Organic electroluminescent diodes

c. W. Tang and S. A. VanSlyke

Research Laboratories. Corporate Research Group. Eastman Kodak Company. Rochester. New York 14650

(Received 12 May 1987; accepted for publication 20 July 1987)

A novel electroluminescent device is constructed using organic materials as the emitting
elements. The diode has a double-layer structure of organic thin films, prepared by vapor
deposition. Efficient injection of holes and electrons is provided from an indium-tin-oxide
anode and an alloyed Mg:Ag cathode. Electron-hole recombination and green
electroluminescent emission are confined near the organic interface region. High external
quantum efficiency (1 % photon/electron), luminous efficiency (1.5 lm/W), and brightness
( > 1000 cd/m2) are achievable at a driving voltage below IO V.

Organic materials have previously been considered for isopropyl alcohol and water ( I: 1) and degreased in toluene
the fabrication of practical electroluminescent (EL) de- vapor. The first organic layer (about 750 A) on top of the
vices. I The primary reason is that a large number of organic substrate is an aromatic diamine9 of molecular structure
materials are known to have extremely high fluorescence shown in Fig. 1. The second organic layer is the luminescent
quantum efficiencies in the visible spectrum,2.3 including the film, about 600 A. It belongs to a class of fluorescent metal
blue region. some approaching 100%. In this regard, they chelate complexes. 10 The specific example shown in Fig. I is
are ideally suited for multicolor display applications. 8-hydroxyquinoline aluminum (Alq3)' The top electrode is
However, the development of organic EL devices has an alloy or mixture of magnesium and silver with an atomic
not been successful so far, one reason being that high voltage ratio of 10: I. The organic layers, as well as the Mg:Ag elec-
is generally required to inject charges into organic crystals trode, were all deposited by vacuum deposition (_10- 5
(e.g., anthracene). In early attempts by Helfrich and Torr). The substrate was nominally at room temperature
Schneider,4 Dresner, I and Williams and Schadt,5 the drive and the deposition rates for the organic layers were about 2-
voltage was on the order of 100 V or above in order to 5 A/s. The Mg:Ag electrode was deposited by simultaneous
achieve a significant light output. Therefore, the EL device evaporation from two separate sources at a total rate of
power-conversion efficiency is quite low, typically less than about 10 A/s.
0.1 % W /W, despite the reported high external quantum ef- The organic diode shown in Fig. I can be operated in a
ficiency of ~ 5% photon/electron. In an attempt to reduce continuous dc or pulsed mode. It behaves like a rectifier, the
the drive voltage, Vincett et al. n used thin organic films of forward bias corresponding to a positive voltage on the ITO
similar materials in their EL devices. They reported EL op- electrode. Light emission, seen only in forward bias, was
eration below 30 V. However, the quantum efficiency of measurable from as low as about 2.5 V. Figure 2 shows the
their EL diodes was only about 0.05%, presumably owing to continuous dc current vs voltage (1- V) and the radiance exi-
the inefficiency of electron injection and the inferior quality tance vs voltage (B- V) curves. The shape of the J- V curves
of the evaporated anthracene films. Other organic thin-film for most diodes is relatively independent of the thickness of
EL work 7.X reported similar performance. Another factor the diamine layer but strongly dependent on that of the Alq3
for the lack of development is perhaps the question of long- layer, indicating that most of the bias voltage is across the
term stability of organic EL diodes. There are very few re- Alq3layer. The J- V curve can be fitted to an injection-limited
ported data on the organic EL stability in the literature.o model where the electron current is limited by electron emis-
In this letter, we report a novel thin-film organic device sion from the cathode into the Alq3 layer. The radiance exi-
with superior EL characteristics. It is efficient and can be tance in mW /cm 2 was measured from a diode with an emit-
driven to high brightness by a low dc voltage. In contrast to
most organic EL cells, which use a single layer of organic
material sandwiched between two injecting electrodes, our
EL diode consists of a double layer of organic thin films, with
one layer capable of only monopolar transport. The organic
materials were chosen such that the morphological, trans-
port, recombination, and luminescent properties were com-
patible with the construction and operation of the thin-film
EL diodes. In addition, we used a low-work-function alloy
prepared by vapor codeposition as the cathode for efficient
electron injection.
Figure I shows the structure of the present EL cell. The
substrate is an indium-tin-oxide (ITO) coated glass with a
sheet resitance of about 10-20 % (Nesatron ™ from PPG
Industries). It was cleaned by ultrasonication in a mixture of FIG. \. Configuration ofEL cell and molecular structures.

913 Appl. Phys. Lett. 51 (12). 21 September 1987 0003-6951/87/380913-03$01.00 © 1987 American Institute of Physics 913
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 1
if 10 emISSIOn spectrum is identical to the photoluminescence
spectrum of the Alq.l thin film. This result indicates that the
N
1 100 ,
N
radiative recombination of injected electrons and holes takes
'E 10
u E place in the Alq, layer. Detailed analysis 1\ shows that this
« u
E ~ recombination is confined to the Alq \ layer adjacent to the
0° 10- 1
E diamine layer to a distance of about 300 A. The diamine
~
en ~ layer, which is known to transport holes only, 'I blocks the
c Ui
<ll ler l 10-l C electrons injected from the Mg:Ag electrode. Therefore, the
"0
2
C c interface between the diamine and Alq, layer effectively con-
e ~
10- 2 10- 3
-l
trols the recombination processes.
:J W
()
The morphological properties of the organic layers are
10- 3 10- 4 critical in the construction of thin-film devices without pin-
0 5 10 holes. It is necessary that both layers in the EL device be
Bias voltage (V) smooth and continuous. The transmission electron micro-
FIG. 2. Brightness-current-voltage characteristics of an ITO/diaminei graphs show that the evaporated diamine layer appears to be
Alq,/Mg:Ag EL cell. amorphous, whereas the Alq, film is microcrystalline with
an average grain size of about 500 A. The ability to form
smooth films in both layers in the present EL diode is related
ting area of 0.1 cm:' by a radiometer (EGG model 550-1). to the low order of symmetry as well as large molecular ge-
The emitting surface is Lambertian for viewing angles within ometry of the constituent molecules. In addition, the two-
60° from the normal to the surface. The brightness in units of layer structure partially alleviates the shorting problem by
cd/m~ was separately measured by a spot photometer (Min- minimizing the probability of having overlapping pinholes.
olta Luminance Meter, III - 1/3°). A radiance exitance of The Mg:Ag alloy used as the cathode is important in the
0.1 m W /cm:' is equivalent to a brightness of 100 cd/m:' for reduction of the drive voltage. Mg is a low-work-function
the EL diode with Alq, as the emitter. As shown in Fig. 2, metal ideally suited for electron injection into organic mate-
the EL diode can be driven to produce high brightness rials. However, it is susceptible to atmospheric oxidation
( > 1000 cd/m:') with a dc voltage of less than 10 V. In and corrosion. The incorporation of Ag in the Mg:Ag film is
pulsed operation, the response of the diode has a rise and found to retard these degradation processes. In addition, Ag
decay time on the order of a few microseconds. improves the sticking coefficient of Mg on the organic film
The light output from the EL diode is linearly propor- during vapor deposition. Other common cathode materials
tional to the input current in the current range from 10 - I to such as In, Ag, and Al generally result in much higher vol-
1O~ mA/cm~. The external quantum efficiency of the EL tage drive and inferior stability.
diode is about 1%. At the power output of 0.1 mW/cm:', The EL diode has been tested for stability in a contin-
which is visible in ambient lighting, the required drive vol- uous dc operation. Under constant current drive of 5 mAl
tage is 5.5 V and the corresponding power conversion effi- cm=' and in an argon ambient, the EL emission (with initial
ciency is 0.46%. The equivalent luminous efficiency is 1.5 output of about 0.05 m W /cm=' or 50 cd/m~) shows a rela-
Im/W, which compares favorably with the commercially tively fast degradation in the initial hours (about 30% loss in
available light-emitting diodes or ZnS-based EL devices. II 10 h) and then decays at a much slower rate to about half of
The emission spectrum of the EL diode is shown in Fig. the initial value at the end of a 100-h test The steady degra-
3. The peak intensity is at 550 nm, the FWHM is about 100 dation is accompanied by a concomitant increase in the drive
nm, and the color is green. The EL emission spectrum is voltage from the initial 6 or 7 V to about 14 V during this test
independent of the drive voltage or current but is sensitive to period. The nature of degradation is not clearly understood.
the thickness of the organic layers. The latter effect is due to Some of the failure is attributed to the degradation of both
the interference phenomenon of emission in front of a re- hole and electron injecting contacts, the latter resulting in
flecting mirror. I:' For thin organic films (as in Fig. I) the EL the formation of dark nonemissive spots.
In conclusion, we have shown a novel organic electrolu-
minescent diode with a double-organic-Iayer structure. The
diode has unique characteristics of high electroluminescent
emission efficiency, fast response, low voltage drive, and
simplicity offabrication. It demonstrates that organic mate-
rials can indeed be viable alternatives for optoelectronic ap-
plications such as displays.

'1. Dresner, RCA Rev. 30,322 (1969).

400 500 600 700 800
'K. H. Drexhage, in Topics in Applied Physics: Dye Lasers, edited by F. P.
Wavelength (nm) Schafer (Springer, New York, 1977), Vol. I, p. 144.
FIG. J. Ekctroluminescence spectrum of ITO/diaminel Alq ,IMg:Ag. 'H. Gold. in The Chemistry a/Synthetic Dyes, edited by K. Venkataraman

AppL
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2011 to Lett., Vol. 51, No. Redistribution
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1987 to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
subject
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915 Appl. Phys. Lett .• Vol. 51. No. 12.21 September 1987 c. W. Tang and S. A. VanSlyke 915
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