is observed. Depending on the value of Vds however, the
hole current-contribution is already observed for Vg < 20 V . The
assymetry in electron and hole contributions to the total current
in (a) and (b) is due to the larger field-effect mobility for holes as
compared to the electrons.
104 Ambipolar organic field-effect transistors
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This is schematically represented in Fig.9.5. For a large negative Vg and a small neg-
ative Vds the transistor behaves as a unipolar hole accumulation transistor (Fig.9.5a)). If
in a unipolar device Vds is increased beyond Vds = Vg − Vso , where Vso is the switch-on
voltage of the field-effect2, a depletion region around the drain will develop and the drain
current saturates. However for an ambipolar transistor, electrons will start to accumulate
at the drain electrode. This electron accumulation region forms a pn-junction in the chan-
nel with the hole accumulation region at the source electrode (Fig.9.5b)). This electron
accumulation region is responsible for the observed current increase at high Vds . When
the transistor is biased in the hole-accumulation mode, the current can be described by a
model based on hopping of charge carriers in an exponential density of states (DOS) as
was described in chapter 2 [17, 18]:
A h W Ci 2 TD O S,h 2 TD O S,h
Ids = −Vg + Vso T − −Vg + Vso + Vds T , (9.1)
L
where Ah is a prefactor for the hole current [17, 18], Ci the insulator capacitance per unit
area, TD O S,h is the width of the exponential DOS for holes [18], and [[x]] = 12 x + 12 |x|.
For a complete description of the electron accumulation mode, we should consider the
injection-limited current. This has recently been modelled by thermally assisted hop-
ping from the electrode into the localized states of the organic semiconductor, which are
broadened due to disorder [20]. For the sake of simplicity, however, we will neglect the
2 We defined the switch-on voltage as the gate voltage that needs to be applied to reach the flat-band condition
(see Chapter 2) [17]
9.4 CMOS-like inverter operation 105
observed injection barrier for electrons here. Then, in the electron accumulation mode,
the current can be described analogous to Eq.9.1:
−Ae W Ci 2 TD O S,e 2 TD O S,e
Ids = Vg − Vso T − Vg − Vso − Vds T , (9.2)
L
where Ae is a prefactor for the electron current, and TD O S,e is the width of the exponential
DOS for electrons. Under bias conditions where both holes and electrons accumulate in
the channel, the transistor can be described by two transistors in series, one of length
L h where only holes accumulate and one of length L e where only electrons accumulate.
The source-drain current can readily be calculated from the condition of current continuity
across the pn-junction and the relation L e + L h = L. From these considerations it follows
that the total current is simply the sum of the source-drain currents in Eq.9.1 and Eq.9.2.
The ambipolar transistor can be represented as a p-type and n-type transistor, both with
length L, connected in parallel. Here it is implicitly assumed that charge transfer across
the pn-junction is not a limiting factor in the device performance.
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9.5 Conclusions
In conclusion, we have demonstrated ambipolar thin-film field-effect transistors, based
on interpenetrating networks of the solution-processed organic semiconductors OC1 C10 -
PPV and PCBM. Complementary logic based on these ambipolar transistors has the po-
tential to significantly simplify the design and improve the operation of organic integrated
circuits, while keeping the technology as simple as for unipolar logic.
References
[1] H.E.A. Huitema, G.H. Gelinck, J.B.P.H. van der Putten, K.E. Kuijk, C.M. Hart, E.
Cantatore, P.T. Herwig, A.J.J.M van Breemen and D.M. de Leeuw, Nature (London)
414, 599 (2001).
[3] G.H. Gelinck, T.C.T. Geuns and D.M. de Leeuw, Appl. Phys. Lett. 77, 1487 (2000).
[4] J.H. Burroughes, D.D.C. Bradley, A.R. Brown, R.N. Marks, K. Mackay, R.H. Friend,
P.L Burn and A.B. Holmes, Nature 347, 539 (1990).
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[6] C.Y. Yang, Y. Cao, P. Smith and A.J. Heeger, Synth. Met. 53, 293 (1993).
[7] P.W.M. Blom, M.J.M. de Jong and M.G. van Munster, Phys. Rev. B. 55, R656 (1997).
[8] A. Dodabalapur, H.E. Katz, L. Torsi and R.C. Haddon, Science 296, 1560 (1995).
[9] A.Dodabalapur, H.E. Katz, L. Torsi and R.C. Haddon, Appl. Phys. Lett. 68, 1108
(1996).
[10] B. Crone, A. Dodabalapur, Y.-Y. Lin, R.W. Filas, Z. Bao, A. LaDuca, R. Sarpeshkar,
H. E. Katz and W. Li, Nature 403, 521 (2000).
[11] K. Tada, H. Harada and K. Yoshino, Jpn. J. Appl. Phys. 35, L944 (1996).
[12] J.K.J. van Duren, V.D. Mihailetchi, P.W.M. Blom, T. van Woudenbergh, J.C. Hum-
melen, M.T. Rispens, R.A.J. Janssen and M.M. Wienk, submitted.
[13] S.C. Veenstra, A. Heeres, G. Hadziioannou, G.A. Sawatzky and H.T. Jonkman,
Appl. Phys. A, 75, 661 (2002).
[14] S.M. Sze, ”Physics of Semiconductor devices” (Wiley, New York, 1981).
[15] S.E. Shaheen, C.J. Brabec, N.S. Sariciftci, F. Padinger, T. Fromherz and J.C. Hum-
melen, Appl. Phys. Lett. 78, 841 (2001).
[16] G.W. Neudeck, H.F. Bare and K.Y. Chung, IEEE Trans. Electr. Dev. 34, 344 (1987).
108 References
[17] E.J. Meijer, C. Tanase, P.W.M. Blom, E. van Veenendaal, B.-H. Huisman, D.M. de
Leeuw and T.M. Klapwijk, Appl. Phys. Lett. 80, 3838 (2002).
[18] M.C.J.M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998).
[19] C. Detcheverry and M. Matters, Proc. ESSDERC, 328 (2000).
[20] T. van Woudenbergh, P.W.M. Blom, M.C.J.M. Vissenberg and J.N. Huiberts, Appl.
Phys. Lett. 79, 1697 (2001).
[21] K.Y. Chung, G.W. Neudeck and H.F. Bare, IEEE J. Solid-State Circ. 23, 566 (1988).
Chapter 10
Abstract
With the coming of age of organic semiconductors, envisioned applications in the area
of light-emitting diodes, plastic solar cells and integrated circuits are becoming a reality.
The promise of low-cost flexible integrated circuits for high volume applications such as
electronic paper, demands a flexible semiconductor layer, preferably a polymer, which
for ease of processing should be deposited from solution, via for instance spincoating
or inkjet technology. For organic integrated circuits an important improvement in circuit
performance is the step from unipolar logic, which uses either p-type or n-type transistors,
to complementary metal-oxide-semiconductor (CMOS) logic, which uses both n-type and
p-type transistor channels. Here we expand the work on blends described in the previous
chapter. We report on the fabrication of ambipolar field-effect transistors and inverters
based on the solution-processed organic semiconductor poly(3,9-di-tert-butylindeno[1,2-
b] fluorene) (PIF).
110 Ambipolar transistors based on a single organic semiconductor
10.1 Introduction
Q
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Figure 10.1: Schematic cross-section of the FET geometry used in this study.
The molecular structure of PIF is given.
10.2 Experimental
As low band gap organic semiconductor in the ambipolar transistors we have used poly(3,9-
di-tert-butylindeno[1,2-b] fluorene) (PIF) [4] which has a band gap of 1.55 eV. Gold, with
a workfunction of 5.1 eV, is used for the source and drain injecting contacts. In the exper-
iments we use heavily doped Si wafers as the gate electrode, with a 200-nm-thick-layer of
thermally oxidized SiO2 as the gate-insulating layer. Using conventional lithography, the
gold source and drain interdigitated contacts are defined with a channel width W of 2 cm
and length L of 10 µm. The SiO2 layer is treated with the primer hexamethyldisilazane.
The transistors are completed by spinning a solution of 1wt% PIF in chloroform onto the
substrate. The molecular structure of PIF and a schematic cross-section the transistor ge-
ometry are given in Fig.10.1. The measurements are performed in a vacuum of 10−4 mbar
at room temperature, after annealing the sample for an hour at 90 o C.
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Figure 10.2: The output characteristics of the PIF ambipolar transistor, oper-
ating in (a) hole-enhancement, and in (b) electron-enhancement
mode.
10.3 The PIF ambipolar transistor and inverter 113
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Figure 10.3: The transfer characteristics of the PIF ambipolar transistor. (a)
For Vg < −15 V only the hole contribution is observed in the
current, whereas for Vg > −15 V the electron current is seen. (b)
For Vg > 10 V only the electron contribution to the current is ob-
served. The hole current-contribution is observed for Vg < 10 V .
114 Ambipolar transistors based on a single organic semiconductor
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tics in the linear operating regimes of the transistor (see Fig.3) we calculate the field-effect
mobility using:
L ∂ Ids
µ F E Vg = (10.1)
W Ci Vds ∂ Vg
For the holes (at Vg = −30 V ) and electrons (at Vg = 30 V ) we find a µ F E of
4·10−5 cm2 /Vs and 5·10−5 cm2 /Vs respectively. We find that in the present transistor the
onset of the field-effect for the electron accumulation was at Vg = 10 V , and for the hole
accumulation at Vg = −15 V (see Fig.10.3).
The combination of a single material for the source and drain electrodes and a single
material for the semiconductor layer, with evenly matched field-effect mobilities for the
holes and electrons allows the most simple fabrication of a logic voltage inverter. Inverter
operation is observed for two identical PIF ambipolar transistors connected in accordance
with the schematic diagram given in the inset of Fig.10.4. The ambipolar inverter operates
in the first and the third quadrant, depending on the applied supply voltage, V D D . This
behavior was also observed for ambipolar inverters based on a blend of n-type and p-type
semiconductors (see previous Chapter) [2].
To demonstrate that the ambipolar behavior observed in FETs based on PIF, is not
particular to the semiconductor used here, but is more widely applicable to other semicon-
ductors, we also performed measurements on a solution-processed pentacene film. The
sample was measured in vacuum after an anneal of 10 hours at 90o C, and showed electron
enhancement at high applied positive Vg , as is shown in Fig.10.5. The electron current is
higher than the observed gate currents in the transistor. Also, the electron current is only
observed after thermal anneal in vacuum and is not observed anymore if the sample is
10.4 Conclusions 115
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exposed to air. This demonstrates that there are organic semiconductors that can achieve
ambipolar transistor operation.
10.4 Conclusions
In conclusion, we have demonstrated ambipolar field-effect transistors based on the solution-
processed organic semiconductor poly(3,9-di-tert-butylindeno[1,2-b] fluorene) and also
for solution-processed pentacene. Both charge carrying moieties are injected into the
organic semiconductor from gold electrodes, and the semiconductor is processed from
solution, which is an important prerequisite for low-cost polymer electronics. Functional
CMOS-like inverters have been demonstrated. This result paves the way for CMOS tech-
nology based on a single solution-processable organic semiconductor.
References
mobility of charges directly at the interface with the insulator layer is a useful parameter
in the description of the transistors. In the last paragraph of chapter 2 we link the mobility
obtained from the transistors to the mobility as it is determined in light-emitting diodes.
We conclude that the large differences in mobility obtained for a single polymeric semi-
conductor in these two devices is mainly due to a large difference in charge carrier density
in the two devices.
In chapter 3 the mobility of the charge carriers is measured and analyzed as a func-
tion of temperature. From these data we observe an empirical rule, termed the Meyer-
Neldel rule. Associated with this rule is a characteristic energy, which has a very similar
value for all the studied materials, which implies a common origin of this energy in the
charge transport mechanism. It is argued that a possible origin of the characteristic energy
is due to the fact that a charge carrier can require multiple phonons to hop in the polymer
film, rather than just one phonon. In chapter 4 this empirical rule is also related to the
experimentally observed electric field dependence of the mobility.
For practical applications, it is not only of importance to understand the charge trans-
port through the polymer film, but also to gain insight in how the charge carriers are in-
jected into the polymer film. The electrodes that we used in this study consist of gold. The
charges do not go from the gold to the polymer layer without resistance. To get an idea
of the resistance involved in this injection process, in chapter 5 we looked at series of
transistors, where the length of the transistor is systematically varied. In this way we can
separate the charge transport process in the polymer film from the charge injection process
at the electrodes. We find a correlation between the injection resistance and the mobility
in the polymer itself and interpret this by considering injection from the electrode into an
energetical distribution of states in the polymer.
Certain polymers, with promising properties for applications, also have their draw-
backs in terms of air and light stability. In chapters 6 and 7 we look at the polymer
poly(3-hexyl thiophene), which has a conductivity that increases with time under the in-
fluence of light and oxygen exposure. This is the result of a doping process where an
increasing amount of charge carriers is present in the polymer layer, that contribute to
the conductivity. In chapter 6 we look first at impedance analysis techniques applied to
metal-insulator-semiconductor diodes (MIS diodes), to be able to determine the amount
of dopants in the polymer. We find that the measurement frequency used in the impedance
technique can not be too high, because otherwise the low mobility of the charge carriers
in the polymer will dominate the measurement results instead of the dopant density. In
chapter 7 this technique is applied to determine how efficient the dopant charges form un-
der the influence of light and oxygen. In chapter 8 we demonstrate that the dopant density
changes can also directly be determined from field-effect transistor measurements. Fur-
thermore we are able to relate the mobility of charge carriers in the polymer bulk to the
dopant density.
In the previous chapters we have mainly looked at unipolar p-type transistors, which
means: transistors in which predominantly positively charged carriers move. In chapter
9 we show that a suitable combination of the electrode material with a mixture of a p-type
and an n-type semiconductor can be used to construct ambipolar field-effect transistors.
These transistors enable a simplification of the circuit design of integrated circuits. At the
same time the circuit performance may improve. Logic gates (such as a voltage inverter,
Summary 121
as is demonstrated in chapter 9) switch in a better defined region of the voltage axis and
a have a steeper crossover in voltage upon going from high to low voltage as compared
to unipolar logic gates. In chapter 10 we demonstrate that ambipolar transistor operation
can also be realized on the basis of a single semiconducting polymer. These findings
contribute to develop organic electronics more towards complementary logic, by using
the properties of the semiconductors as optimally as possible for electronic circuitry.
Samenvatting
Uit het modelleren concluderen we dat de startspanning een bruikbare fysische param-
eter is voor de beschrijving van organische transistoren. Voorts wordt de mobiliteit van
de ladingsdragers, welke aangeeft hoe gemakkelijk ladingen bewegen door de polymeer
laag heen, experimenteel bepaald als functie van de ladingsdichtheid in de transistor. We
concluderen dat de gemiddelde mobiliteit van ladingen direct aan het oppervlak met de
isolator een goede parameter is voor de beschrijving van de transistoren. In de laatste
paragraaf van hoofdstuk 2 wordt deze ladingsdichtheidsafhankelijke mobiliteit in veld-
effecttransistoren gelinkt met de mobiliteit zoals die bepaald wordt uit lichtemitterende
diodes. We concluderen dat de grote verschillen in mobiliteit, die waargenomen wor-
den voor een enkel polymeer in de twee verschillende structuren, voor een groot deel
het gevolg zijn van een aanzienlijk verschil in ladingsdichtheid tussen de transistor en de
lichtemitterende diode.
In hoofdstuk 3 wordt de mobiliteit van de ladingsdragers bekeken als functie van
de temperatuur. Aan de hand van deze data, nemen we een empirische regel, getiteld de
Meyer-Neldel regel, waar. Aan deze regel is een karakteristieke energie verbonden die
voor de bestudeerde materialen steeds eenzelfde waarde oplevert. Dit feit duidt mogelijk
op een gemeenschappelijke oorsprong van deze energie in het ladingstransport in de ver-
schillende materialen. Er wordt beargumenteerd dat een mogelijke grondslag voor deze
karakteristieke energie gelegen is in het feit dat een lading voor een sprong tussen twee
plaatsen in het polymeernetwerk meerdere phononen per sprong nodig heeft, in plaats van
slechts een enkel phonon. In hoofdstuk 4 wordt deze empirische regel tevens gekoppeld
aan de experimenteel waargenomen veldafhankelijkheid van de mobiliteit.
Voor praktische toepassingen is niet alleen het begrip van het ladingstransport belan-
grijk, maar ook hoe ladingen geı̈njecteerd worden in de polymeerlaag. De elektrodes, die
we hiervoor gebruikt hebben, bestaan uit goud. De ladingen gaan niet zonder enige weer-
stand de polymeerlaag in vanuit het goud. Om een idee te krijgen van de weerstanden
die hierbij belangrijk zijn, hebben we in hoofdstuk 5 gekeken naar series van transistoren
waarbij de lengte van de transistor systematisch veranderd wordt. Zo kunnen we het lad-
ingstransport in de polymeerlaag loskoppelen van de ladingsinjectie van het goud naar
de polymeerlaag. We vinden een correlatie tussen de injectieweerstand en de mobiliteit
in het polymeer zelf en interpreteren dit in de context van de verdeling van energetische
toestanden in het polymeer.
Bepaalde polymeren met veelbelovende eigenschappen hebben ook nadelen ten aan-
zien van hun lucht- en lichtgevoeligheid. In hoofdstukken 6 en 7 kijken we naar het
polymeer poly(3-hexyl thiofeen), waarvan de geleiding in de tijd toeneemt onder invloed
van zuurstof en licht uit de omgeving. Dit is het gevolg van een doteringsproces waar-
bij er steeds meer ladingsdragers in het polymeer aanwezig zijn, die bijdragen tot de
geleiding. In hoofdstuk 6 wordt allereerst gekeken naar de impedantieanalysetechniek
toegepast op metaal-isolator-halfgeleider diodes (MIS diodes), voor het bepalen van de
hoeveelheid dotering in het polymeer. We vinden dat de meetfrequentie waarbij de bepal-
ing wordt gedaan niet te hoog mag zijn omdat anders de mobiliteit van de ladingsdragers
in het polymeer de meting domineert in plaats van de hoeveelheid dotering. In hoofd-
stuk 7 wordt deze meettechniek toegepast om te bepalen hoe efficiënt doteringsladingen
gevormd worden onder invloed van zuurstof en licht. In hoofdstuk 8 laten we zien dat
de doteringsveranderingen ook direct aan de hand van veldeffecttransistoren bepaald kun-
Samenvatting 125
10. Unification of the hole transport theories in light-emitting polymeric diodes and
field-effect transistors,
C. Tanase, E.J. Meijer, P.W.M. Blom and D.M. de Leeuw, submitted. [Chapter 2]
128 List of Publications
Patent Application
Solution-processed ambipolar organic field-effect transistors
D.M. de Leeuw, E.J. Meijer, S. Setayesh
European Patent Application EP 03100177.9
Curriculum Vitae
1998 Visiting student at Xerox Palo Alto Research Center, Palo Alto,
USA, in collaboration with dr. R.B. Apte. Subject: Morphology
study of anodized porous aluminum oxide.
Eduard