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Oleds: Organic Light Emitting Diodes
Oleds: Organic Light Emitting Diodes
SEMINAR
OLEDs
Organic Light Emitting Diodes
Contents
1 Introduction 3
6 Conclusion 16
7 References 17
2
1 Introduction
The basic idea of organic LED (OLED) operation is fairly simple and similar to that of inorganic
LED's. Electrons and holes are injected into an "active" region. There, they recombine resulting in
photon emission. Electrons are injected in the conduction band of the appropriate organic material and
holes are injected into the valence band. These carriers then move by diffusion until they meet and
recombine to form excitons. When these excitons decay to their ground state, photon emission occurs.
This is the same process as in fluorescence, but here caused by induced electricity and thus called
electroluminiscence.
In the 1960s the first LEDs on the basis of semi-conducting metals were developed and rapidly
found their way to applications. At the same time, the phenomenon of electroluminescence was also
observed for organic materials (anthracene single crystals).
But it was not until 1987 the research group at Eastman Kodak Research Laboratories reported an
organic electroluminescent diode with some remarkable characteristics [1]. By choosing organic
instead of inorganic semiconductors in a novel device resembling a conventional p-n diode, they
produced intensive electroluminescence while using a low-drive voltage. This efficiency indicated
great potential for display applications, and intense research and development efforts on OLED ensued
in numerous industrial laboratories, particularly in Japan. A little more than a decade later, the first
OLED displays have been commercialized, and the technology is poised to challenge the dominance
of liquid-crystal displays (LCDs) in many applications.
OLEDs do not have to be manufactured in semiconductor factories (like LEDs). Nor are they
limited to relatively small sizes. Organic LEDs can potentially be made with a low-cost printing line,
much like you print a newspaper, so very high resolution of displays which consume little power is
achievable.
OLED devices can be divided into two classes: depending on the type of organic layer [8]:
Small-molecule devices are fabricated using vacuum evaporation techniques, whereas polymer
structures can be applied using spin-casting or even ink-jet printing techniques. Originating at Eastman
Kodak Co. (Rochester, NY), the small-molecule technology has achieved commercialization first.
There has been a big advance recently also on PLEDs first discovered by researchers at Cambridge
University in 1989. OLEDs based on “small molecules” have tris (8-hydroxyquinolinato) aluminum
(Alq3) as the prototype (Figure 1), and only a few derivatives have been proposed so far.
OLEDs based on polymers have poly-paraphenylene-vinylene (PPV) as the prototype (Figure 1),
but over the years a number of derivatives of PPV or other polymers have been proposed and used.
3
2 The physics behind OLEDs
SMOLEDs are constructionally more similar to LEDs than PLEDs are, thus we first take a look at
conductivity properties of polymer materials used in PLEDs. The question arrising is: How polymer
becomes conductive? How can plastic conduct electricity?
Polymers are made of long chain molecules entangled between each other. The polymer chains are
formed by connecting many small molecular units called monomers (Fig. 2)[9].
Most polymers are organic compounds, which means they are composed mostly of carbon chains with
hydrogen, oxygen and nitrogen atoms. These atoms form covalent bonds where the electrons are
localized in the low energy bonding orbitals of the chain molecule. Hence polymers typically do not
conduct electricity and are used in electronic application as insulator.
The prototypical conducting polymer is polyacetylene (PA), (CH)n (Fig. 3). Every bond contains a
localized “sigma” (σ) bond which forms a strong chemical bond. In addition, every double bond also
contains a less strongly localised “pi” (π) bond which is weaker. A π molecular orbital is thus formed
when two carbon atoms form a double bond and the 2pz orbitals have the same symmetry. The
electrons in this π orbital have equal probability of being around each carbon nucleus.
Morover, π-bonding, in which the carbon orbitals are in the sp²pz configuration and in which the
orbitals of successive carbon atoms along the backbone overlap, leads to electron delocalization along
the backbone of the polymer. (Delocalized electrons are electrons that are shared by more than two
atoms). This electronic delocalization provides the “highway” for charge mobility along the backbone
of the polymer chain. [2]
As a result, therefore, the electronic structure in conducting polymers is determined by the chain
symmetry (i.e. the number and kind of atoms within the repeat unit), with the result that such polymers
can exhibit semiconducting or even metallic properties.
Actually because of the Peierls Instability with two carbon atoms in the repeat unit, the π-band is
divided into π- and π* bands (Fig. 4) [10]. What Peierls showed is that due to the coupling between
electronic and elastic properties the polymer develops a structural distortion such as to open a gap in
the electronic excitation spectrum.
4
Figure 4: Bonding and anti-bonding (*) π orbitals
Since each band can hold two electrons per atom (spin up and spin down), the π-band is filled and the
π*-band is empty. The energy difference between the highest occupied state in the π-band and the
lowest unoccupied state in the π*-band is the π-π* energy gap, Eg. The bonding orbital (π) corresponds
to the valence “band” of the semiconductor and the antibonding orbital (π*) corresponds to the
conduction “band”. Each conjugated part of a molecule in a conjugated material is characterized by a
band-like energy distribution in the electronic density of states with an energy gap between the
Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital
(LUMO). This energy band structure is similar to a semiconductor. In this form polymer is a poor
electrical conductor. In a diatomic molecule, a molecular orbital (MO) diagram can be drawn showing
a single HOMO and LUMO, corresponding to a low energy π orbital and a high energy π* orbital.
Every time an atom is added to the molecule, a further MO is added to the MO diagram (Fig. 5).
Thus for a PPV chain which consists of ~1300 atoms involved in conjugation, the LUMOs and
HOMOs will be so numerous as to be effectively continuous. And this results in two bands we
mentioned above. They are separated by a band gap which is typically 0-10eV and depends on the
type of material. PPV has a band gap of 2.5eV.
5
disorder (which tends to localize the wavefunctions) and by the Coulomb interaction, which binds
electrons when transferred to a nearby repeat unit to the positive charge left behind (a hole).
The construction of the remarkably successful SSH Hamiltonian is based on two assumptions [2]:
(a) The π-electronic structure can be treated in the tight-bonding approximation with a transfer integral
t ≈ 2.5 eV, and (b) The chain of carbon atoms is coupled to the local electron density through the
length of the chemical bonds.
t n ,n +1 = t o + α (u n +1 − u n ) (1)
where t n ,n +1 is the bond-length dependent hopping integral from site n to n +1 and u n is the
displacement from equilibrium of the n th carbon atom. The first assumption defines the lowest order
hopping integral, t o , in the tight-binding term that forms the basis of the Hamiltonian (Eqn. 2). The
second assumption provides the first-order correction to the hopping integral. This term couples the
electronic states to the molecular geometry, giving the electron-phonon (el-ph) interaction where α is
the el-ph coupling constant. The precise form of Eqn. (1), in which the dependence of the hopping
integral on the C-C distance is linearized for small deviations about t o , is the first term in a Taylor
expansion.The resulting SSH Hamiltonian is then written as the sum of three terms:
p n2 1
H SSH = ∑ [−t o + α (u n +1 − u n )](c +
n +1,σ c n ,σ + c +
n ,σ c n +1.σ ) + ∑ + K ∑ (u n +1 − u n ) 2 (2)
n ,σ n 2m 2 n
where p n are the nuclear momenta, u n are the displacements from equilibrium, m is the carbon mass,
+
and K is an effective spring constant. The c n ,σ and c n ,σ are the fermion creation and annihilation
operators for site n and spin σ. The last two term are, respectively, a harmonic »spring constant« term
which represents the increase in potential energy that results from displacement from the uniform
bonds lenghts in (CH)x and a kinetic energy term for the nuclear motion.
Figure 6: Electronic structure of semiconducting PA; left - Band structure, right - Density of
states. The energy opens at k = π/2a as a result of Peierls distortion
The spontaneous symmetry breaking due to the Peierls instability implies that for the ground state
of a pristine chain, the total energy is minimized for u n > 0 .Thus to describe the bond alternation in
the ground state, we use:
u n → u n = (−1) n u o (3)
With this mean-field approximation, the value uo which minimizes the energy of the system can be
calculated as a function of the other parameters in the Hamiltonian. Qualitatively, however, one sees
6
that uo and - uo both minimize the energy for trans-polyacetylene since the bonds all make the same
angle with respect to the chain axis. Hence, the energy as a function of u has a double minimum at
± uo , as shown in Fig. 7 [2,12].
Strictly speaking, the SSH model is directly applicable only to polyacetylene; however, recent
work has shown that the primary excitation in luminescent polymers like PPV can also be described
within the linear chain model. In PPV and its derivatives, the lowest excitonic wave function extends
over several repeat units; the properties of excitons are therefore not very sensitive to the delicate
structure within the unit.
However, it is not the iodide or sodium ions that move to create the current, but the electrons from the
conjugated double bonds.
The mechanisms of conductivity in doped polymers are based on the motion of charged defects
within the conjugated framework. In solid state physics these charged excitations are usually described
as positive or negative solitons (ion defects) and polarons (radical ion defects) respectively [13].
The trans-structure of polyacetylene possesses a two-fold degenerate ground state (Fig. 8) and
single and double bonds can be interchanged without changing energy. A break in pattern of bond
alternation separates degenerate ground-state structures.
7
This break leads to a free radical defect, a so-called neutral soliton which is relatively stable
(Figure 9). Addition of an acceptor removes an electron and creates a positive soliton (or a neutral one
if the electron removed is not the free electron). The resulting carbocation is stabilised by having the
charge spread over several monomer units and the charged solitons are responsible for making
polyacetylene a conductor
A further type of charge storage occurs when the generated charge and the radical are coupled to
each other via local resonance of the charge and the radical. This type of charge transport is present in
polymers like PPV. This combination of a charge site and a radical dependent of each other is called a
polaron. A new localised electronic state is created in the band gap, with the lower energy states being
occupied by a single unpaired electron. Unlike the soliton, the polaron cannot move without first
overcoming an energy barrier so movement is by a hopping motion.
FIGURE 10: Radical cation (”polaron”) formed by removal of one electron on the 5th carbon
atom of a undecahexaene chain (a ―> b). The polaron migration shown in c ―> e.
If a second electron is removed from an already oxidised section of the polymer, either a second
independent polaron may be created or, if it is the unpaired electron of the first polaron that is
removed, a bipolaron is formed (with lower energy than 2 polarons) (Figure 11). The two positive
charges of the bipolaron are not independent, but move as a pair, like the Cooper pair in the theory of
superconductivity. While a polaron, being a radical cation, has a spin of 1/2, the spins of the
bipolarons sum to S = 0.
8
Figure 11: Band theory model in polymers. At high doping level, the soliton regions tend to
overlap and create new mid-gap energy bands that may merge with the valence and conduction
bands allowing freedom for extensive electron flow. However, for most heavily doped conjugated
polymers it is conceivable that the upper and the lower bipolaron bands will merge with the
conduction and the valence bands respectively to produce partially filled bands and metallic like
conductivity. Conduction occurs because the mean free path of a charge carrier extends over a
large number of lattice sites. The residence time on each site is small compared with the time it
would take for a carrier to become localized.
The mechanisms of charge transport in polymers are still not fully elucidated. One example is that a
stretched polyacetylene shows a better conductivity than the same material without orientated
morphology and it remains under investigation how inter-chain charge transfer takes place.
c
Eg = h (4)
λ
where h is Planck’s constant and c is the speed of light. PPV produces yellow-green luminescence (Eg
= 2.5 eV).
9
Figure 12: Photoluminiscence and electroluminiscence in conjugated polymers. a) Irradiation can
excite an electron from the LUMO in the HOMO and two new energy states are generated. Both
are filled with an electron of opposite spin (singlet exited state). Relaxation to the ground state
leads to the emission of light of smaller frequency. b) In order to show electroluminescence,
radical ions have to be produced in the polymer by the application of an electric field. When
radical ions of opposite charge combine, so-called excitons (singlet or triplet excited state) are
formed and the decomposition of this neutral excited state (recombination) leads to radiative
emission.
10
When a forward bias is applied, electrons are injected from the cathode into the LUMO of the
polymer and holes are injected from the anode into the HOMO of the polymer. Thus, the electrons
must overcome the barrier (electron injection barrier) between the Ca Fermi level and the LUMO level
of the polymer. Low work function metals such as Mg or Ca are typically used to minimize this barrier
and provide an ohmic contact. A good energy match between cathode and LUMO means that not
much energy is lost when electrons are injected. Similarly, to ensure ohmic injection of holes from the
ITO Fermi level into the HOMO of the polymer, the ITO may be treated in various ways (e.g.,
exposure to an ultraviolet-ozone cleaning) to lower its Fermi level. (barrier is here called hole injection
barrier.)
Figure 15: A basic OLED device structure consists of a hole-transport layer and an electron
transport layer sandwiched by a cathode and anode.
One of the most basic SMOLED device structures uses an organic material called NPB (naphthyl
substituted benzidine derivative) as HTL and Alq3 as ETL. In this typical structure we use indium tin
oxide (ITO) as the transparent anode and magnesium-doped silver (Mg:Ag) as the cathode.
When voltage is applied, charge injection of electrons through the cathode and hole through the
anode occurs. Electrons are transported to the LUMO of the ETL, and holes to the HOMO of the HTL.
Recombination of these charges occurs across the barriers, with holes primarily moving into alq3 (Fig.
16). Excitons formed in Alq3 in this case emit green fluorescence. See Flash movie [16].
11
This two-layer design also is important because it provides the necessary energetic barriers at the
interface to effectively localize the recombination of the oppositely charged carriers at or near the
interface region. As a result, this organic interface region, on the order of 100 to 200 Å thick, is also
primarily responsible for the light generation from the SMOLED device.
Even though highly fluorescent dyes increase EL efficiencies for small-molecule OLEDs, they
only harness a fraction of all electrically generated excitons. Two types of excitons are formed when
electrically injected carriers recombine: singlet excitons with total spin S = 0 and triplet excitons with
total spin S = 1. Since the ground state of organic molecules has S = 0, and the relaxation of a
molecule through the radiative recombination of an exciton must conserve spin, fluorescent emission
from singlet excitons is the only allowed process that generates photons. Hence, for typical
fluorescent-based OLEDs, all triplet excitons are wasted. For small-molecule devices, it is believed
that only 25% of the emissive singlet excitons are formed during electrical excitation. However, some
materials do exhibit light emission from triplet excitons. In these materials, the singlet and triplet
states are mixed and hence the excited triplet states share some singlet character and radiative decay to
the ground state is allowed. This process is known as phosphorescence. Adding a heavy metal atom
such as iridium to an organic molecule increases the spin-orbit coupling that mixes singlet and triplet
excited states allowing for efficient radiative decay of triplet excitons.
The energy level schematic of an OLED employing an iridium-based phosphorescent small
molecule is shown in Figure 18. Here, two ETL layers are used - one (CBP) hosts the phosphorescent
iridium complex and one (BCP) acts solely as a hole (and exciton) blocking layer. Upon injection,
holes are transported in the HTL and recombine with the electrons that have been injected into the hole
blocking layer and have drifted to the CBP ETL. Both singlet and triplet excitons are formed in the
CBP host and then both types of excitons are transferred nonradiatively to the emissive state of the
iridium complex. This state then emits light through phosphorescence. The net effect is that both the
singlet and triplet excitons created in CBP are utilized for light emission. And this clearly
demonstrates the potential of high efficiency OLEDs based on phosphorescence.
12
Figure 18: Schematic energy level diagram of an optimized small molecule OLED employing the
phosphorescent complex: Ir(ppy)3 doped into a CBP host. HTL is a thin film of (α-NPD). A BCP
molecule with a large HOMO-LUMO spacing is used here as both a carrier and exciton blocking
layer. A bilayer cathode consisting of a thin (<10 Å) layer of LiF, followed by a thicker layer of
Al, is used to efficiently inject electrons. The emission between the two dashed lines within the
CBP energy level gap schematically depicts radiative recombination of both singlet and triplet
excitons on the Ir(ppy)3 molecule.
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5 Matrix types of OLEDs, Products
An OLED is a current-driven device. That is, the intensity of the output light is directly
proportional to the electrical current flow through the device. An OLED display, therefore, requires
the control and modulation of electrical current levels through individual elements (pixels) in order to
display text or graphic images.
There are two types of OLED display architectures: passive matrix and active matrix. In a
passive-matrix OLED display, the columns provide the data signal, and the rows are addressed one at
a time. The current flow through a selected row is necessarily pulsed to a level that is proportional to
the total number of rows in the display. This instantaneous current requirement places a restriction on
the size and resolution of the passive matrix design. This restriction is removed in an active-matrix
OLED display, where each individual pixel can be designed to switch on or off within a frame time.
As a result, the device does not suffer the resolution limitations or the high-instantaneous-current
requirements of a passive-matrix design. The size and resolution of these displays are determined by
practical considerations such as the constraints of the substrates rather than the OLED component.
Because the pixel architecture and electrode geometry for the OLED element are already defined on
the substrate, the fabrication of the OLED component is straightforward. The cathode is continuous
over the entire display area, requiring no patterning.
In 1998 Pioneer put on the market first commercially available passive matrix OLED displays in
car radio CD-players (Fig. 20).
Figure 20: 2004 range of Pioneer car radios ; left - Pioneer DEH-P 6600 with blue OLED
display (280$), right - Pioneer DEH-P 8600 with full color OLED display (550 $)
These small molecule based displays were also found in Motorola cellular phones by 2000. Recently
also mobile phones from other manufactorers came on market, with external 256 colors OLEDs as
complement to bigger internal LCDs like in Samsung presented below (Figure 21). In 2003 Kodak
introduced a digital camera incorporating the first commercially available active matrix OLED
display. After Motorola
Figure 21: a) Samsung SGH-E 700 b) Kodak EasyShare LS633 (120.000 SIT)
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Nearby Future
a) Big screens - The technology will provide competitive full-size computer displays and flat-panel
TV screens that consume less power than possible with flat panel technologies available today.
Figure 22: Technical details: The 20-inch prototype is a top-emitting full-color active-matrix
display. It has WXGA resolution (1280 x 768 pixels) and a power consumption of 25 Watt at a
brightness of 300 cd / m² (its desktop display brightness, can exceed 500 cd/m2) [19].
b) FOLEDs - flexible OLEDs [7] are organic light emitting devices built on flexible substrates (Fig.
23). Flat panel displays have traditionally been fabricated on glass substrates because of structural
and/or processing constraints. Flexible materials have significant performance advantages over
traditional glass substrates.
For the first time, FOLEDs may be made on a wide
variety of substrates that range from optically-clear
plastic films to reflective metal foils. These materials
provide the ability to conform, bend or roll a display into
any shape. This means that a FOLED display may be
laminated onto a helmet face shield, a military uniform
shirtsleeve, an aircraft cockpit instrument panel or an
automotive windshield [20].
FOLEDs will also generally be less breakable, more impact resistant and more durable compared to
their glass-based counterpart [7].
c) Lightning applications - The rapid progress in efficiency and performance demonstrated by OLED
technology over the last decade has caused many companies to consider OLEDs as a potential solid-
state light source for lighting applications. In terms of application potential, OLEDs nicely
complement inorganic LEDs - a technology more often associated with solid-state lighting (SSL). In
particular, since inorganic LEDs are bright point sources of light, they are naturally suited for
applications such as spot or task lighting that require spatial control over the illuminating beam. In
contrast, OLEDs represent a diffuse source of light and so are naturally suited to large area general-
lighting and signage applications where, for instance, fluorescent lighting is used today.
15
6 Conclusion
The future prospect looks bright for OLED flat panel displays. OLED displays have been used in
aftermarket car audio for the last several years. They are starting to find use in cell phones as
secondary displays and are expected to enter the market this year in the form of full color displays for
cell phones. Many industry analysts predict OLED displays for laptops and computer monitors will
start to enter the market as soon as 2006. Other applications, such as flexible displays for outdoor
advertising signage and billboards, are further out in time. This application requires over 50 times
performance improvement in OLED materials in brightness and lifetime, and also requires a complex
active matrix drive scheme, inkjet deposition for low cost manufacturing, and flexible substrates.
Therefore, given the requirements and capabilities of billboard application, it may not be realized
within the next five years. Another advanced application for OLED materials includes replacement for
fluorescent room lighting, which again depends upon substantial improvement in the performance of
materials, in particular, energy efficiency. Meanwhile, in the short term, OLED displays have started
and will continue to penetrate the $30 billion dollar display market and have begun to realize their
bright future ahead.
16
7 References
[1] C.W.Tang and S.A. Van Slyke, Organic electroluminiscent diodes; Appl. Phys. Lett. 51, 913
(1987)
[2] Alan J.Heeger, Semiconducting and Metallic Polymers: The fourth generation of polymeric
materials, Nobel Lecture, December 8, 2000
[3] C.W. Tang, S.A. VanSlyke and C.H. Chen, Electroluminiscence of doped organic thin films;
J. Appl. Phys. 65, 3610 (1989)
[4] G.Parthasarathy et al., Organic Light Emiiting Devices; The Electrochem. Soc. Int, Summer 2003
[6] Ioannidis et al., C-V characteristic of OLEDs; Appl. Phys. Lett. 72, 3038 (1998)
[7] Anna. B. Chwang et al., Thin film encapuslated flexible organic electroluminiscent displays;
Appl. Phys. Lett. 83, 413 (2003)
Internet:
[8] http://www.calpoly.edu/~drjones/chem447/Polymers%20CD/Files/LED/pledsoleds.htm
[9] http://classes.engr.arizona.edu/mse110/Lab/CP.pdf
[10] http://www.colby.edu/chemistry/CH145/CH145Lab/MO%20Lab%20-CH1452001.pdf
[11] http://www.ilorentz.org/~saarloos/Correlateds/soundvel.html
[12] http://www.nobel.se/chemistry/laureates/2000/public.html
[13] http://www.chemonaut.de/dateien/CHEM364.pdf
[14] http://www.electrochem.org/publications/interface/summer2003/IF6-03-Pages42-47.pdf
[15] http://oemagazine.com/fromTheMagazine/feb01/brightness.html
[16] http://www.optics.arizona.edu/oled/INTRO.HTM
[17] http://oemagazine.com/fromTheMagazine/jun02/pdf/polymers.pdf
[18] http://www.tu-darmstadt.de/fb/ms/fg/em/OLED.pdf
[19] http://www.idtech.co.jp/en/news/press/20030312.html
[20] http://www.universaldisplay.com/foled.php - FOLED movie
other links:
www.osram-os.com/
http://www.erc.arizona.edu/Education/REU/Student%20Reports%2003/chris%20report.pdf
http://www.research.ibm.com/journal/rd/451/curioni.html
http://www.eurekalert.org/pub_releases/2003-03/giot-nta032103.php
http://www.rochester.edu/college/workshop/presentations/MarkThompson/MT_2003.pdf
http://www.usc.edu/org/techalliance/Anthology2003/Final_Crawford.pdf
http://www.physicstoday.org/pt/vol-54/iss-12/p42.html
http://www-mtl.mit.edu/MEngTP/John_Ho_Proposal.pdf
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