All solution processed blue multi-layer light emitting diodes realized by

thermal layer stabilization and orthogonal solvent processing

Sebastian Naua, Roman Trattniga, Leonid Pevznerb, Monika Jgera, Raphael Schlesingerc, Marco V.
Nardic, Giovanni Ligorioc, Christos Christodoulouc, Niels Schultee, Stefanie Winklerd, Johannes
Frischc, Antje Vollmerd, Martin Baumgartenb, Stefan Saxa, Norbert Kochc,d, Klaus Mllenb, Emil J.
W. List-Kratochvila,f,*
a

NanoTecCenter Weiz Forschungsgesellschaft mbH, Franz Pichler Strasse 32, A-8160 Weiz,
Austria; b Max-Planck-Institut fr Polymerforschung, Ackermannweg 10, D-55128 Mainz,
Germany; c Institut fr Physik, Humbold-Universitt zu Berlin, Brook-Taylor-Strasse 6, D-12489
Berlin, Germany; d Helmholz Zentrum Berlin fr Materialien und Energie GmbH,
Eletktronenspeicherring BESSY II, Albert-Einstein Strae 15, D-12489 Berlin, Germany; e Merck
KGaA, Frankfurter Strae 250, D-64293 Darmstadt, Germany; f Institut fr Festkrperphysik, Graz
University of Technology, Petersgasse 16, A-8010 Graz, Austria
ABSTRACT
Herein we report on the fabrication and the properties of two highly efficient blue light emitting multilayer polymer light
emitting diodes (PLEDs). The first device structure combines a thermally stabilized polymer with a material processed
from an orthogonal solvent, allowing for the fabrication of a triple layer structure from solution. The well known
poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine) (TFB), which can be stabilized in a bake-out procedure,
was used as a hole transporting layer. A novel pyrene triphenylamine (PPyrTPA) copolymer was used as emissive
layer. The stack was finalized by a poly(fluorene) - derivative with polar side-chains, therefore being soluble in a polar
solvent which allows for the deposition onto PPyrTPA without redissolving. The resulting PLED showed bright-blue
electroluminescence (CIE1931 coordinates x=0.163; y=0.216) with a high efficiency of 1.42 cd/A and a peak
luminescence of 16500 cd/m. The second presented device configuration comprises a thermally stabilized
indenofluorene triphenylamine copolymer acting as hole transporter, and an emissive copolymer with building blocks
specifically designed for blue light emission, effective charge carrier injection and transport as well as for exciton
generation. This multilayer PLED led to deep-blue emission (CIE1931 x=0.144; y=0.129) with a remarkably high device
efficiency of 9.7 cd/A. Additionally, atomic force microscopy was carried out to investigate the film morphology of the
components of the stack and x-ray photoemission spectroscopy was performed to ensure a full coverage of the materials
on top of each other. Ultraviolet photoemission spectroscopy confirmed the desired type-II band level offsets on the
individual interfaces.
Keywords: polymer light-emitting diode, PLED, multilayer, solution processing
*emil.list-kratochvil@ntc-weiz.at; phone 0043 316 876 8000; fax 0043 316 876 8040; http://www.ntc-weiz.at

1. INTRODUCTION
Since the first reports on the properties of organic semiconductors1 tremendous progress with respect to fundamental as
well as application related aspects has been made. Based on these continuous advancements, organic light emitting
diodes (OLEDs) shift more and more into the focus of industrial research. Different applications in the field of lighting2
or displays3 can already be found on the market since several years. Still, there are quests for improvement related to e.g.
cost-efficient fabrication, long-term colour stability and long lifetimes in the range of ten thousands of hours. Therefore
several requirements have to be met such as chemical stability of the organic materials with very low concentrations of
chemical defects and other impurities.

Organic Light Emitting Materials and Devices XVII, edited by Franky So, Chihaya Adachi, Proc. of SPIE
Vol. 8829, 88290Z 2013 SPIE CCC code: 0277-786X/13/$18 doi: 10.1117/12.2024146

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Stable green and red emitting polymer emitter materials are already well established and impressive efficiencies as well
as device lifetimes from polymer light emitting diodes (PLEDs) have been demonstrated. Yet, blue PLEDs still show an
approx. 10 times shorter lifetime compared to their red and green counterparts. In order to achieve comparable lifetimes
for each colour, further progress in the material synthesis of blue emitting polymers as well as in the optimization of
device structures is required.
In the class of blue light emitting polymers pyrene based 4 and poly(paraphenylene) (PPP) 5 type materials are
particularly promising materials. While pristine PPPs show a UV-violet emission, their bridged derivatives can be
tailored with respect to their emission colour by increasing the number of aryl-aryl bridges, resulting in an increased
conjugation length and in a shift of the emission spectrum.6,7,8,9,10,11
On the other hand, pyrene-based compounds are as well thoroughly investigated candidates for blue light emitting
devices. It is known that pyrenes often show a red-shift of the emission colour due to excimer formation resulting from
- - stacking of the planar molecule. Recently it was shown that this undesired property can fully be prevented by
introducing different side chains12,13 making pyrenes to good candidates as blue emitters in PLEDs.
Apart from stable emitter materials, further issues such as efficient charge-injection as well as chargetransport need to
be addressed to achieve highly efficient and stable devices. Since the basic configuration of a PLED comprises at least
one conjugated organic material between two electrodes, efficient charge injection can be achieved by selecting proper
electrode materials 14 with workfunctions close to the highest occupied- and lowest unoccupied molecular orbital
(HOMO, LUMO), respectively. Further improvements can be obtained by ensuring an enhanced charge transport form
the electrode interfaces towards the emission layer, either by additional transport layers or by improvement of the
inherent transport properties within the emissive layer by additional functionalized groups.
Along these lines, a principle design guideline for OLEDs is the multilayer structure, combining layers of conjugated
materials and/or insulators with different band offsets, band gaps and transport properties. Such multilayer OLEDs are
typically assembled by thermal evaporation of molecular organic materials layer-by-layer in a vacuum coating unit.
Certainly, this is a technologically demanding process, suffering e.g. from a slow processing speed or an increased
material waste. Alternatively, polymers can be used instead of molecular materials. These are typically soluble in an
organic solvent and can therefore be processed from solution by using technologies as spin-casting, spray-coating15,
doctor blading16 or ink-jet printing17,18. Especially the latter paves the way for material-efficient, structured and large area
fabrication of PLEDs on different substrates.
Irrespective of the employed PLED fabrication technique, the desired multilayer setup leads to a serious challenge
related to the deposition of the individual polymer layers on top of each other. The crucial issue during the fabrication of
solution based multilayer PLEDs is not to redissolve or modify the preceding polymer layer by the solvent used to
deposit the polymer of the subsequent layers in a bottom up device preparation process.
So far, various approaches have been suggested to overcome this problem like liquid buffer layers between the individual
polymer layers19, in situ converted or crosslinked polymer layers20,21,22 or layer-stabilizing curing processes23,24,25.
Moreover, polymers can be tailored with respect to their solubility. If one material is soluble in a polar solvent and the
second is soluble in a non-polar solvent, the mutual interaction or redissolving can be minimized to a high degree. This
approach was successfully applied by e.g. Sax, et al.26 by spin-coating a poly(fluorene) derivative from a polar solution
onto a non-polar soluble poly(indenofluorene) derivative. A 20-fold efficiency enhancement was obtained by this
approach.

2. BRIGHT-BLUE SOLUTION PROCESSED TRIPLE LAYER PLEDS WITH

POLY(PYRENE) AS EMITTER
Herein we describe the fabrication and characterization of fully solution processed triple-layer PLEDs. As previously
described27,29 this approach can lead to highly enhanced luminance as well as efficiency values.
For the PLEDs, ITO coverd quartz glass (purchased from Delta Technologies, ltd.) was used as transparent substrate /
anode. A 60 nm layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulphonic acid) (PEDOT:PSS) (CLEVIOS P VP
AI 4083, Brayton) was deposited by spin casting and dried at 200C on a hotplate. Subsequently, TFB was deposited
from a xylene solution, baked at 200C in argon atmosphere and spin-rinsed with pure solvent to remove any solvable
residuals.28 Afterwards PPyrTPA was spin-cast from toluene solution and dried at 120C in high vacuum conditions. The

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final layer of 9,9-bis(3-(5',6'-bis(4-(polyethyleneglycol)phenyl)-[1,1':4',1-terphenyl]-2-yl)propyl)-9,9-dioctyl-2,7polyfluorene (PEGPF) was deposited from a methanol solution.

The device stack ITO/PEDOT:PSS/TFB/PPyrTPA/PEGPF was finalized by a thermally evaporated calcium/aluminium
multilayer cathode (10 nm / 100 nm). The chemical structures of the employed materials are shown in Figure 1.

Figure 1. Chemical structures of the used compounds. Top Left: poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine)

(TFB, purchased from Luminescence Technology Corp. (LUMTEC)), top right: 9,9-bis(3-(5',6'-bis(4-(polyethylene glycol)phenyl)[1,1':4',1 -terphenyl]-2-yl)propyl)-9,9-dioctyl-2,7-polyfluorene (PEGPF); The poly(ethylene glycole) bearing side-chains ensure a
solubility in polar solvents like methanol. PEGPF was synthesized as reported elsewhere27. bottom: Pyrene-Triphenylamine copolymer (PPyrTPA); PPyrTPA was synthesized as reported in [4]. Figure taken from [27], with permission from John Wiley and
Sons.

2.1 Film Morphology, Wettability and Coverage

The mutual interaction of the polymers and especially of the solvents is the crucial point during the fabrication of a
multilayer structure. Redissolving of the underlying material is strongly reduced when using the presented approach of
orthogonal soluble materials, however due to the different polarities of the materials undesired side-effects like a bad
wettability of the materials during deposition can occur, resulting in an inhomogeneous film formation or only partial
coverage.
In the following the desired multilayer stack consisting of ITO, PEDOT:PSS, TFB, PPyrTPA and PEGPF was
investigated for such effects. Figure 2 shows the surface topographies as obtained by atomic force microscopy (AFM).
The ITO surface can be seen in Figure 2a, clearly showing a quite rough surface (RMS-roughness, Rq) of 2.6 nm.
Additionally, distinct spikes were found. Spin-casting a layer of PEDOT:PSS on top strongly reduces Rq to 1.2 nm.
Subsequently, TFB was coated on PEDOT:PSS and annealed at 200C to insolubilize the layer. In order to remove the
soluble residuals, a spin-rinsing step was performed. The resulting surface after this procedure can be found in Figure 2c,
clearly showing a very smooth topography (Rq = 0.3 nm). The thickness of the layer and the surface morphology did not
change upon repeated spin-rinsing. The next layer (PPyrTPA) was deposited afterwards from toluene solution. To
investigate the impact on the morphology, the solvent of the sequent layer (methanol) was applied in a spin-rinsing step.
Figure 2d demonstrates that the PPyrTPA layer did not show any changes in the morphology and remained intact. (Rq =
0.8 nm). The ETL was deposited as the last layer from a methanol solution, resulting in a smooth film with Rq=0.5 nm.

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0.0

1.Hemm
15.0 nm

5.0um
0.0

1:Helnm
0.0

15.0 nm

5.0Ym

Figure 2. AFM topography of a) ITO; b) ITO/PEDOT:PSS; c) ITO/PEDOT:PSS/TFB (spin-rinsed); d)

ITO/PEDOT:PSS/TFB/PPyrTPA (spin-rinsed) and e) ITO/PEDOT:PSS/TFB/PPyrTPA/PEGPF surface. The RMS-surface
roughness was 2.6, 1.2, 0.3, 0.8 and 0.5 nm, respectively. The 5 m x 5 m micrographs were recorded in AFM tapping mode.
Figure modified from [27], with permission from John Wiley and Sons.

15.0 nm

5.0 pm

Besides AFM investigations, the whole stack was studied layer-by-layer using x-ray photoelectron spectroscopy (XPS).
XPS is a suitable tool to study the film formation behaviour of the individual layers i.e. if the layer shows full coverage
on the preceding layer. From Figure 3a and 3b it becomes evident, that the double peak signals of the indium (In3d) and
tin (Sn3d) core levels vanish completely upon PEDOT:PSS deposition on ITO. Instead, strong signals from sulfur (S2p)
and carbon (C1s) can be detected. As expected the oxygen (O1s) core level emission is strong for both materials. After
the deposition of TFB the sulfur and oxygen related signals are strongly attenuated. In exchange, nitrogen (N1s) and
bromine (Br3d) peaks show up in the spectrum. While the N1s peak originates from the nitrogen atom in the
triphenylamine group of the polymer, the bromine peak was identified as remainder from the TFB synthesis. The Br3d
double peak vanished upon PPyrTPA deposition. The nitrogen related peak gets attenuated as well, which is reasonable
due to the much lower amount of TPA groups present in the pyrene-based polymer. The XPS-spectrum of PEGPF finally
shows just peaks from carbon and oxygen. In contrast to the other materials, the carbon peak actually constitutes a
distinct double peak. This double feature is assigned to a chemical shift due to different binding energies between the
carbon-carbon and carbon-oxygen bonds in the polymer.
Complete coverage can be concluded from the fact that elemental core levels specific to the underlying layers were
strongly attenuated or vanished completely upon overlayer deposition.
The results of the AFM and the XPS - investigations display perfectly that, by the described combination of a layer
stabilizing hard-bake process and an orthogonal solvent approach, TFB, PPyrTPA and PEGPF are well suitable for a
solution processed multilayer assembly.

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ITO

Intensity (a.u.)

6000

6000

5000

In3d
Sn3d

4000
C1s

3000
2000
1000

4000
O1s

2000
1000

N1s

S2p

0
0

100

200

300

400

500

600

100

200

300

400

500

600

Binding Energy (eV)

Binding Energy (eV)

ITO/PEDOT:PSS/TFB (Tol spin-rinsed)

ITO/PEDOT:PSS/TFB/PPyrTPA (MeOH spin-rinsed)

6000

5000
Intensity (a.u.)

5000
Intensity (a.u.)

C1s

3000

6000

5000
Intensity (a.u.)

7000

ITO/PEDOT:PSS
O1s

4000
3000

C1s

2000
1000

N1s
Br3d

0
0

100

4000
3000

C1s

2000
1000

O1s

N1s

S2p

0
200

300

400

500

600

O1s

Si2p

100

Binding Energy (eV)

200

300

400

500

600

Binding Energy (eV)

ITO/PEDOT:PSS/TFB/PPyrTPA/PEGPF

6000

Intensity (a.u.)

5000
4000
O1s

C1s

3000
2000
1000
0
0

100

200

300

400

500

600

Binding Energy (eV)

Figure 3. Layer-by-layer XPS spectra obtained from for a) ITO; b) ITO/PEDOT:PSS; c) ITO/PEDOT:PSS/TFB (spin-rinsed); d)
ITO/PEDOT:PSS/TFB/PPyrTPA (spin-rinsed) and e) ITO/PEDOT:PSS/TFB/PPyrTPA/PEGPF. The specific core levels for the
respective materials are highlighted. The signals of the core levels of the preceding layers vanish completely upon deposition of the
materials. Complete coverage of each individual layer can be concluded from these results.
Figure modified from [27], with permission from John Wiley and Sons.

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2.2 Chracterization of single and multilayer PLED devices

0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9

15000

0.50

10000

0.00
400 450 500 550 600 650

0.25

wavelength (nm)

5000
0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6

bias (V)

norm. EL

-2

0.75

2000
1800
1600
1400
1200
1000
800
600
400
200
0

luminance (cd/m )

wavelength (nm)

5000

current density (A m )

10000

0.00
400 450 500 550 600 650

0.25

1.00

20000
2

15000

0.50

0.75

160
140
120
100
80
60
40
20
0

luminance (cd/m )

1.00
norm. EL

20000
-2

current density (A m )

Aside from the triple-layer structure, each material was investigated in a single layer PLED configuration
(ITO/PEDOT:PSS/TFB, PPyrTPA, PEGPF/Ca/Al). The results can be found in Figure 4. The TFB based PLED showed
a deep-blue emission with the CIE1931 coordinates x = 0.173; y = 0.102, a maximum current efficiency of 0.02 cd/A
and a maximum luminance value of 157 cd/m. Also PEGPF exhibited a deep-blue emission spectrum, prototypical for
poly(fluorene) (CIE1931 coordinates x=0.164; y=0.145) with a maximum efficiency of 0.2 cd/A and a maximum
luminance of 1870 cd/m. The emission spectrum of the PPyrTPA co-polymer showed a bright-blue emission with
CIE1931 coordinates of x=0.159; y=0.197, a maximum efficiency of 0.27 cd/A and a maximum luminance of 2924
cd/m.

bias (V)

3500

0.50

10000

0.00
400 450 500 550 600 650

0.25

wavelength (nm)

5000

2500

15000

3000
luminance (cd/m )

0.75

-2

current density (A m )

20000

norm. EL

1.00

2000
1500
1000
500

0
0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9
bias (V)

Figure 4. Current-Voltage characteristics and electroluminescence spectra of the single layer devices: Current density (line with
squares) and luminance (line with circles) as a function of the applied bias voltage in an ITO/PEDOT:PSS/TFB/Ca/Al device (top
left), an ITO/PEDOT:PSS/PEGPF/Ca/Al device (top right) and an ITO/PEDOT:PSS/PPyrTPA/Ca/Al device (bottom). The insets
show the electroluminescence emission spectra of the same devices at a current density of 1000 A/m2 and at a bias around 6.8 V,
4 V and 5.7 V, respectively. Figure modified from [27], with permission from John Wiley and Sons.

In a next step, TFB was implemented on the anode side: the ITO/PEDOT:PSS/TFB/PPyrTPA/Ca/Al PLED showed blue
emission (CIE1931 coordinates x = 0.157; y = 0.174) and an improvement in maximum luminance to 7817 cd/m as well
as of the efficiency to 0.43 cd/A (Figure 5a). Since the EL spectrum of this double layer structure did not exhibit any
significant shifts compared to the PPyrTPA single layer device, it can be concluded that the charge carrier recombination
zone is mostly located in the PPyrTPA layer. For comparison, a device without TFB, but with the PPyrTPA/PEGPF

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heterostructure was fabricated (Figure 5b). Also for the ITO/PEDOT:PSS/PPyrTPA/PEGPF/Ca/Al device, no distinct
shift in the emission spectrum (CIE1931 coordinates x=0.153, y=0.188) as compared to the PPyrTPA single layer device
was found. Also this structure showed an enhancement in luminance and efficiency to 4269 cd/m2 and 0.34 cd/A.
By introducing both transport layers - TFB on the anodes side and PEGPF on the cathodes side - the efficiency and the
maximum luminance was further enhanced significantly. For the efficiency a value of 1.42 cd/A was obtained leading to
a 5.3 fold magnification as compared to the single layer device. This final triple layer structure showed a maximum
luminance of 16 540 cd/m with CIE1931 coordinates of x=0.163; y=0.216. Also for the triple layer assembly the
emission spectrum is almost equal to the PPyrTPA single layer device, demonstrating that the emission zone is pinned to
the PPyrTPA layer and TFB and PEGPF act as HTL/ETL solely (Figure 5c).
This strong increase can be firstly explained by the hole/electron mobilities of the HTL/ETL and secondly by the
favourable type-II band level alignment at the TFB/PPyrTPA interface and the PPyrTPA/PEGPF interface.27 Therefore,
TFB introduces an additional energy step on the anodes side for the injection of holes, whereas electron extraction is
constrained at this interface. On the cathodes side, PEGPF acts vice versa by introducing an additional step for electrons
and an additional extraction barrier for holes.

wavelength (nm)

4000

0
0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9

0.50

10000

0.00
400 450 500 550 600 650

0.25

wavelength (nm)

5000

8000
4000

0
0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9

bias (V)

bias (V)

16000

0.50

10000

0.00
400 450 500 550 600 650

0.25

wavelength (nm)

5000

12000
2

15000

luminance (cd/m )

-2

0.75

norm. EL

1.00

20000
current density (A m )

12000
2

15000

luminance (cd/m )

-2

8000

5000

0.75

norm. EL

0.00
400 450 500 550 600 650

12000

16000

1.00

20000
current density (A m )

10000

0.25

0.50

luminance (cd/m )

15000

norm. EL

0.75

-2

current density (A m )

16000

1.00

20000

8000
4000

0
0
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9
bias (V)

Figure 5. Current-Voltage characteristics and electroluminescence spectrum of the multilayer layer devices: Current density (line
with squares) and luminance (line with circles) as a function of the applied bias voltage in an
ITO/PEDOT:PSS/PPyrTPA/PEGPF/Ca/Al device (top left), an ITO/PEDOT:PSS/TFB/PPyrTPA/Ca/Al device (top right) and an
ITO/PEDOT:PSS/TFB/PPyrTPA/PEGPF/Ca/Al device (bottom). The insets show the electroluminescence emission spectra of the
same devices at a current density of 1000 A/m2 and at a bias around 4.9 V, 5.2 V and 5.1 V, respectively. Figure modified from
[27], with permission from John Wiley and Sons.

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3. EFFICENT DEEP BLUE MULTILAYER PLEDS UTILIZING

POLY(INDENOFLUORENE) COPOLYMERS
The second presented group of blue light emitting materials are poly(indenofluorene) based co-polymers. Similar to the
previous chapter, the PLED builds up as a multilayer device consisting of a hole transporting co-polymer comprising a
indenofluorene and a triphenylamine building block and an emissive co-polymer comprising an indenofluorene unit, a
phenanthrene unit, diphenyl(4-styrylphenyl)amine emissive unit and transporting units based on diphenylamino-benzene
(further denoted as CP-AE and CP-ABCD). The chemical structure and details on the synthesis can be found in [29]. The
building blocks of CP-ABCD are designed specifically for blue light emission, effective charge carrier injection and
transport as well as exciton generation.
3.1 Characterization of multilayer devices

1.0

1.0

0.8

0.8

0.6

0.6

0.4

0.4

0.2

0.2

0.0
300

350

400 450 500

wavelength (nm)

550

norm. photoluminescence

norm. absorbance

The fabrication of the multilayer stack is based on a thermal insolubilization step of CP-AE. CP-AE was spin coated onto
a layer of PEDOT:PSS and was subsequently baked at 200C in argon atmosphere. From previous works30, its known
that such a harsh procedure can result in the formation of ketonic defects on the indenofluorene units which may also
modify the transport properties of the polymer. Therefore photoluminescence and absorbance spectra of CP-AE were
taken before and after the bake out. As it is evident from Figure 6, the thermal annealing did not alter of the optical
properties. Furthermore, the following spin-rinsing step did not lead to any reduction of the film thickness (confirmed by
AFM layer thickness measurements).

0.0
600

Figure 6. Absorbance (squares) and photoluminescence (circles) spectra of a thin film of CP-AE on a glass substrate. Spectra were
recorded before (closed symbols) and after (open symbols) the 200C bake-out procedure in argon atmosphere. No changes in the
emission characteristics were observed. Figure taken from [29], with permission from John Wiley and Sons.

After confirming the stability of CP-AE, CP-ABCD was deposited from toluene solution, followed by a thermally
evaporated cathode stack comprising 0.15 nm cesium carbonate (Cs2CO3) and 100 nm aluminum. The resulting
ITO/PEDOT:PSS/CP-AE/CP-ABCD/Cs2CO3/Al multilayer PLED (Figure 7) showed deep blue electroluminescence
emission (CIE color space coordinates: x = 0.144, y = 0.129), a high maximum luminance of 10600 cd/m and very high
device efficiency of 9.7 cd/A. This value is, up to the knowledge of the authors, among the highest ever reported
efficiencies for blue PLEDs.

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15000
1.00
0.50

3000

0.25

12000
-2

0.75

9000

2000 400 450 500 550 600 0.00

6000

1000

3000

wavelength (nm)

0
0

4
5
bias (V)

luminance (cd m )

4000

norm. EL

-2

current density (A m )

5000

Figure 7. Current-Voltage characteristics and electroluminescence spectrum of the ITO/PEDOT:PSS/CP-AE/CP-ABCD/Cs2CO3/Al

multilayer layer device: Current density (line with squares) and luminance (line with circles) as a function of the applied bias
voltage The insets show the electroluminescence emission spectra with the CIE color space coordinates: x = 0.144, y = 0.129.
Figure modified from [29], with permission from John Wiley and Sons

In addition to the innovative material concept, these performance parameters are a result of the beneficial type-II energy
band alignment at the CP-AE/CP-ABCD hetero-junction. Valence-band-region spectra and the secondary electron cutoff were measured with ultraviolet photoemission spectroscopy (UPS) for each layer in the device stack. As depicted in
Figure 8, the photoemission onset of CP-AE was found to be 0.6 eV below the Fermi level (EF) and 0.9 eV below EF for
CP-ABCD. The workfunction, as determined by the secondary electron cut-off, was 4.9 eV for both materials.
Consequently, the ionization energy was 5.5 eV for CP-AE and 5.8 eV for CP-ABCD. From the optical bandgaps, the
onset of the lowest unoccupied molecular orbital (LUMO) was calculated; for CP-AE the LUMO is 2.6 eV below
vacuum level, for CP-ABCD the LUMO can be calculated at 2.8 eV below the vacuum level. Figure 8b shows a sketch
of the energy level diagram as determined by the described measurement. The additional energy step introduced by CPAE, allows for a stepwise and thus more efficient hole injection into CP-ABCD. The step between the LUMO levels
blocks the electrons at this interface, additionally increasing efficiency.

PEDOT:PSS

norm. intensity (a.u.)

CP-ABCD
= 4.9 eV

0.9 eV

5.0 eV

CP-AE

CP-ABCD

2.6 eV

2.8 eV

vacuum level

LUMO
CP-AE
= 4.9 eV

0.6 eV

5.5 eV

EF

5.8 eV

PEDOT:PSS

= 5.0 eV

4
5
4
kinitec energy (eV)

b
3
2
1
binding energy (eV)

HOMO

0 = EF

Figure 8. Energy band alignment along the multilayer stack. a) Secondary electron cut-off and valence-band-region spectra for each
layer in the device stack; b) sketch of the energy levels in the PEDOT:PSS/CP-AE/CP-ABCD device stack.
Figure modified from [29], with permission from John Wiley and Sons.

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3.2 Color-stability
It is known that the cathode interface with the organic material is distinctively prone to degradation resulting in
discoloration, mostly due to the very reactive nature of usually used low workfunction cathode materials.31 Recently, it
was shown that direct contact of the light emitting polymer with PEDOT:PSS can also lead to undesired discolorations.29
Figure 9 demonstrates this effect on the basis of an ITO/PEDOT:PSS/CP-ABCD/Ca/Al single layer structure and an
ITO/PEDOT:PSS/CP-AE/CP-ABCD/Ca/Al multilayer device. While for the single layer a strong discoloration was
found for higher bias voltage levels, spectra obtained from the multilayer device were mostly stable. The spectral shifts
observed in the single layer device were found to be fully reversible, being a proof that the changes are not due to
general device degradation, but due to a shift of the charge carrier recombination zone towards the PEDOT:PSS/CPABCD interface. The shift of the emission zone is also responsible for the slight colour changes in the multilayer device
at high bias. While in the single layer device the emission zone is shifted towards the interface with PEDOT:PSS, here
the emission zone is shifted partly into the CP-AE layer, resulting in a slight broadening of the electroluminescence
spectrum.
Therefore, not only efficiency enhancement is a beneficial point of multilayer PLEDs, but also the prevention of the
direct contact of the light emitting polymer with the cathode and PEDOT:PSS. The related interface degradation effects
can be eliminated or at least minimized by introducing suitable interlayers, which shift the emission zone away from the
interface with PEDOT:PSS or the cathode.
1.2
norm. electroluminescence

norm. electroluminescence

1.2
1.0
0.8
0.6
0.4
0.2
0.0
400

450

500

550

600

1.0
0.8
0.6
0.4
0.2
0.0
400

wavelength (nm)

450

500

550

600

wavelength (nm)

Figure 9. Electroluminescence emission spectra from an ITO/PEDOT:PSS/CP-ABCD/Ca/Al single layer PLED (left) and from an
ITO/PEDOT:PSS/CP-AE/CP-ABCD/Ca/Al multilayer PLED (right) recorded at different driving voltage (4 V, full squares; 6 V
full circles; 8 V, full triangles; 10 V, full stars; 12 V open squares; 14 V open circles). For the single layer device, a distinct peak
develops at around 425 nm, assigned to chemically degraded CP-ABCD. This behavior is not observed for the multilayer device.
The slight color shift can here be assigned to the movement of the charge carrier recombination zone into the CP-AE layer. Figure
taken from [29], with permission from John Wiley and Sons

4. SUMMARY AND CONCLUSIONS

To summarize, we were able to demonstrate the fabrication of highly efficient blue emitting multilayer structures from
solution. In the first presented approach, TFB was used as hole transport layer. Since parts of the TFB-layer can be
stabilized by a thermal 'hard-bake' procedure, the light emitting polymer, PPyrTPA could be deposited on top without
dissolving the underlying TFB. Subsequently, the polar soluble poly(fluorene)-derivate PEGPF was deposited from
methanol solution. The orthogonal polarity of this solvent to PPyrTPA ensures that the underlying PPyrTPA layer is not
harmed by the deposition process. AFM measurements confirm that the individual layers are stable upon treatment with
the solvent of the following. Full coverage of the individual layers can be concluded from vanishing core level features

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in the XPS spectra. The resulting solution processed triple layer structure showed bright blue emission (CIE1931
coordinates x=0.163; y=0.216), a high maximum luminance of 16500 cd/m and a high efficiency of 1.42 cd/A.
In a second approach, poly(indenofluorne) based materials were used as hole transporting and emissive material. The
novel hole transporting co-polymer CP-AE can be stabilized in a thermal bake-out step. Photoluminescence and
absorbance spectra confirm that this bake out procedure does not alter the photophysical properties of the material. CPABCD was deposited afterwards using the very same solvent. The resulting ITO/PEDOT:PSS/CP-AE/CPABCD/Cs2CO3/Al PLED showed deep blue emission (CIE color space coordinates: x = 0.144, y = 0.129) and a
remarkably high efficiency of 9.7 cd/A. Additionally, it was demonstrated that PEDOT:PSS can lead to a degradation of
the the light emitting polymer at the interface due to its acidity. This effect can be prevented effectively by implementing
an acid-stable interlayer (like CP-AE).

ACKNOWLEDGEMENTS
S. N. and S. S. gratefully acknowledge financial support by the Styrian government (Project POLYLED, GZ:A3-22.B9/2009-9). R. T. gratefully acknowledges financial support by the Christian Doppler Research Association, the Austrian
Federal Ministry of Economy, Family and Youth (BMWFJ), and ISOVOLTAIC AG. Work in Berlin was supported by
the DFG (SFB951) and the EC (HYMEC, GENIUS)

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