Doping as a Versatile Tool to Realize Highly

Efficient Organic Devices

Björn Lüssem∗ , Sebastian Reineke∗ , Hans Kleemann∗ , Philipp Sebastian∗ and Karl Leo∗
Institut für Angewandte Photophysik
Technische Universität Dresden
01062 Dresden
Email: bjoern.luessem@iapp.de

Abstract—Doping of organic layers is a key technology for

organic electronics. Several examples demonstrating the capa-
bilities of the organic doping technology are presented: highly
efficient white organic light emitting diodes (OLEDs) reaching
the efficiency of fluorescent tubes, highly reproducible organic
memory devices, and organic Zener Diodes with precisely ad-
justable breakdown voltages.

I. I NTRODUCTION
Organic electronics have been extremely successful in the
past decades and are starting to enter commercial markets.
Energy efficient displays and luminaries based on Organic
Light Emitting Diodes (OLEDs), Organic Solar Cells, back-
planes for e-Readers consisting of organic transistors, or Radio
Frequency Identification Tags (RFID) have been commercial-
ized or are close to commercialization. The main strengths
of organic compared to inorganic electronics are the ease
of fabrication on large areas, low temperature deposition
on flexible substrates and the possibility to produce organic
devices by a low-cost roll-to-roll fabrication.
Doping of organic layers is a key technology for the prepa-
ration of highly efficient and reproducible organic devices [1].
It works in a similar fashion as doping of inorganic semicon-
ductors. A small amount of impurities is doped into a semi-
conducting matrix and donates either free electrons or holes
to the matrix. The advantages of doping in organic electronics
are numerous. Doping of transport layers of OLEDs helps to
avoid ohmic losses and the devices can be driven close to the
thermodynamic limit [2]. Doping can be used to control the
position of the Fermi level [3] and the thickness of charge
depletion zones [4] in organic layers, which enables novel
organic devices for information processing and storage.
In this paper, the versatility of doping is shown by several
novel organic devices based on electrically doped layers.
Beside a highly efficient white OLED for lighting applications
[5], the design of an organic memory [6] and an organic Zener
diode [7] is discussed.
II. H IGHLY E FFICIENT W HITE O RGANIC L IGHT E MITTING
D IODES
Ever since the first publications by Tang and VanSlyke in
1987 [8], the performance of OLEDs has improved steadily.
Due to their high efficiency, OLEDs are considered as a
Fig. 1. The stack design of a highly efficient white OLED is shown on top
[5]. The device consists of electron and hole transport layers (BPhen:Cs and
MeO-TPD:NDP2), electron and hole blocking layers (NPB and TPBi) and
several emission layers.
The design of our white OLED, which reaches the highest
efficiency reported in the scientific literature so far, is shown
in Figure 1 [5]. The device is based on the p-i-n-concept, i.e.
it consists of electrically doped p and n layers enclosing an
intrinsic emitting layer [9]. We use ITO (on high index glass,
nhigh = 1.78) as anode, MeO-TPD1 doped with NDP22 as
p-doped hole transport layer, NPB3 as electron blocking layer,
Ir(MDQ2(acac)4 doped into the matrix material TCTA5 as red
emitter, FIrpic6 doped into the matrix TPBi7 as blue emitter,
Ir(ppy)38 doped into TPBi as green emitter, TPBi as hole
blocking layer, BPhen9 doped with Cs as electron transport
layer, and finally Ag as cathode.
Doping leads to extremely low driving voltages, which is
shown in the top part of Figure 2. A brightness of 1000 cd/m2 ,
which is relevant for lighting applications, is already reached
1 N,N,N’,N’-tetrakis(4-methoxyphenyl)-benzidine
2 Novaled AG
3 N,N’-di(naphtalen-1-yl)-N,N’)-diphenyl-benzidine
4 iridium(III)bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)
5 4,4’,4”-tris(N-carbazolyl)-triphenylamine
6 iridium(III)-bis(4,6,-di-fluorophenyl-pyridinato-N,C2)-picolinate
7 2,2’,2”(1,3,5-benzenetriyl) tris-(1-phenyl-1H-benzimidazole
8 fac-tris(2-phenylpyridine)iridium

potential technology for future lighting sources. 9 4,7,-diphenyl-1,10-phenanthroline

978-1-4577-0430-7/11/$26.00 ©2011 IEEE 1


Fig. 2. IVL characteristic of the white OLEDs shown in Figure 1 (top). A
luminance of 1000 cd/m2 is reached at driving voltages of approximately
3V. In the bottom part of the Figure, the luminous efficacy is shown [5].
The efficacy is either measured without any outcoupling enhancement, with
a pyramidal outcoupling structure or with a half-sphere. Efficiencies beyond
120 lm/W are reached for the half-sphere measurement and 90 lm/W for the
pyramidal outcoupling sheet.
at a voltage of approximately 3 V. As the driving voltage is
inversely proportional to the luminous efficacy, a low driving
voltage directly relates to a high efficiency.
The luminous efficacy and several techniques to enhance the
outcoupling efficiency are shown in the bottom part of Figure
2. Due to the high refractive index of the organic layer, the ITO
and the glass, light can be reflected at the interface between
glass and air, and the OLED forms an optical microcavity.
Without optimizing the optics of the device, approximately
four out of five photons are trapped inside the cavity. The
black line in Figure 2 denotes the efficiency measured without
any outcoupling enhancement, the green line is measured with
a structure of small pyramids cut into a sheet of high index-
glass applied to the substrate and the red line is obtained by
applying a half sphere to the substrate and coupling out all
glass modes.
The highest efficiency at 1000 cd/m2 is reached when a
half-sphere is applied to the substrate. However, this out-
coupling solution is not scalable to large areas and thus
not practicable for later products. The pyramidal outcoupling
structure is scalable and although the luminous efficacy drops
to 90 lm/W, this value is still the highest efficiency reached so
far for white OLEDs and surpasses the efficiency of fluorescent
tubes.
Although several parameters such as the color point of these
devices (0.41, 0.49) and the lifetime still need to be improved,
these experiments clearly demonstrate the potential of white
OLEDs. In the literature, several alternative approaches like
Fig. 3. Organic resistive memory based on charge trapping. The device
shows two clearly distinguishable states, one high-resistive state and one low-
resistive state. The ON/OFF ratio can be tuned by the magnitude of the applied
field.
the triplet-harvesting concept are discussed [10] that combine
high efficiency with long lifetime and good color quality.
III. O RGANIC M EMORY
In comparison to OLEDs, which are already very mature,
organic memory devices are still in the research phase and
for many concepts a clear understanding of the working
mechanism is missing [11]. Nevertheless, organic memory
concepts have gained a lot of attention in recent years due
to the fact that most organic memory storage media are non-
volatile, i.e. they can store information without a continuous
supply of energy.
We have recently developed an organic memory that shows
a high reproducibility and good performance [6]. The working
mechanism is based on charge trapping in organic n-type ma-
terials, which is a common effect in most electron transporting
materials. The device is a resistive memory, i.e. the resistance
between the two contacts can be switched between a high
(OFF) state and a low (ON) resistive state. The characteristic
of the device is shown in Figure 3. The two states are clearly
visible. The switching ratio, i.e. the ratio between the OFF
and the ON state resistance is in the order of 10 and can be
tuned by the magnitude of the applied voltage.
A remarkable feature of the memory is the large number
of possible switching cycles. A typical experiment is shown
in Figure 4. The device is erased by a voltage pulse of -4 V,
written by a voltage pulse of +4 V and read at a voltage of 1
V. Although only four switching cycles are shown in Figure
4, the device can be switched up to 104 times.
The individual devices can be integrated into a passive
crossbar structure to build larger memory blocks. However,
care has to be taken in a passive crossbar structure that
parasitic currents flowing through non-selected devices are
suppressed. This can be accomplished by a series connection
2

Fig. 4. The organic memory can be switched ON and OFF by short voltage
pulses of ±4 V. The devices can be read out at lower voltages (1 V). The
ON and OFF state of the device can still be distinguished after 104 switching
cycles.
Fig. 5. Organic Zener Diode based on electrically doped layers. The
breakdown voltage can be precisely tuned by the doping concentration of
the doped layers, whereas the forward direction is not affected by the change
in doping concentration [7].
of the memory device with an organic diode, or, to realize
re-writable memory, Zener-diodes.
IV. O RGANIC Z ENER D IODES
Besides their significance for organic memory structures,
Zener-Diodes are probably the best example to show that
doping is not only a technique to realize low driving voltages
but can also be used to realize devices thus far only known
from inorganic semiconductors [7].
The current vs. voltage characteristic of an organic Zener-
Diode is shown in Figure 5. It is based on the p-i-n concept and
consists of Al (100nm) as Anode, Ir(piq)310 doped with NDP2
as p-doped layer, a mixed layer consisting of BAlq211 and
10 Tris(1-phenylisoquinoline) iridium(III)
11 aluminium- (III)bis (2-methyl-8-quninolinato)- phenylphenolate
Fig. 6. Mott-Schottky plot of Zener-Diodes consisting of Al(100nm)/ MeO-
TPD:F4TCNQ (4wt%,50nm)/ Balq2:NPB[50wt%](7nm)/ Bphen:Cs(50nm)/
Al(100 nm). At increased negative voltages, the thickness of the charge
depletion zones increases. This leads to a linear relationship between the
square of the capacitance and the inverse voltage up to a voltage of -6 V.
Beyond -6 V, charges are injected into the intrinsic layer leading to a decrease
of the capacitance and a deviation from the linear relationship [7].
NPB as intrinsic layer (7 nm), Ir(piq)3 doped with NDN112
(16wt%, 50nm) as n-doped layer, and Al (100nm) as cathode.
At positive voltages, the device shows the expected diode
behavior with an current onset at approximately 2 V. At
negative voltages, the device shows a reversible breakdown.
The breakdown voltage can be precisely tuned by the doping
concentration in the p-layer.
It can be concluded from the dependence of the capacitance
of Zener Diodes on the applied voltage (see Figure 6) that
the thickness of the depletion zone d of the p-i-n diode
(including the thickness di of the intrinsic layer) can be
described by Equation 1, which is well-known for inorganic
semiconductors.
r
20 NA + ND
d= (Vbi − V ) + d2i (1)
e NA ND
where e is the elementary charge, 0 the permittivity, A the
active area, di the intrinsic layer thickness, NA the number
of active acceptor states in the p-doped layer, ND the number
of active donor states in the n-doped layer , Vbi the built-in
potential, and V the external bias voltage [4].
The validity of Equation 1 is a direct proof that the p-
and n-layer of the Zener-Diode are partially depleted and that
the thickness of the charge depletion zone in organic diodes
depends on the doping concentration. This dependency can
explain the increase of the breakdown voltage with decreasing
doping concentration. By decreasing the doping concentration,
the thickness of the charge depletion zone in the p-i-n junction
is increased, the electric field inside the depletion zone is
decreased and Zener tunneling is reduced.
Thus, the characteristic of the Zener diode can be precisely
adjusted by the doping concentration of the organic layers,
12 Novaled AG
3
which is a key requirement for the use of Zener-diodes as
selection element in passive matrix memory arrays to prevent
parasitic currents flowing through non-selected memory ele-
ments.
V. C ONCLUSION
Organic Electronics is a rapidly evolving field of research
and development. One strength of organic electronics is its
versatility and the large variety of functions that can be real-
ized. Doping is a key technology enabling novel functionalities
of organic devices. Beside the most well-know applications of
organic electronics as, for example, OLEDs, novel applications
such as organic memories and organic Zener diodes can be
built.
ACKNOWLEDGMENT
The authors thank the Free State of Saxony and EU
(EFRE) for financial support under project NKOE (12712)
and Novaled for providing the HTL dopant NDP2 and the
ETL dopant NDN1. This work has been partially funded by
the BMBF under Contract No. 13N 10142, project acronym
“Multifunktionale Speicherkonzepte”.
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