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3 LIGHT-EMITTING DIODES 87
LIGHT-EMITTING DIODES
Introduction
The role of polymers in light-emitting diodes (LEDs) traditionally has been asso-
ciated with the use as a structural material. Epoxy resins are routinely applied
as the transparent packaging material in conventional LEDs in which light is
generated at the junction of two inorganic semiconductors. The polymer provides
the structural integrity of the device and serves as the optical medium that en-
ables the extraction of light (1). During the last decade, however, LEDs have been
developed in which the semiconducting, electroluminescent (EL) material itself
is a polymer. These devices are usually referred to as polymer LEDs or PLEDs
and have attracted signicant attention in both academic and industrial environ-
ment. The principal interest in the use of EL polymers is based on their promise
to combine the ease of processability and mechanical exibility of macromolecular
materials with the exceptional, readily-tailored properties of organic semiconduc-
tors. PLEDs offer the prospective of low production costs, light weight, large area,
fast switching times, low power consumption, high brightness, large viewing an-
gle, and crisp colors. Thus, the new technology may feature distinct advantages
over existing at-panel display devices such as conventional emissive displays, in-
organic LEDs, and liquid crystal displays (LCDs). As a result, the list of potential
applications of PLEDs ranges from small, low information-content displays for
simple electronic devices such as pagers and portable phones to high resolution
video-rate displays for use in desktop monitors and ultrathin television sets. In ad-
dition, PLEDs may be employed as at lighting devices, for example in automotive
rear lights or as backlights in LCDs.
Since the rst demonstration of a PLED in 1990 (2), the eld has progressed
with an almost unbelievable pace, and the technology has matured to the edge
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
88 LIGHT-EMITTING DIODES Vol. 3
The LED reported then materialized the most simple device conguration of
a PLED which, in accordance with the number of organic layers used, is usually
referred to as a single-layer device (Fig. 1). The semiconducting polymer lm
(typical thickness 50500 nm) is sandwiched between two electrodes, of which
at least one has to be (semi)transparent in order to allow the generated light
to escape from the device. Adopting a standard Schottky-conguration, a high
work function anode such as semitransparent indium tin oxide (ITO) and a low
work function cathode such as Al, Mg or Ca are employed, leading to nonlinear
rectication and, thus, rendering the device into a diode. If an external voltage,
or bias, is applied, oppositely charged carriersholes and electronsare injected
above a threshold voltage from the electrodes into the conduction band (CB) and
the valence band (VB), respectively, of the semiconducting polymer (Fig. 2). These
electronic levels correspond to the electron afnity (EA) and ionization potential
(IP) of the polymer. Because of the applied electric eld (typically of the order
Vol. 3 LIGHT-EMITTING DIODES 89
Fig. 1. Schematic drawings of the congurations of a single-layer PLED (top) and a two-
layer PLED (bottom).
EV
EA
CB C
A
IP
Cathode
EG
Anode
VB
gap (EG) of the EL polymer. The triplet excited states, by contrast, decay through
nonradiative processes.
The theoretical internal quantum efciency of a PLED, int , is dened as the
number of photons generated per injected electron:
int = PL r (1)
pow is the optical power output divided by the electrical power input, and is
calculated from ext using the applied voltage U and the average energy E of the
emitted photons. Since the human eye is usually the detector for visible LEDs,
the key performance parameter of an LED is the luminous efciency lum (units:
lm/W) which is a product of ext and the relative eye sensitivity curve S which has
been dened by the Commission Internationale de LEclairage, CIE):
Reference values that are frequently used to evaluate the performance of PLEDs
are the luminous efciencies of conventional inorganic LEDs (0.1520 lm/W) or
unltered incandescent lamps (17 lm/W) (1). Finally, the absolute brightness of an
LED, or luminance (usually quoted in cd/m2 ), and luminance per current density
(cd/A) are also frequently used parameters to describe the performance of LEDs.
Here, the brightness of a laptop computer (200 cd/m2 ) or of a TV cathode ray tube
(500 cd/m2 ) are often employed as benchmarks (19).
As can be deduced from equation (1), the optimizations of charge-injection
and charge-transport (both of which directly inuence the fraction of injected
charge carriers that form excited states, r ) are important aspects for the design
Vol. 3 LIGHT-EMITTING DIODES 91
Materials
of between 4.5 and 5.0 eV (relative to vacuum level), which matches the IP of
frequently used conjugated organic polymers and allows for reasonably efcient
hole-injection. Unfortunately, the electronic characteristics of ITO depend quite
strongly on the manufacturing conditions and cleaning treatments. In addition,
its surface structure can vary substantially, making the use of ITO often rather
cumbersome.
As mentioned before, the two-layer architecture has become the preferred
PLED embodiment (Fig. 1), thus requiring a rst polymer layer with efcient
hole-transport characteristics (6). Poly(vinylcarbazole) (PVK) is an extensively
investigated, commercially available hole-conductor, which has been frequently
used in this context (Fig. 3). Alternatively, polymeric triphenyldiamines have been
employed (23). More recently, poly(aniline) (PANI) and poly(3,4-ethylene dioxy
thiophene) (PEDOT) which are commercially available from Ormecon and Panipol
Ltd. and Bayer AG, respectively, have found widespread application instead (4,10).
Used in their electrically conducting form, these polymers not only allow efcient
hole-injection and hole-transport, but also offer an effective electron transport. As
a result, the electric eld across this layer is dramatically reduced, limiting the
undesired migration of charged species from the anode through the device (see
LEDs (Light Emitting Diodes)).
Light generation is achieved in the actual light-emitting layer which, in a
typical two-layer conguration, usually also acts as an electron-transport ma-
terial; the design considerations for EL polymers are discussed in detail below,
together with an overview of typical material systems.
Finally, a low work function cathode is required for electron-injection. A va-
riety of different cathode materials have been employed, including Ca, Li, Mg, Al,
Cr, or alloys of these metals, sometimes also combined with Ag. Since electron-
injection is often a limiting factor for the device efciency, the metal with the lowest
work function of the above series (Ca, 2.9 eV) is a preferred option. However, while
Ca-based devices may work well in the laboratory, the practical application of this
metal is stied by its sensitivity toward oxidation. Changing the cathode mate-
rial to Mg (work function 3.7 eV) or Al (4.3 eV) leads to improved device stability,
however, usually at the expense of an increase in driving voltage and a reduced
device efciency.
Vol. 3 LIGHT-EMITTING DIODES 93
gain upon dissolution (and also reduce interchain interactions) and, thus, render
the polymer soluble (Fig. 4b); (3) the introduction of exible spacer units between
the conjugated moieties which reduce the overall rigidity of the polymer backbone,
again leading to improved solubility (Fig. 4c); and (4) the use of nonconjugated,
processable polymers which feature the conjugated moieties in the form of side
chains (Fig. 4d) or (5) as guest molecules which are not covalently connected to
the matrix polymer but are rather dissolved or dispersed in the latter.
The so-called precursor route represents a particularly attractive way to
synthesize and process underivatized -conjugated polymers which were initially
employed in many of the early studies on PLEDs, including PPVs and poly(p-
phenylene)s (PPPs) (26,27). The concept relies on the three steps of synthesiz-
ing tractable, nonconjugated precursor macromolecules comprising appropri-
ately selected leaving groups, processing of these precursor polymers according
to standard (mostly solution-based) techniques, and converting the precursor
Vol. 3 LIGHT-EMITTING DIODES 95
disclosed prototypes or pilot products that offer a luminous efciency lum between
10 and 22 lm/W at an (average) brightness between 100 and 1000 cd/m2 (4,10,32).
Thus, these devices clearly meet the brightness requirements for many display
applications and also match the efciency of conventional inorganic LEDs incan-
descent lamps. However, it should be noted that bright and efcient devices are
primarily available in the green range of the emission spectrum, while presently
available blue- and red-light-emitting materials result in devices which are sub-
stantially less bright and efcient (4,7). Thus, substantial progress regarding the
availability of different colors is required before full-color devices based on red,
green, and blue pixels can be made available.
Probably, one of the most critical aspects from an application point of view
is that of device lifetime. Although the requirements for the latter strongly de-
pend of the particular application, operating lifetimes of >10,000 h are usually
targeted (4,5), often at elevated temperatures. Detailed studies conducted at a
variety of laboratories (4,10) have indeed demonstrated that this requirement
can, in principle, be met when adequately packaging the device. However, most
of the successful lifetime studies were conducted under constant current con-
ditions, and a gradual rise of the driving voltage was reported to maintain the
initial current and brightness. This situation not only suggests an irreversible
degradation of the device but also presents a challenge for the electronic device
drivers.
The most basic device architecture of PLEDs has been described above; most
technical applications rely on much more sophisticated designs. For example, al-
most every display application will demand arrays of many individually address-
able pixels, similar to conventional LCDs (Fig. 7). Pixilated PLEDs rely on the
creation of a grid of intersecting anode and cathode rows, which is usually gen-
erated by photolithographic patterning of the ITO anode into columns and vapor
deposition of the cathode rows through a corresponding mask. As it is well known
for LCDs (33), the devices can be operated in either passive- or active-matrix
mode. Passive-matrix addressing relies on the consecutive addressing of the rows
(typically within a period of 1/30 s or less) and on applying a simultaneous bias to
the columns holding active pixels. Where an active row and column intersect, the
electric eld directly causes EL emission. This format, which is usually used for
low resolution applications, requires high scanning rates in order to avoid icker-
ing of the image. Moreover, because each pixel is active only for a short fraction of
the cycle, it will require to generate very high intensity (ie, >10,000 cd/m2 ) under
a high current density during its on state in order to produce an acceptable aver-
age luminance. The active matrix architecture moderates the need to cycle at high
rates by giving every pixel a memory in the form of a capacitor and a transis-
tor. While this architecture seems mandatory for high resolution and large-area
displays, it adds, of course, another layer of complexity to the device.
Another step toward high end application is, of course, the creation of multi-
color devices, featuring red, green, and blue pixels. A variety of approaches have
been suggested to achieve the latter, including (1) the use of uv or blue LEDs
and external color conversion through green and red-light-emitting uorescent
dyes applied to the appropriate pixels, (2) the use of white LEDs in combination
with conventional absorbing color lters, (3) the stacking of individual, indepen-
dent device segments in vertical fashion, and (4) the use of advanced deposition
98 LIGHT-EMITTING DIODES Vol. 3
Fig. 7. Polymer LED passive matrix display; 160 160 pixels with pitch of 300 m.
Picture provided by Nobel Laureate Dr. Alan J. Heeger, courtesy of Uniax Corp., Santa
Barbara, Calif.
BIBLIOGRAPHY
30. F. Wudl, P. M. Allemand, G. Srdanov, Z. Ni, and D. McBranch, Materials for Nonlinear
Optics: Chemical Perspectives, American Chemical Society, Washington, D.C., 1991,
pp. 683.
31. D. Braun and A. J. Heeger, Appl. Phys. Lett. 58, 1982 (1991).
32. URL: www.cdtltd.co.uk; www.covion.com; www.dow.com; www.dupont.com;
www.philips.com; www.uniax.com.
33. L. K. M. Chan, in R. J. Brook, M. C. Flemings, and S. Mahajan, eds., The Encyclopedia
of Advanced Materials, Vol. 2, Elsevier Science Ltd., Oxford, 1994, pp. 1294.
34. M. Grell and co-workers, Adv. Mater. 11, 895 (1999).
35. D. E. Mentley, Laser Focus World 35(5), 111 (1999).
ANDREAS GREINER
Marburg Germany
Universitat
CHRISTOPH WEDER
Case Western Reserve University