Proceedings of the Seventeenth

Sixteenth (2007)
(2007)
International
International
Offshore
Offshore
andand
Polar
Polar
Engineering
Engineering
Conference
Conference
Lisbon, Portugal, July 1-6, 2007
Copyright © 2007 by The International Society of Offshore and Polar Engineers(ISOPE)
ISBN 978-1-880653-68-5; ISBN 1-880653-68-0(Set); ISSN 1098-6189 (Set)

Nanotechnology in Flexible Electronic Devices: Principles - Processes and Applications

S. Logothetidis
Lab for Thin Films - Nanosystems & Nanometrology (LTFN)
Physics Department, Aristotle University of Thessaloniki
Thessaloniki, Greece

ABSTRACT deposition and printing of organic light-emitting polymers and active

Nanotechnology is rapidly exploding worldwide and it will revolution-
ize all aspects of our everyday life, since it will lead to fundamental
breakthroughs in the way materials, devices and systems are under-
stood, designed and manufactured. In this work, the advances and pros-
pects of Nanotechnology in the fields of novel active and functional
thin films and nano-materials to be used for the production of flexible
electronic devices, such as flexible Organic Light Emitting Diodes –
OLEDs, and Organic Photovoltaics –OPVs, will be described.
KEY WORDS: Flexible Electronic Devices; OLED; OPV; polymer;
nanotechnology; roll-to-roll; large scale.
INTRODUCTION
Flexible Electronic Devices (FEDs) will have a major impact on our
daily life and they will revolutionize the visualization of information,
communications, information technology, energy generation through
renewable resources, building lighting, among others. Among the
envisaged applications, the most promising are the flexible displays
(Flexible Organic Light Emitting Diodes – FOLEDs) and lighting
modules, flexible Organic PhotoVoltaic cells (OPVs), data systems and
media, etc. During the past four decades, inorganic Si and GaAs
semiconductors, SiO2 insulators, and metals such as Cu and Al were the
backbone of the semiconductor industry. Nowadays, the replacement of
rigid Si substrates by flexible polymeric substrates represents one of the
key challenges for the production of novel display, lighting and energy
generation systems.
The innovations associated with the development of FEDs are the use
of novel materials, (conductive polymers, printable metals, organic
semiconductors, etc.), the replacement of rigid substrates, such as glass,
with flexible polymeric substrates (Polyethylene Terephthalate,
Polyethylene Naphthalate, etc.) and the integration of these into large-
scale roll-to-roll (r2r) production processes (Yanaka, 2001; Laskarakis,
2006; Haas, 1999). In this way, the use of FEDs will offer substantial
rewards such as lightweight, thin, robust, conformable, and the ability
to be rolled when not in use. In addition, plastic-based substrates,
coupled with new and intelligent production techniques for the
matrix thin-film transistor arrays, open up the possibility of cost-
effective, r2r processing in high volumes. Thus, they will provide
unique technologies and generate new applications to address the
growing needs in numerous scientific, technological and industrial
areas and in everyday life (Logothetidis, 2006).
The performance, efficiency and lifetime of FEDs are greatly affected
by the optical, electrical, and structural properties of the polymer
substrates and the subsequent active and functional organic and
inorganic films. Therefore, these should meet specific and advanced
requirements, such as high optical transparency, ultra low atmospheric
gas permeability, electrical conductivity, structural stability, film-
substrate adhesion etc (Logothetidis, 2006). These properties are
determined and controlled by the bonding structure of the materials,
and on the surface and interface nanostructure and chemistry. The
detailed knowledge of the bonding structure, mechanical response and
surface nano-topography of the polymer substrates and of the
functional nano-layers are of significant importance and affect all the
production steps.
In this work, we will discuss and summarize on the latest advances in
the production processes and materials such as flexible polymeric
substrates, protection layers (high barrier inorganic and hybrid organic-
inorganic materials), electrodes and conductive organic materials.
FLEXIBLE ELECTRONIC DEVICES
Figure 1 shows the structure of a typical FOLED that is consisted of the
flexible polymeric substrate, the barrier layer, the electrode layers
including the transparent conductive oxide and the conductive organic
layers for the charge generation and transport through the device layers.
One crucial factor that affects the operation and lifetime of the device is
the protection against harsh environmental conditions. The permeation
of the atmospheric O2 (OTR) and H2O molecules (WVTR) into the
FED structure induces degradation and corrosion to the electrode and
active layers. This permeation is controlled by the defects of the
polymeric substrate and the barrier nano-layers induced by intrinsic
surface roughness, the surface and structure inhomogeneities and by
cracks of the inorganic nano-layers created by bending and/or tension
of the flexible polymeric substrates (Laskarakis, 2006; Schwab, 2006).

Paper No. 2007-Nano-49 Logothetidis 2807 Total number of pages 7

The commercially supplied polymer films that are used as flexible
substrates for FEDs production, exhibit the highest permeability values
[10-1 – 102 cm3/m2dbar (OTR) and g/m2d (WVTR)], and are just
sufficient for food packaging applications. The deposition of one single
inorganic layer, such as SiOx of a thickness ~40 nm, increases their
barrier response by more than 30 times. Experimental combinations of
different functional or organic-inorganic layers in combination with
inorganic layers allow for an improvement of a factor of 1000
(Flexonics Project, 2007).
Encapsulation film Thin Film, polymeric film, etc.
Transparent Barrier layers Inorganic, oxides, etc.
Cathode layer Ca, Ba, etc.
Organic layer stack Conductive organics, e.g. P3HT
Anode layer (e.g. ITO) Transparent Conductive Oxides
Transparent Barrier layers Inorganic, oxides, etc.
Polymer Substrate e.g. PET, PEN
Fig. 1. Representative structure of a Flexible OLED device (flexible
display or flexible lighting system).
However, the requirements in O2 (OTR) and H2O (WVTR)
transmission for FEDs ask for values lower by another 2-3 orders of
magnitude in the range of 10-6 cm3/m2dbar (OTR) and g/m2d (WVTR),
respectively, which cannot be obtained by any of the current r2r
processes. (Schwab, 2006). The solution to this problem is the
development of ultra-barrier materials consisted by alternating nano-
layers of inorganic and hybrid organic/inorganic materials (Schwab,
2006). In this way, the significant increase of the diffusion path results
to the reduction of the atmospheric gases permeability (Schwab, 2006).
a. Flexible Polymeric Substrates
In order to replace glass in the production of FEDs, a polymer substrate
should have enhanced structural, optical, mechanical and chemical
properties, such as i.e. controllable optical transparency, dimensional,
mechanical and thermal stability, chemical resistance, low coefficient of
thermal expansion, smooth surface and finally, enhanced resistance to gas
and water vapor penetration. Most of the above properties are controlled
by the bonding structure as it is affected by the synthesis processes.
The flexible polymeric substrates that have been used the most in organic
electronics are the polyesters, polyethylene terephthalate (PET) and
polyethylene naphthalate (PEN). Polyimide, and polycarbonate have also
been used, whereas paper is also of great interest for printing electronics.
Paper has been used for printing antennas, and as a support for sensors
and various types of displays. However, compared with polymeric films,
the surface of paper is very rough, which limits some of its use in organic
electronics. Also, its temperature capability is limited, and it is not
generally compatible with solution processing.
PET and PEN are excellent candidates to be used as flexible substrates
for the r2r production of FEDs. The unit cell of PET, which is triclinic
with a density of 1.455 gr/cm3, is consisted by an aromatic ring and an
ester function, that form the terephthalate group, and by a short
aliphatic chain that constitutes the ethylene segment, whereas the unit
cell of PEN includes a second phenyl ring, forming the naphthalene
group. It can be crystallized into two polymorphs, α and β in both
which the ethylene glycol unit has a trans conformation, whereas the
ester group can adopt the trans (α-polymorphism, ρ=1.407 gr/cm3) or
the trans and cis (β- polymorphism, ρ=1.439 gr/cm3) arrangements
(Kimura, 1997).
Spectroscopic Ellipsometry (SE) in a wide spectral region from the IR
2808
to the Vis-fUV has been implemented in order to investigate the optical
and electronic properties of the PET and PEN films. SE is based on the
determination of the ratio between the parallel and perpendicular
complex reflection coefficients, through which the complex dielectric
function ε(ω)=ε1(ω) + iε2(ω) is determined. The optical response
functions of PET and PEN films in the Vis-fUV spectral region (1.5-6.5
eV) measured with the plane of incidence parallel to the MD, are
shown in Fig. 2. The optical absorption of PET and PEN starts at ~4
and ~3 eV, respectively. The dielectric function ε(ω) of PET at energies
above 4 eV, is dominated by four characteristic features at ~4.15 (peak
I) and 4.3 eV (peak II), whereas two stronger bands are centered at ~
5.0 (peak III) and 6.3 eV (peak IV). The ε(ω) of PEN shows similar
features due to the similarities in the molecular structure between the
monomer units of PET and PEN. However, the existence of two phenyl
rings in the naphthalene group in PEN, instead of the benzene ring in
PET, leads to the significant shift of the characteristic absorption bands
to lower energies as well as a characteristic split in all of them.
Therefore, we observe an energy shift of peaks I and II to 3.4 and 3.6
eV respectively, although this energy shift is much more pronounced in
peaks III and IV, which are appeared at 4.4 and 5.1 eV, respectively,
along with a characteristic split in three components (Laskarakis,
2006).
7 5
(a) PET film IV
6
III
4
5 3
ε1(ω)
ε2(ω)
4 2
3 1
2 0
I II
1 <ε1(ω)> -1
<ε2(ω)>
0
(b) PEN film IVa
-2
8 IVb 7
7 <ε1(ω)> 6
6 <ε2(ω)> 5
IVc
5 4
ε1(ω)
ε2(ω)
4 IIIc 3
I
II
3 2
2 1
IIIb
1 0
IIIa
0 -1
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
Photon Energy (eV)
Fig. 2. Dielectric function of PET (a) and PEN (b) films as measured in
the Vis-fUV spectral region.
As it has been discussed by Laskarakis (2006), the peaks I and II have
been attributed to the electronic transition of the non-bonded electron of
the carbonyl O atom from the n state to the π* unoccupied valence state
orbital (n→π* transition). The peak III of PET (PEN), which is
possibly attributed to the spin-allowed, orbitally-forbidden 1A1g→1B1u
transition, is composed by two (three) sub-peaks of parallel polarization
dependence. The higher broadening can be attributed to the break of the
symmetry of the phenyl (naphthalene) rings due to the substitution of
carbon atoms. Finally, peak IV in both PET and PEN has been found to
be composed by two sub-peaks with different polarization at 6.33 and
6.44 eV for PET (4.8 and 5.5 eV for PEN) after molecular orbital
calculation based on π electron approximation, and it can be attributed
to the 1A1g→1B1u electronic transition of the paradistributed benzene
(naphthanene) rings with polarization rules on the plane of the rings.
The optical response of PET and PEN films in the IR spectral region
are shown in Fig. 3. The strong absorption bands, at 900-1800 cm-1,
indicate the contribution of the vibrational modes corresponding to the
IR-active chemical bonds of PET and PEN. Above 1800 cm-1, both
films are optically transparent and their Fourier Transform IR As it has been described above, the use of flexible polymeric substrates
Spectroscopic Ellipsometry (FTIRSE) spectra are dominated by Fabry– will revolutionize the production of organic electronic devices, and it will
Perot oscillations due to the multiple reflections of light at the film provide added-value since new applications will be generated. However,
interfaces. Among the more intense characteristic vibration bands in the flexible polymeric substrates (in the form of films with thickness of some
FTIRSE spectra of PET, we observe the vibration modes at ~940 and µm and lengths of some km) produced by large scale roll-to-roll (r2r)
~971 cm-1 (trans) that could be attributed to the C-O stretching mode, processes are characterized by relatively high permeability values for
the aromatic CH2 stretching mode at ~1125 cm-1, the ester mode at various substances, such as gases or water vapor. This is a major
~1255 cm-1, the in-plane deformation of the C-H bond of the para- problem, since the permeation of atmospheric O2 (OTR) and water vapor
substituted benzene rings at ~1025 and ~1410 cm-1 and furthermore, the (WVTR) through the polymeric substrate into the active layers of the
characteristic vibration band at 1720 cm-1 corresponding to the device leads to corrosion and degradation effects, significantly limiting
stretching vibration of the carbonyl C=O groups. The band at 1342 cm-1 their operation time and stability.
is attributed to the wagging mode of the ethylene glycol CH2 groups of In order to achieve the necessary improvements in barrier properties of
the trans conformations. Also, we observe at 1470 cm-1 and 1505 cm-1 the polymeric substrates, additional barrier layers have to be used. As it
the characteristic peaks corresponding to the CH2 bending mode, and can be seen in Fig. 4, the barrier layers available on the market are
C-H in plane deformation. sufficient for packaging of technical parts and food or pharmaceutical
Due to the existence of naphthalene ring structure in the monomer unit products (OTR and WVTR: 100-10-1 cm3/m2dbar and g/m2d,
of PEN instead of a benzene ring structure, in PET, the PEN shows a respectively). However, in the case of flexible organic electronic devices,
similar IR response, however, with some additional vibration bands. the values of OTR and WVTR have to be improved to 10-6 cm3/m2dbar
These include the bands at 1098 cm-1 that has been attributed to the and g/m2d, respectively, and furthermore the barrier layers have to be
stretching and bending modes of ethylene glycol attached to the characterized by additional functionalities, such as high transparency and
aromatic structures of the PEN monomer units. Moreover, the dimensional stability.
characteristic band at 1184 cm-1 corresponds to the C-C stretching
modes of the naphthalene group. The complex bands at 1335 and 1374 (a)
cm-1 reveal the bending mode of the ethylene glycol CH2 group in the Product Pyramid
OTR WVTR
(cm3/m2/dbar) (g/m2/d)
gauche and trans conformations, respectively. The C=C stretching
modes of the aromatic (naphthalene) ring structures of PEN can be Flexible OLEDs 10-6 10-6
observed at ~1635 cm-1. Moreover, the stretching vibration of the Organic Solar Cells
carbonyl C=O group appears in lower energy in case of PEN (1713 cm-
1
) than in PET (1720 cm-1). This could be the result of the increased Flexible LCDs
10-2 10-2
conjugation due to the existence of naphthalene (PEN) instead of
Solar Cell Encapsulation
benzene (PET) rings structures, which shifts the maximum absorbance 10-1 10-1
to lower wavenumbers. State-of-the-art
Packaging of Technical Parts 100 100

8 1255 cm
-1
1720 cm
-1 Fig. 4: Barrier layer technology. Products on top have the highest
6 (a) PET
ester mode C=O str. mode requirements.
4
A new class of barrier materials consists by inorganic-organic nano-
ε2(ω)

2 composites, which have shown to provide very good barrier properties.

0 These inorganic-organic hybrid polymers (ORMOCER®s, trademark of
-2 -1
the Fraunhofer-Gesellschaft zur Forderung der angewandten Forschung
1125 cm
-4 CH2 str. mode e.V., Germany) combine the properties of organic polymers with the
-1
940 cm properties of silicones and glass-like materials. These materials, which
-6 C-O str. mode
are synthesized via the sol-gel process, have strong covalent or ionic-
-8
6 covalent bonds between the inorganic and the organic phases and
-1
(b) PEN 1257 cm
-1
1713 cm
combine key properties such as high transparency, hardness, chemical
5 -1 C=O str. mode
1184 cm ester mode

4
C-C str. mode and thermal stability, low processing temperatures and flexibility.
-1
1135 cm
CH2 str. mode
In order to achieve the desired OTR and WVTR values for the flexible
3 organic electronics applications, the use of multilayered structures
ε2(ω)

2 consisting of inorganic (such as SiOx and AlOx) and hybrid

(inorganic/organic) nano-layers deposited onto the flexible polymeric
1
substrates, has been realized. This provides a tortuous path that increases
0 the length for permeation and reduces the molecule diffusion inside the
-1 flexible organic electronic device. The latest advances in the production
of these ultra high barrier layers include the achievement of OTR and
900 1000 1100 1200 1300 1400 1500 1600 1700 1800
-1 WVTR values in the range of 10-3 with the use of two inorganic-hybrid
Wavenumber (cm )
bilayers. (Flexonics Project, 2007)
Fig. 3. Imaginary part ε2(ω) of the dielectric function of the PET and
PEN films as measured by FTIRSE, where the main vibration bands are
c. Transparent Conductive Oxides
shown (Laskarakis, 2006).
The electrode layers represent an important part of the FED structure.
Transparent electrodes consisted by conducting oxides (TCO) have
attracted a considerable amount of interest and they have been
b. High Barrier nano-layers extensively investigated since they constitute a major stage of the

2809
production of electronic devices both on rigid and flexible substrates. The
use of flexible polymeric substrates for the production of FEDs, which
have poor thermal endurance, imports more strict requirements
concerning the deposition parameters of the TCO thin films that should
be deposited at low temperatures (Logothetidis, 2005, Laskarakis, 2006)
Zinc oxide (ZnO), which is a wide direct band-gap semiconductor with a
appeared at ~6.5 eV. Large differences are found between the ε(ω) of the
initial and final stages of growth. At the initial stages of growth small
islands and nano-crystals are presented with a lot of deficiencies are
presented, not permitting the excitons to move and reduces the optical
response.
3,5

hexagonal crystal structure of wurtzite, is a most promising material for ZnO bulk ε2(ω) at start of deposition
3,0 ZnO bulk ε2(ω) at end of deposition
the production of the new generation of FEDs, and it has gained great
commercial and scientific interest compared with the other TCO films, 2,5
such as indium tin oxide (ITO) (Androulakis, 2005; Hosono, 2002).
Some of its numerous advantages include the electrical conductivity 2,0

ε2(ω)
modified by appropriately doped or post-annealing, its good ultraviolet
1,5
absorption behaviour, the compatibility with large scale processes, the
low cost, abundance, non-toxicity and easy fabrication (Fortunato, 2005; 1,0
Suchea, 2005).
In-situ and real-time SE gives the opportunity of monitoring the growing 0,5

thin films and extracting information about the evolution of their optical
0,0
parameters and growth mechanisms. Fig. 5 shows the imaginary parts of 2 3 4 5 6 7 8
the measured pseudo-dielectric functions (Logothetidis, 2006) of a Photon Energy (eV)
growing ZnO thin film on PEN substrate, using the real-time facility. The Fig. 6. The evolution of the imaginary part of the bulk dielectric
gradual change of the spectra’s feature during the deposition indicates the function ε2(ω) of the growing ZnO thin film on a PEN substrate, for
growth of the ZnO thin film. every 1 minute of deposition time, calculated by the TL dispersion
9
PEN - Start of deposition
model.
8 Real-time spectra during ZnO deposition
ZnO/PEN - End of deposition
7
Finally, Fig. 7 shows the time-dependence of the thickness of the growing
ZnO thin film (Koidis, 2007).
6
PEN
5 90
<ε2(ω)>

4
80

3
70
ZnO layer
2
ZnO layer Thickness (nm) 60
PEN substrate
ZnO/PEN
1
50

0
3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 40
Photon Energy (eV)
30

Fig. 5. The evolution of the imaginary part [<ε2(ω)>] of the real-time
pseudo-dielectric function of the growing ZnO thin film on a flexible
PEN substrate, given at every 1 minute of deposition (Koidis, 2007).
For the parameterization of the optical properties of ZnO, the Tauc–
Lorentz (TL) dispersion model for amorphous semiconductors was
employed. TL dispersion model uses a combination of the Tauc joint
density of states and the quantum mechanical Lorentz oscillator model
in order to describe the spectral dependence of the dielectric function
(Gioti, 2000; Jellison, 1996). The TL dispersion model is described by
the following relations in which the real part ε1(ω) is determined by the
imaginary part ε2(ω) by the Kramers-Kroning integration (Tauc, 1966):
⎧ Aω0C(ω − ωg ) 1 2
⎪ ω > ωg
ε 2 (ω) = ⎨ (ω 2 − ω02 ) 2 + C 2ω 2 ω (4)
⎪ development of conductive organic active materials has become one of
⎩0 ω ≤ ωg
∞ ξε 2 (ξ )
ε1 (ω) = ε ∞ +
2
π
Ρ ∫ω g ξ 2 - ω2
dξ (5)
The analysis of these spectra using the Tauc-Lorentz model with the two
oscillators allowed the calculation of the bulk complex dielectric function
ε(ω) of the growing film as depicted in Fig. 6, and to the determination of
the complex optical conductivity,. From Fig. 6 it is clear that the ZnO
films have a fundamental gap Eg at ~3.15 eV. The maximum absorption
appears at two distinct energy gaps at E1≈3.4 eV due to the presence of
the absorption exciton, (Thomas, 1959) and at energy E2, which is
20
10
0
0 2 4 6 8 10 12 14 16 18 20
Deposition Time (min)
Fig. 7. The time-dependence of the thickness of the ZnO film during
deposition.
d. Organic conductive active layers
The active materials of FEDs are consisted by organic conductive
layers, for the charge generation and transport that will lead to the light
emission and generation of electricity for organic light-emitting devices
OLEDs and OPVs, respectively. Therefore, during the past decade, the
the fore most topics in chemistry and applied physics. Due to the
variety of organic materials and their physical and chemical properties
such as the fluidity of their precursors and their compatibility with a
range of foils and other substrates, a large number of new and adapted,
fast and direct structuring techniques can be applied.
The usual structure of a FED, as it has been shown in Fig. 1 consists of
an anode such as indium tin oxide (ITO) film, deposited onto a flexible
transparent substrate, and followed by two conducting layers, a hole
injection layer an electron transport layer, which sandwich the emissive
organic layer. The structure is topped with a reflective metal cathode of
Mg-Ag alloy or Li-Al.
Materials which is used as hole injection layer are Copper

2810
Phthalocyanine (CuPc) (Hur, 2004), Poly(3,4-ethylenedioxythiophene)
poly(styrenesulfonate) (PEDOT:PSS) (Pettersson, 1999; Schubert,
2004), Polyaniline (PANI) (Al-Attara, 2003; Bormashenko, 2004)) and
Tetracyanoethylene (TCNE). As hole transport materials used
Polyphenylene vinylene (PPV), Poly(vinyl nitrate) (PVN), N,N8-bis-
(3-methylphenyl)-N,N8-bis-(phenyl)-benzidine (TPD) and
naphthylphenylbiphenyl diamine (NPD). The structure of these
materials shows in the Fig. 8.
Fig. 8. The structure and monomer units of the materials that are used
as hole injection layers in FEDs.
In the case of OLEDs, the color of the emitted light depends upon the
precise composition of the material. Red, green, and blue emissive
materials can be used together to produce the full color spectrum.
Usually green emitters is aluminum tris(8-hydroxyquinoline (Alq3)
(Lian, 2007; Kumar, 2005), 2,9-Dimethyl-4,7-diphenyl-1,10-
phenanthroline (BCP) and Polyphenylene vinylene (PPV)(Bianchi,
2004; Kumar, 2003). As red emitters used poly(2,5,2’,5’-tetrahexyloxy-
7,8’-dicyanodi-p-phenylenevinylene) (CN-PPV) and
(dicyanomethylene)-2-methyl-6-[(4-dimethylaninostyryl)-4-H-pyran]
(DCM) (Xiao, 2007) and as blue emitters poly(9,9-dioctylfluorenyl-2,7-
diyl) (PFO), poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)-
diphenylamine) (TFB) and Polyphenylene vinylene (PPV).
Polyaniline is one of the most promising conductive polymers due to its
high environmental and chemical stability in air and excellent
processibility. It can be deposited by spin-casting process and it is
characterized by high transparency in broad near and middle IR bands
and in the Visible region shows three dominant electronic transitions
located at energies 1.5, 2.9 and 3.6 eV (Hur, 2004; Pettersson 1999).
5,0
<ε1(ω)>
4,5 <ε2(ω)>
4,0
3,5
<ε1(ω)>
3,0
2,5
2,0
2 3 4 5
Photon Energy (eV)
Fig. 9. The measured <ε(ω)> of a thin film of PEDOT-PSS deposited
onto a PEN flexible substrate, in the energy range 1.5-6.5 eV.
PEDOT is a low band gap polymer with promising properties for
applications such as transparent electrode materials or ElectroChromic
devices. It shows a high electrical conductivity (up to 5.50 S/cm) in the
doped state and a good thermal and chemical stability. PEDOT-PSS
thin films are deposited by spin coating and exhibit anisotropy in
optical and electrical properties. Figure 9 shows the measured
pseudodielectric function <ε(ω)> of a PEDOT-PSS thin film grown
onto a flexible PEN substrate by spin-coating technique. The analysis
of the measured <ε(ω)> by the use of two TL oscillators revealed that
the thickness of the PEDOT film is 285 nm, whereas two electronic
transitions have been found at ~5.2 and 6.4 eV.
Another class of conductive organic materials that is used for FEDs is
the PPV, which have been considered as promising candidate materials
for full-color roll-up displays, large-area panels, moving text displays,
and in solar cell applications. The PPV family exhibits two main
advantages as active materials for polymer light-emitting diodes when
compared with other materials. First, they are easily synthesized and
processed as thin films by different techniques: casting, spin-coating,
self-assembly, Langmuir-Blodgett, etc. Second, the PPV derivatives,
obtained by the addition of different chemical groups in the monomeric
units, cover a wide range of emission colors. However, the instability of
electrical and optical properties of PPVs has negative consequences to
the efficiencies and lifetimes of the devices. The absorption spectrum
of PPV exhibit two peaks, centered at 2.25 eV, and 2.7 eV (Bianchi,
2004; Kumar, 2003).
Finally, Alq3 is one of the most widely used materials as the emission
layer (EML) and electron transport layer (ETL) in organic light
emitting devices (OLEDs) due to its good luminescent properties, high
electron mobility, and excellent thermal stability (Lian, 2007). It is easy
to synthesize and can be vacuum evaporated into thin film form and the
absorption spectrum shows a peak near 3.18 eV and another at ~4.7 eV.
The organic materials like Alq3 are usually susceptible to
environmental aging and photooxidation which influences their
viability for commercial utility (Kumar, 2005).
Another major application of the organic electronics is the polymer
based photovoltaic devices. In the last 4-5 years, there has been an
enormous increase in the understanding of the operational principle of
4-
polymer based photovoltaic devices. This has led to a rapid increase in
the power conversion efficiencies of such devices, through the
optimization of the used materials and device architectures (Sariciftci
2004). Some of semi-conducting polymeric donors used of polymer
based photovoltaic cells are, poly-3-hexylthiophene (P3HT), poly[2-
methoxy-5-(3’,7’-dimethyloctyloxyl)]-1,4-phenylene vinylene
(MDMO-PPV), PFDTPT and poly(di-2 thienylthienopyrazine)
(PBEHTT) and some of acceptors which used in many research labs
worldwide are pentacecene, 2,9-Dimethyl-4,7-diphenyl-1,10-
phenanthroline (BCP) Copper Phthalocyanine (CuPc) (Hur, 2004),
poly-(2-methoxy-5-(2’-ethylhexyloxy)-1,4-(1-cyanovinylene)-
3,0
phenylene) (CN-MEH-PPV) and N,N’-dialkyl-perylene-3,4,9,10-
2,5
dicarboximide (PCBM). The structure of these materials is shown in
2,0
Fig. 5.
1,5
<ε2(ω)>
1,0
0,5
0,0
-0,5
-1,0
-1,5
-2,0
6
Fig. 10. The structure and monomer units of the materials that are used
as emission and electron transport layers in flexible electronic devices.
CuPc is a material which exhibits a high thermal and chemical stability
and high optical absorption in the visible range at ~2 and ~3.6eV,
together with optical anisotropy. It is used as acceptor material in OPVs
and deposited by spin coating & vacuum deposition techniques
(Gordan 2004). Finally, the P3HT/PCBM is the best performing
material system for application in bulk heterojunction
polymer/fullerene plastic solar cells. It is deposited by spin casting and
2811
exhibit high degree of crystallinity and high environmental stability and
the best performance of P3HT:PCBM = 1:1 wt. ratio. In the UV
spectral region the electronic transitions have been determined at 2.5
and 3.7 eV (Erb, 2006).
PRODUCTION PROCESSES OF FLEXIBLE ELECTRONIC
DEVICES
The fabrication of organic electronics onto flexible polymeric
substrates by large scale production processes, offers many exciting
new opportunities, and will also reduce several technical limitations
that characterize the production processes of conventional
microelectronics. In conventional Si microelectronics, patterning is
most often done using photolithography, in which the active material is
deposited initially over the entire substrate area, and selected areas of it
are removed by physical or chemical processes. Despite its high-
resolution, the photolithographic process is very complex, expensive,
uses extremely expensive equipment, requires many steps, is time
consuming, subtractive, and only suitable for patterning of small areas.
Moreover, the harsh conditions required for dissolving resists, etching
the underlying layers, and removing the photo-resist destroys the
activity of most organic electronic materials. Furthermore, the
temperatures and harsh reaction conditions required for
photolithography are incompatible with most flexible polymeric
substrates. For the above reasons, the advantages of flexible organic
electronic devices are that they overcome the technical limitations of
the conventional microelectronic fabrication processes.
Organic materials can be made soluble and/or solution processable.
This, in combination to the potentiality in use of flexible polymeric
substrates, which are in the form of web rolls with width of many cm,
and length of some km, enables a variety of deposition techniques, such
as printing or printing-like processes. In these processes, the deposition
of the individual organic and functional (e.g. barrier, electrodes) nano-
layers is realized on the moving web rolls (roll-to-roll techniques) and
they are characterized by high volume and lowest cost.
Flexible
Polymeric
Substrate Transparent Barrier
Printed Organic Electrode
Printed Photoactive layer
Printed Counter Electrode
Encapsulation
Roll-to-Roll
Process
FED Product
Fig. 11. Roll-to-Roll process for the production of a FED product.
During the printing processes, the web rolls are commonly run at
speeds of hundreds of m/min. with webs several meters wide, and are
used to deposit (and cure) many different materials simultaneously. The
essential steps of the r2r manufacturing of FEDs are the nano-layer
deposition, the patterning and the encapsulation of the device. Figure
11 shows a representative r2r process for the production of flexible
organic electronic devices in which all production steps are integrated
into a single production line. These processes are characterized by high
throughput, low cost and friendly environmental profiles.
CONCLUSIONS
The purpose of this work was to describe and discuss the current status
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of the materials and processes for the production of FEDs. This work
has skimmed only the surface of many promising technologies that will
contribute to the field in the future. Although the field of flexible
organic electronic devices has made significant advances in scientific,
technical and process capabilities in the last years, much more work
needs to be done before the field is ready to be scaled up for roll-to-roll
process technology. If this technology will be advanced as it is
expected in the next five years, new substrate materials and cheap,
innovative printing and encapsulation techniques must be combined
with creative product development to result to compelling flexible
electronics applications. The combination of novel consumer products
and the ability to manufacture them using an ultra low cost production
capability such as r2r processing will motivate companies to invest in a
full-scale flexible electronics factory.
ACKNOWLEDGEMENTS
This work was partially supported by the EU STREP Project
FLEXONICS Contract No. NMP3-CT-2005–013883.
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