Chapter 2 Historical background

2. HISTORICAL BACKGROUND

LEPs are unique class of conjugated organic macromolecules that exhibit

semiconducting behavior and emit electromagnetic radiation when electric current is passed
through them. This electrically driven radiative emission, generally referred as
electroluminescence (EL), was supposed to be limited to inorganic semiconductors and
small-molecule organic dyes until early 1970s. In 1976, the first organic EL device with
polymer PVK (polyvinyl carbazole) doped with perylene tetraphenyl butadiene or acridine
orange was tested but required very high voltage to stimulate light emission.

The development of organic electroluminescence progressed to the point of practical

importance through the effort of Tang and his coworkers in Kodak Research Laboratories in
1987. They deviced the first two layered OLED with appropriately low operating voltage
with a p-type hole transporting layer of aromatic diamine and a n-type emitting layer of
electron transporting metal chelate tris-hydroxyquinoline aluminium (Alq3) sandwiched
between ITO anode and low work function alloy of magnesium as electron injecting cathode.

Shortly afterwards in 1990, Prof. Richard H.Friends group at Cambridge University

discovered electroluminescence from conjugated polymers during an investigation on the
electrical properties of PPV (Poly phenylene vinylene). They fabricated first PLED with a
layer of pure conjugated PPV placed between ITO and Al electrode. Yellow-green light with
emission maximum at 551nm was observed from this bright yellow polymer upon excitation
with a flow of electric current between two electrodes.

Further researches in light emission in conjugated polymers lead to a key patents in

Cambridge University to exploit which CDT (Cambridge Display Technology) was founded
in 1992. CDT has been active ever since in material and technology issues to promote the
commercial development of PLEDs.

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Chapter 2 Historical background

Table 1. History of investigations in the field of EL organic materials

Year Authors and references Materials/structure

1953 Bernanose et. al Blue emission from LED on

li complex

1963 Pope et. al. EL from anthracene crystals

1976 Kalinowski et.al. EL from tetracene

1983 Partridge EL from organic (PVK)

polymer

1987 Tang and Van Slyke Double layer OLED

1990 R.H. Friends et. al. Single layer PLED

1993 Greenham et. al. Double layer PLED

2007 M. Hack et. Al. Flexible OLED technology

PPV used in first fabricated PLED, although an excellent LEP, is insoluble in

common solvents and as such required special processing steps to produce conjugated thin
film. In 1991, Heeger and coworkers at University of California used soluble derivative of
PPV namely poly [2- methoxy-5-(2 ethyl hexyloxy)-1, 4- phenylene vinylene] (MEH-PPV)
as LEP in polymer LED. However due to its susceptibility to photoxidation, this polymer
could not succeed as a candidate for commercial use.

This was followed by fabrication of blue PLEDs by Unchinda et al. using polyalkyl
fluorene (PF) as LEP .Since then many LEPs have been developed for LED applications, e.g.
Poly (1,4-phenylene) (PPP) 2 , polythiophenes (PTs) 3, polyfluorenes (PFs) .

Explosion of research activities in LEPs in last two decades led to enormous progress
in various aspects such as development of new LEPs, improvement in device structure and
enhanced efficiency so as to realize commercial applications. The pursuit for efficient and
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Chapter 2 Historical background

long lasting PLEDs has seen significant effort in materials and device structure. The emission
colours of these polymers have covered the entire visible spectrum and it has be achieved by
improvement in molecular structures of polymer like PPV, PFO (9, 9 dialkyl fluorene) and
their derivatives and copolymers Materials are critical factor for both efficiency and life time.
The utilization of new materials has allowed revolutionary improvements in PLED
efficiency. From the first generation fluorescent materials used in first PLEDs to novel
transport and emission layer host materials, the efficiency of PLEDs have grown more than
tenfold and can now challenge and defeat LEDs in terms of efficiency at wavelength close to
550nm. Moreover continued development of PLED materials have allowed for devices with
enhanced operating lifetime.