24 Annual report 1996

Nearly Monochromatic Light Emitting Diodes

Based on Organic Thin Films

Siegfried Dirr, Hans-Hermann Johannes, Stefan Wiese,

and Wolfgang Kowalsky
Electroluminescent devices with narrow emission bandwidths in the red, green, and blue spec-
tral region based on thin films of lanthanide complexes or microcavity structures are investigated
in terms of color purity for multicolor display applications. Multilayer organic light emitting
diodes (OLEDs) with the β-diketonates tris-(2,4-pentanediono)-1,10-phenathroline terbium (III)
(Tb(ACAC)3 Phen) and tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanediono)-1,10-phenanthroline eu-
ropium (III) (Eu(TTFA)3 Phen) show nearly monochromatic electroluminescence in the green and
red spectral region, respectively. We have also demonstrated, that vacuum-deposited thin films
of the novel complex tris(4,4,4-trifluoro-1-phenyl-1,3-butanediono)-1,10-phenanthroline dyspro-
sium (III) show luminescent lines for use as active layer in white-light emitting diodes. In case of
microcavity electroluminescent cells with the fluorescent dye aluminum-tris(8-hydroxychinoline)
(Alq3 ), spectral bandwidths of about 23 nm have been achieved at a resonance wavelength of
475 nm. This corresponds to a spectral narrowing by a factor of about 3.5 in comparison with
noncavity OLEDs.

1. Introduction

The technology for low-cost flat panel displays using organic electroluminescent devices is under
intense current research [1,2]. Brightness and device lifetime are sufficient for most potential
applications [3]. One of the problems still remaining is to obtain narrow emission bands at the three
primary colors red, green, and blue for multicolor displays. White-light OLEDs can be realized
using a combination of three emitter layers or fabricating a multimode microcavity device, but
there is still no single fluorescent organic material producing white light.
Due to the relatively broad bands of the organic dyes, mixed colors cannot be reached satisfactorly.
One way to realize nearly monochromatic light sources is the use of fluorescent lanthanide com-
plexes [4]. It has also been shown that the electroluminescence spectrum can be narrowed and the
emission intensity can be enhanced by incooporating the light emitting diodes into a Fabry-Perot
microcavity structure [5,6].

2. Thin Film and Device Preparation

Ultrathin organic films of the devices with and without the microcavity have been subsequently
grown by the organic molecular beam deposition (OMBD) technique under UHV conditions at
Institut für Hochfrequenztechnik, TU Braunschweig 25

Fig. 1: Molecular structures

and room temperature thin
film luminescence spectra of
(a) Dy(BTFA)3 Phen, (b)
Eu(TTFA)3 Phen, and (c)
Tb(ACAC)3 Phen.

a base pressure of about 10 9 hPa [7]. Smooth and homogenous films are obtained by adjusting

growth rates of about 2-8 nm/min. The microcavity device consists of a dielectric Bragg reflector
with alternate layers of SiO2 and TiO2, which have been prepared by e-beam evaporation. Then
the mirror is coated with the transparent ITO anode by a magnetron-sputtering process obtaining
sheet resistances of about 70 Ω . For the noncavity OLED, an ITO coated glass substrate with


a sheet resistance of 30 Ω has been used. Evaporation of 120 nm Mg followed by 120 nm Ag



defines a 3 mm2 cathode contact, which serves also as a metal mirror.

3. Lanthanide Complex based OLEDs

Three volatile lanthanide β-diketonates chelates have been synthesized according to methods de-
scribed in the literature [8,9]. The molecular structures and the room temperature thin film lumi-
nescence spectra are shown in Fig. 1. The fluorescence spectra with linewidths of only about 5
to 10 nm are due to an intramolecular energy transfer from the organic ligands triplet level to the
ion followed by radiative energy transitions from the excited 4f levels of the trivalent lanthanide
ion. The novel complex tris(4,4,4-trifluoro-1-phenyl-1,3-butanediono)-1,10-phenanthroline dys-
prosium (III) (Dy(BTFA)3 Phen) shows intense luminescent lines at 484 nm and 576 nm. Thin
26 Annual report 1996

Fig. 2: Device structures and

transport layer molecular
structures of (a) the Tb
complex and (b) the Eu
complex based OLEDs.

films of the complexes tris(4,4,4–trifluoro–1–(2–thienyl)–1,3–butanediono)–1,10–phenanthroline

europium (III) (Eu(TTFA)3 Phen) and tris–(2,4–pentanediono)–1,10–phenathroline terbium (III)
(Tb(ACAC)3 Phen) show emission peaks at 614 nm and 543 nm, respectively. The device struc-
tures of the multilayer OLEDs and the molecular structures of the carrier transport materials are
depicted in Fig. 2. The Tb complex based OLED (a) is a single heterostructure device with a 30 nm
CuPc and a 10 nm TAD double hole transporting layer sequence and a 30 nm Tb(ACAC)3 Phen
emitter layer. The double heterostructure OLED with a 5 nm Eu(TTFA)3 Phen emitter layer con-
sists of an electron transporting layer of 30 nm Alq3 and a 30 nm hole transport layer of TAD. To
prove color purity of the both EL cells and the Dy(BTFA)3 Phen thin film, the CIE coordinates are
shown in Fig. 3. Nearly monochromatic emission in the green (x=0.37, y=0.59) and red (x=0.66,
y=0.34) spectrum can be observed. The sublimability and the thin film luminescence color of the
Dy(BTFA)3 Phen (x=0.36, y=0.38) proves the applicability as white-light emitter in electrolumi-
nescent devices only from a single active layer.

Fig. 3: CIE color coordinates

of (a) the Tb complex, (b) the
Eu complex based OLED and
(c) the Dy complex thin film.
Institut für Hochfrequenztechnik, TU Braunschweig 27

Fig. 4: Device structure, simulated and measured electroluminescence spectra, and CIE coordi-
nates of the single mode microcavity OLED for detection angles of 0 and 30 .
 

4. Microcavity Organic Electroluminescent Devices

To study the possibility of a microcavity Alq3 based OLED emitting in the blue spectral region, a
multilayer device have been fabricated for a Fabry Perot resonance wavelength of about 475 nm.
This corresponds to the blue tail of the Alq3 emission spectrum. The device structure, the angle
dependent spectral characteristics, and the corresponding color coordinates of the device are sum-
marized in Fig. 4. The EL device consists of a distributed Bragg reflector with three λ 4 pairs of


SiO2 (n=1.49 at 530 nm) and TiO2 (n 2 20 at 530 nm) followed by a λ 4 layer of the ITO anode
  

(n=2.0 at 530 nm), a single mode etalon (λ 2) of CuPc, TAD and Alq3 layers each with thicknesses


of 50 nm, and finally a metal mirror of Mg/Ag. The reflectivity of the dielectric mirror has been
determined to nearly 80% at the design wavelength.
The peak wavelengths at 0 and 30 detection angle are 475 nm and 465 nm, respectively. The
 

calculated EL spectra determined with a modified transfer matrix method by incorporating the Alq3
fluorescence spectra as an isotrop radiative dipole are in very good agreement with the measured
28 Annual report 1996

EL spectra. Thus the angle dependent spectra can be predicted. The halfwidth of the 0 spectrum


is of about 23 nm corresponding to a spectral narrowing by a factor of about 3.5 in comparison

with a conventional Alq3 OLED. A blue shift in the spectrum can be observed comparing the
CIE color coordinates of a conventional Alq3 OLED (x=0.25, y=0.47) with the 0 emission of the


microcavity OLED (x=0.19, y=0.30).

5. Conclusions

The aim of this work was to demonstrate narrow line emission from organic electroluminescent
devices. Nearly monochromatic red and green emission have been obtained following the device
concept of Eu and Tb complex based OLEDs, respectively. The color purity is sufficient for
application in multicolor displays. A novel Dy complex can be used to prepare thin films for
white-light emitting diodes. To realize blue light emitting diodes, a microcavity Alq3 based EL
device has been successfully prepared.

Acknowledgements

We gratefully acknowledge the generous financial support of the Bundesministerium für Bildung
und Forschung (BMBF) and the Volkswagenstiftung.

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