U.S. patent application number 10/393952 was filed with the patent office on 2003-10-09 for organic electroluminescent device.
This patent application is currently assigned to International Manufacturing and Engineering Services Co., Ltd., International Manufacturing and Engineering Services Co., Ltd.. Invention is credited to Hayashi, Takeshi, Kido, Junji.
Application Number | 20030189401 10/393952 |
Document ID | / |
Family ID | 28043836 |
Filed Date | 2003-10-09 |
United States Patent
Application |
20030189401 |
Kind Code |
A1 |
Kido, Junji ; et
al. |
October 9, 2003 |
Organic electroluminescent device
Abstract
An organic electroluminescent device includes at least two
light-emissive units provided between a cathode electrode and an
anode electrode opposed to the cathode electrode, each of the
light-emissive units including at least one light-emissive layer.
The light-emissive units are partitioned from each other by at
least one charge generation layer, the charge generation layer
being an electrically insulating layer having a resistivity of not
less than 1.0.times.10.sup.2 .OMEGA.cm.
Inventors: |
Kido, Junji; (Yamagata-ken,
JP) ; Hayashi, Takeshi; (Kanagawa-ken, JP) |
Correspondence
Address: |
Marina F. Cunningham
McCormick, Paulding & Huber LLP
185 Asylum Street, CityPlace II
Hartford
CT
06103
US
|
Assignee: |
International Manufacturing and
Engineering Services Co., Ltd.
Fujisawa-shi
JP
|
Family ID: |
28043836 |
Appl. No.: |
10/393952 |
Filed: |
March 21, 2003 |
Current U.S.
Class: |
313/504 ;
313/506; 428/212; 428/690; 428/917 |
Current CPC
Class: |
H01L 51/005 20130101;
C07C 211/58 20130101; C07C 2603/18 20170501; C09K 2211/1014
20130101; H01L 51/5284 20130101; H01L 51/5278 20130101; H01L
51/5036 20130101; C09K 11/06 20130101; H01L 51/0058 20130101; H01L
51/5044 20130101; H01L 51/5088 20130101; C07C 211/61 20130101; H01L
51/5221 20130101; C09K 2211/1003 20130101; H01L 51/5056 20130101;
H01L 51/56 20130101; H01L 51/0056 20130101; H01L 51/006 20130101;
Y10T 428/24942 20150115; H01L 51/5262 20130101; C09K 2211/1007
20130101; H01L 51/5206 20130101; H01L 51/5072 20130101; C09K
2211/1011 20130101; H01L 51/5092 20130101 |
Class at
Publication: |
313/504 ;
428/690; 428/917; 428/212; 313/506 |
International
Class: |
H05B 033/12 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 26, 2002 |
JP |
2002-86599 |
Mar 14, 2003 |
JP |
2003-70135 |
Claims
What is claimed is:
1. An organic electroluminescent device comprising: at least two
light-emissive units provided between a cathode electrode and an
anode electrode opposed to said cathode electrode, each of said
light-emissive units including at least one light-emissive layer;
wherein said light-emissive units are partitioned from each other
by at least one charge generation layer, said charge generation
layer constituting an electrically insulating layer having a
resistivity of not less than 1.0.times.10.sup.2 .OMEGA.cm.
2. The organic electroluminescent device according to claim 1,
wherein the charge generation layer constitutes an electrically
insulating layer having a resistivity of not less than
1.0.times.10.sup.5 .OMEGA.cm.
3. The organic electroluminescent device according to claim 1 or 2,
wherein said charge generation layer comprises at least one of a
laminated and mixed layer formed from two different materials;
wherein a charge transfer complex including a radical cation and a
radical anion is formed upon an oxidation-reduction reaction
between said two materials, and a radical cation state and a
radical anion state in said charge transfer complex is transferred
to a direction of the cathode and a direction of the anode,
respectively, when a voltage is applied to said device, so that a
hole is injected into the light-emissive unit which is located on a
cathode side of the charge generation layer and is adjacent
thereto, and an electron is injected into the light-emissive unit
which is located on an anode side of the charge generation layer
and is adjacent thereto.
4. The organic electroluminescent device according to claim 1,
wherein said charge generation layer comprises one of a laminated
and a mixed layer comprising: an organic compound having an
ionization potential of less than 5.7 eV and a hole transporting
property or electron donating property; and one of an inorganic and
organic material capable of forming a charge transfer complex
through the oxidation-reduction reaction thereof with said organic
compound; wherein said charge generation layer contains a charge
transfer complex formed upon the oxidation-reduction reaction
between said organic compound and one of an inorganic and organic
material.
5. The organic electroluminescent device according to claim 4,
wherein said organic compound comprises an arylamine compound,
wherein said arylamine compound is represented by the following
formula (I): 12wherein Ar1, Ar2 and Ar3 each independently
represents an aromatic hydrocarbon group which may have
substituents.
6. The organic electroluminescent device according to claim 5,
wherein said organic compound comprises an arylamine compound
having a glass transition temperature of not lower than 90.degree.
C.
7. The organic electroluminescent device according to claim 6,
wherein said arylamine comprises one of .alpha.-NPD, 2-TNATA,
spiro-TAD, and spiro-NPB.
8. The organic electroluminescent device according to claim 4,
wherein said inorganic material comprises a metal oxide.
9. The organic electroluminescent device according to claim 4,
wherein said inorganic material comprises a metal halide.
10. The organic electroluminescent device according to claim 8,
wherein said metal oxide comprises one of vanadium pentaoxide and
rhenium heptaoxide.
11. The organic electroluminescent device according to claim 4,
wherein said inorganic material is deposited by one of a resistive
heating vapor deposition method, an electron beam vapor deposition
method and a laser beam vapor deposition method.
12. The organic electroluminescent device according to claim 4,
wherein said inorganic material is deposited by a sputtering
method; wherein a sputtering apparatus used in the sputtering
method is a facing target sputtering system which comprises a pair
of opposed targets provided at a certain distance, a reflection
electrode capable of reflecting electrons towards a front
peripheral area of each target, and a magnetic field generation
device capable of forming a parallel magnetic field in the vicinity
of the peripheral portion of each target, said magnetic field
having a portion parallel to the peripheral portion of the
target.
13. The organic electroluminescent device according to claim 4,
wherein said organic material-comprises at least one fluorine as a
substituent group, and possesses at least one of an electron
injection property and an electron accepting property.
14. The organic electroluminescent device according to claim 4,
wherein said organic material comprises at least one cyano group as
a substituent group, and possesses at least one of an electron
injection property and an electron accepting property.
15. The organic electroluminescent device according to claim 13,
wherein said organic material comprises
tetrafluoro-tetracyanoquinodimethane (4F-TCNQ).
16. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive unit comprises, as a layer located
on an anode side of said charge generation layer and being adjacent
thereto, an electron injection layer having a mixture including an
organic compound and a metal functioning as an electron donating
dopant.
17. The organic electroluminescent device according to claim 16,
wherein said electron donating dopant comprises at least one metal
selected from a group including an alkaline metal, an alkaline
earth metal and a rare earth metal.
18. The organic electroluminescent device according to claim 17,
wherein said metal of the electron donating dopant is provided in a
molar ratio of 0.1 to 10 with respect to said organic compound in
said electron injection layer.
19. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive unit comprises, as a layer located
on an anode side of said charge generation layer and being adjacent
thereto, a metal layer having a thickness of not more than 5 nm
formed from a metal selected from an alkaline metal, an alkaline
earth metal and a rare earth metal; wherein said metal constituting
the layer diffuses in the adjacent electron transporting layer to
react with electron transporting organic material; and wherein, as
a result of said diffusion, an electron injection layer is composed
of a mixture including said electron transporting organic material
and a metal functioning as an electron donating dopant is
formed.
20. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive unit comprises, as a layer located
on an anode side of said charge generation layer and being adjacent
thereto, a layer including an organic metal complex compound
including at least one metal ion selected from an alkaline metal
ion, an alkaline earth metal ion and a rare earth metal ion, and a
reaction generating layer which is formed by an in-situ reduction
reaction when a thermally reducible metal, which can reduce a metal
ion in said organic metal complex to a metal in a vacuum is
deposited on the organic metal complex constituting the layer.
21. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive unit comprises, as a layer located
on an anode side of said charge generation layer and being adjacent
thereto, a layer including an inorganic compound including at least
one metal ion selected from an alkaline metal ion, an alkaline
earth metal ion and a rare earth metal ion, and a reaction
generating layer which is formed by an in-situ reduction reaction
when a thermally reducible metal, which can reduce a metal ion in
the inorganic compound to a metal in a vacuum is deposited on the
inorganic compound constituting the layer.
22. The organic electroluminescent device according to claim 20 or
21, wherein the thermally reducible metal includes at least one
selected from Aluminum, Zirconium, Silicon, Titanium and
Tungsten.
23. The organic electroluminescent device according to claim 1,
wherein said light-emissive unit comprises a structure, as a layer
located on an anode side of said charge generation layer and being
adjacent thereto, in which a layer of a mixture including an
organic compound and an electron donating dopant is formed,
thereafter, a reaction generating layer is generated by an in-situ
reduction reaction when a thermally reducible metal, which can
reduce an alkaline metal ion, an alkaline earth metal ion or a rare
earth metal ion to a metal in a vacuum, is deposited on an organic
metal complex compound containing at least one metal ion selected
from an alkaline metal ion, an alkaline earth metal ion and a rare
earth metal ion.
24. The organic electroluminescent device according to claim 1,
wherein said light-emissive unit comprises a structure, as a layer
located on an anode side of said charge generation layer and being
adjacent thereto, in which a layer of a mixture including an
organic compound and an electron donating dopant is formed,
thereafter, a reaction generating layer is generated by an in-situ
reduction reaction when a thermally reducible metal, which can
reduce an alkaline metal ion, an alkaline earth metal ion or a rare
earth metal ion to a metal in a vacuum, is deposited on an
inorganic compound containing at least one metal ion selected from
an alkaline metal ion, an alkaline earth metal ion and a rare earth
metal ion.
25. The organic electroluminescent device according to claim 1 or
2, in which said light-emissive unit comprises, as a layer located
on a cathode side of said charge generation layer and being
adjacent thereto, a hole injection layer comprising a mixture of an
organic compound and an electron accepting compound having a
property capable of oxidizing said organic compound in terms of
Lewis acid chemistry.
26. The organic electroluminescent device according to claim 25,
wherein the electron accepting compound having a property capable
of oxidizing the organic compound in said hole injection layer in
terms of Lewis acid chemistry is provided in a molar ratio of 0.01
to 10 with respect to the organic compound.
27. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive unit comprises, as a layer located
on a cathode side of said charge generation layer and being
adjacent thereto, a hole injection layer including an electron
accepting compound and having a thickness of not more than 30
nm.
28. The organic electroluminescent device according to claim 1 or
2, wherein said light-emissive units each have different emission
spectrums.
29. The organic electroluminescent device according to claim 1 or
2, wherein said organic electroluminescent device emits white light
due to superimposing of different lights from each light-emissive
unit.
30. The organic electroluminescent device according to claim 1 or
2, wherein at least one of said light-emissive units includes a
light-emissive layer containing a phosphorescent material.
31. The organic electroluminescent device according to claim 1 or
2, wherein, in each of said light-emissive units, an optical path
length from a light-emissive site to a light-reflective metal
electrode is an odd-numbered times a quarter wavelength of
light.
32. The organic electroluminescent device according to claim 1 or
2, wherein all the layers including said light-emissive units, said
charge generation layer, and an electrode layer are formed on a
substrate by heating a vaporizable material in a vacuum to deposit
one of a vaporized and sublimed material on the substrate; wherein
upon depositing said one of vaporized and sublimed material on the
substrate, a substrate is transported in a direction of a planar
surface thereof, a deposition area being open in a lower surface of
the substrate; a container is provided, in a lower position of the
transporting substrate, including a vaporizable material having a
deposition width which can cover the deposition area extending in a
direction perpendicular to the transportation direction of the
substrate; and said container is heated to thereby one of vaporize
and sublime so as to deposit the vaporizable material provided in
the container.
33. The organic electroluminescent device according to claim 1 or
2, wherein a combined thickness of said light-emissive units and
said charge generation layers, sandwiched between the cathode and
the anode, is greater than 1,000 nm (1 .mu.m).
34. The organic electroluminescent device according to claim 1 or
2, wherein said organic electroluminescent device is operated at a
driving voltage of more than 25 volts.
35. The organic electroluminescent device according to claim 1 or
2, wherein light can be passed in only one direction which is one
of an anode electrode direction and a cathode electrode direction,
from a light generation site in the organic electroluminescent
device, wherein light advancing in a direction opposite to said
only one direction is absorbed by a light-absorbing medium, and
wherein, in each of said light-emissive units, a light interference
effect is removed so that an adjustment of an optical path length
from a light-emissive site of said light-emissive layers to a
light-reflective metal electrode is substantially not
necessary.
36. The organic electroluminescent device according to claim 1 or
2, wherein a light advancing in one direction which is one of an
anode electrode direction and a cathode electrode direction, from a
light generation site in the organic electroluminescent device is
reflected diffusely by a diffused reflection medium, and wherein,
in each of said light-emissive units, a light interference effect
is removed, so that an adjustment of an optical path length from a
light-emissive site of said light-emissive layers to a
light-reflective metal electrode is substantially not necessary.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an organic
electroluminescent device (hereinafter, abbreviated as an "organic
EL device" or "device") which can be used in planar light sources
and display devices.
[0003] 2. Description of the Related Art
[0004] Recently, attention has been drawn to organic
electroluminescent devices having a light-emitting or luminescent
layer including an organic compound between a cathode electrode and
an anode electrode opposed to the cathode electrode as a large area
display device operable at a low driving voltage. For the purpose
of higher efficiency in an EL device, Tang et al., as is disclosed
in Appl. Phys. Lett., 51, 913 (1987), have successfully achieved a
sufficiently high luminance and high efficiency for practice use,
i.e., a luminance of 1,000 cd/m.sup.2 and an external quantum
efficiency of 1% at an applied voltage no more(greater) than 10
volts, by adopting a structure in which organic compound layers
having different carrier transporting properties are laminated to
thereby introduce holes and electrons with good balance from an
anode and a cathode, respectively, and by having the thickness of
the organic compound layer no more(greater) than 2,000 .ANG..
[0005] Furthermore, according to the disclosures of the patents
invented by Tang et al., (such as Japanese Laid-open Patent
Application Nos. 59-194393, 63-264692 and 2-15595 and U.S. Pat.
Nos. 4,539,507, 4,769,292 and 4,885,211) it is stated that if a
total layer thickness of the organic layers sandwiched between an
anode and a cathode does not exceed about 1 um, an EL device
capable of emitting light at a lower level of the applied voltage
can be provided, and that desirably, if the total layer thickness
is reduced to a range of 1,000 to 5,000 .ANG., an electric field
(V/cm) useful in obtaining a light emission at an applied voltage
no more than about 25 volts can be obtained.
[0006] The reason why Tang et al. have directed their attention to
a reduction of the layer thickness of the organic layers in
attaining a reduction of the driving voltage, as described in the
above-referenced article, resides in overcoming the problem
suggested by Helfrich et al. in the 1960s. Namely, Helfrich et al.
have observed that an external quantum efficiency of about 5% can
be obtained when a sufficient electric field electroluminescence
(EL) is applied to an anthracene single crystal; however, according
to their method, only a low power conversion efficiency (w/w) could
be obtained, since the voltage required to drive such devices is
quite high (greater than 100V).
[0007] Referring to the above-reference Tang et al. patents, the
organic EL devices suggested therein have a multilayered structure
in which an anode, a hole injection (transporting) layer, a
light-emitting layer (having an electron transporting property) and
a cathode are laminated in that order, and the devices can provide
a quantum efficiency of at least about 5.times.10.sup.-4 (0.05%).
Furthermore, the quantum efficiency is defined in Japanese
Laid-open Patent Application No. 59-194393 as the EL quantum
efficiency simply equaling the ratio of photons per second emitted
from the cell, to the electrons per second measured in the external
circuit.
[0008] Presently, as has been already disclosed, when a fluorescent
material (utilizing emission from a singlet excitation state) is
used in the thin layer EL devices suggested by Tang et al., a
quantum efficiency above 5% can be obtained. Furthermore, when a
phosphorescent material (utilizing emission from a triplet
excitation state) is used in the EL devices, a quantum efficiency
approaching to 20% can be obtained.
[0009] As can be appreciated from the above description, the
quantum efficiency is calculated from the number of the photons
actually emitted from (outside of) the device, and thus the quantum
efficiency is called external quantum efficiency. On the other
hand, the number of photons generated internally in the device
might be quite large when compared with the value observed
externally, and it is predicted that such efficiency, called
internal quantum efficiency might reach about 5 times of the
external quantum efficiency. Accordingly, even presently, when
using a phosphorescent material, an internal quantum efficiency can
be exhibited at 100%, and thus it seems that the remaining problem
in the organic EL devices resides only in an increase of the
reliability concerning the operational life-time of the
devices.
[0010] As described above, the suggestions by Tang et al. in their
patents and articles have accelerated a worldwide research and
development in the field of organic EL devices, and thus a great
number of improved EL devices have been developed based on the
basic device structure suggested by Tang et al. Presently,
commercialization of the EL devices has already started in regard
to their use as a display device on a dashboard or in a cellular
phone.
[0011] However, from a viewpoint of durability of the device, the
above-described conventional organic EL devices can barely attain a
half-decay life time exceeding 10,000 hours with a luminance of
only the order of 100 cd/m.sup.2, which is required in display use.
Presently, it is still difficult to attain a required practical
operational life-time (10,000 hours or more) with a luminance of
about 1,000 to 10,000 cd/m.sup.2, which is required in illumination
use, etc. In fact, an organic EL device having a high luminance and
long operational life-time is still not realized and not
commercially available.
[0012] As described above, attention that has recently been drawn
to organic EL devices has been based on the discovery of a thin
film-forming material which drives the resulting device at a low
voltage of not more than 10 volts. However, the resulting device
still suffers from the disadvantage that if the device is intended
to obtain a high luminance emission necessary for illumination
purposes, a higher current density approaching tens of mA/cm.sup.2
to hundreds of mA/cm.sup.2 is necessary. Note that in the best
green light-emitting devices currently available, a luminance of
about thousands to tens of thousands of cd/m.sup.2 still needs the
above-mentioned current density of about 10 to 100 mA/cm.sup.2. It
can be considered that this property is characteristic of charge
injection type devices (like this organic EL device), and such
characteristics can cause a relatively large problem with the
operational life-time of organic EL devices in comparison with an
inorganic LED (light-emitting diode) which is also a charge
injection device and uses an inorganic compound semiconductor which
can be more robust than organic compounds.
[0013] In an organic layer formed from a low molecular organic
material via a vacuum vapor deposition method, the nature of the
electric current passing through the organic layer is defined as a
hopping conduction of electrons and holes between the molecules of
the material. Furthermore, when observing the molecules from the
chemical aspect, it can be described like this; the electron
transporting molecules and the hole transporting molecules which
are generally being as electrically neutral molecules are
repeatedly subjected to a process in which the electron
transporting and hole transporting molecules are shifted to a
radical anion state or a radical cation state, i.e., the
oxidation-reduction reaction in terms of Lewis' chemistry is being
repeated between these molecules. Referring to the above-described
property in the organic EL devices, i.e., that a higher current
density is required to attain higher luminance, this property means
that the oxidation-reduction reactions are repeated at a higher
frequency. Obviously, the deterioration speed of the organic
molecules is proportional to a frequency of the oxidation-reduction
reactions, namely, the current density.
[0014] To solve the above problem, Japanese Laid-open Patent
Application No. 11-329748 (corresponding U.S. Pat. No. 6,107,734)
suggests an organic EL device in which a plurality of organic
light-emitting layers are electrically connected in series through
an intermediate conductive layer, and with regard to the
intermediate conductive layer, describes that many types of
materials may be used in the formation of the intermediate
conductive layer, as long as they (the intermediate conductive
layer) are capable of injecting holes and electrons to one or the
other primary surface side, and capable of keeping an approximate
equipotential in the layer.
[0015] This EL device, however, suffers from the following problem.
For instance, in the display device having a simple matrix
structure, the light emission area upon voltage application should
be defined only to the pixel, i.e., the intersection area,
sandwiched by cathode and anode line, thereby enabling to display a
motion picture. However, in the above-described case in which the
intermediate conductive layer having a substantially equipotential
surface is formed in a substantially overall surface in an area
which is equal to the area of the organic light-emitting layers,
i.e., when the intermediate conductive layer is also formed in
areas other than the intersection area sandwiched by cathode and
anode line, light emission can be generated in areas other than the
intersection areas in which the light emission is desired to be
generated. Specifically, there is a possibility of generating light
emission in all of the crossed area of the cathode with the
intermediate conductive layer, the crossed area of the anode and
with the intermediate conductive layer, and if two or more
intermediate conductive layers are contained, the crossed area
between one intermediate conductive layer and another intermediate
conductive layer.
[0016] Accordingly, it is described in Japanese Laid-open Patent
Application No. 11-329748 that the intermediate conductive layers
of each pixel are separated not only from the intermediate
conductive layer of the adjacent pixels, but also from a power
source. Furthermore, one idea to separate the intermediate
conductive layers from each other in the pixels in the EL device
having a simple matrix structure is also described in this
publication. If an interlayer insulation film is previously formed
and disposed at a layer thickness above 1 um and in the form of a
sharp step pattern, the conductive layer can be automatically
separated in the presence of a suddenly-changed shape of the
interlayer insulation film, even if the conductive layer is formed
using the shadow mask identical to the one for an organic material
deposition.
[0017] However, in this case, although the cathode should not be
separated, the cathode can be separated by the interlayer
insulation film if the cathode has only a thickness of about 0.1
.mu.M (100 nm) as in the conventional organic EL devices. To avoid
this problem, Japanese Laid-open Patent Application No. 11-329748
teaches use of In (indium) as the cathode material at large
thickness, thereby preventing electrical separation of the cathode
line, because indium cannot easily cause problems due to
crystallization (this problem is generally referred to as
"hillock"), even if the cathode is formed at a thickness of 1 .mu.m
or more.
[0018] In this alternative case, however, a problem of the
throughput reduction cannot be also avoided, because a metal such
as Al (aluminum), which is a conventional and low-cost wiring
material, cannot be used as a cathode material and also it is
necessary to stably form "an interlayer insulation film having a
layer thickness above 1 .mu.M and a suddenly-changed shape of the
interlayer".
[0019] Furthermore, the inventors of the present invention have
also proposed another organic EL device in Japanese Patent
Application No. 2001-225847, and has at least two light-emitting
units constituting the conventional organic EL device (the
components in all the elements constituting the conventional
organic EL device except for a cathode and an anode), and the
contained light-emitting units are separated from each other with a
transparent layer acting as an equipotential surface.
[0020] The "equipotential surface" used herein means that when a
voltage is applied, the transparent layer cannot exhibit a
substantial potential difference in both a thickness direction and
a planar (lateral) direction in the layer. In other words, although
the inventors have not specifically disclosed, they have implied
the necessity to construct the equipotential surface from an
electrically conductive material, i.e., any material having a
resistivity less than 1.0.times.10.sup.2 .OMEGA.cm.
[0021] However, as in the above-discussed Japanese Laid-open Patent
Application No. 11-329748, if the two or more light-emitting units
are separated using a material having a high electrical
conductivity (low resistivity) described above, there may be
difficulties in defining light emission areas as required, due to
the conductivity in a planar (lateral) direction (direction
parallel to a substrate).
[0022] In practice, as shown in FIG. 38B, even if the production of
the EL device is carried out in accordance with the method of
Japanese Laid-open Patent Application No. 11-329748 by producing a
cathode 55 and an anode 52, both in the form of a strip having a
width of 2 mm, and arranging the cathode 55 and the anode 52 so
that they are crossed at right angles, thereby producing a light
emission area corresponding to the crossed (intersection) area,
i.e., 2 mm square (.quadrature.), unexpected light emission may be
caused in other areas when there is an area having an equipotential
surface 54 is extended to another area. The undesirable emission in
the EL device is shown in the photograph of FIG. 38A.
[0023] To avoid the above problem, as disclosed in the examples of
Japanese Patent Application No. 2001-225847, the inventors had to
form an equipotential surface using a shadow mask (2 mm square
pattern; .quadrature.) having a patterned opening which corresponds
to the desired light emission area, thereby selectively forming the
equipotential surface only in the desired emission layer. However,
in this method, it is difficult to attain selective emission only
in the desired pixels in the display device, because the display
device has to be produced at a pixel length and pitch (between each
pixel) of about 0.1 mm or less.
[0024] In regard to improving productivity in mass-production of
the EL devices, frequent changing and precise positioning
operations of the shadow mask is not desirable, because it causes
tremendous reduction of throughput.
SUMMARY OF THE INVENTION
[0025] In view of the above problems in the conventional organic
electroluminescent (EL) devices, the present invention provides an
organic EL device which can effectively and stably provide a device
structure capable of achieving a long operational life time with a
light-emission at a higher luminance, which cannot be easily
attained in conventional EL devices. In the production of such
organic electroluminescent (EL) devices, the formation of two or
more light-emissive units (mainly formed from an organic material),
sandwiched between a cathode and an anode, frequent change and
precise positioning of shadow masks for defining a deposition area
is not required during the formation of a charge generation layer,
which is newly introduced in the present invention. A formation of
the interlayer insulation film in a sudden-changed shape which has
a risk of causing disconnection of a cathode line is also not
required, thus enabling to enhance productivity and to simplify the
process of manufacturing simple matrix-type display devices, etc.
According to an aspect of the present invention, an organic
electroluminescent device is provided, including at least two
light-emissive units provided between a cathode electrode and an
anode electrode opposed to the cathode electrode, each of the
light-emissive units including at least one light-emissive layer.
The light-emissive units are partitioned from each other by at
least one charge generation layer, the charge generation layer
constituting an electrically insulating layer having a resistivity
of not less than 1.0.times.10.sup.2 .OMEGA.cm.
[0026] It is desirable for the charge generation layer to
constitute an electrically insulating layer having a resistivity of
not less than 1.0.times.10.sup.5 .OMEGA.cm.
[0027] It is desirable for the charge generation layer to include a
laminated and/or mixed layer formed from two different materials. A
charge transfer complex including a radical cation and a radical
anion is formed upon an oxidation-reduction reaction between the
two materials, and a radical cation state and a radical anion state
in the charge transfer complex is transferred to a direction of the
cathode and a direction of the anode, respectively, when a voltage
is applied to the device, so that a hole is injected into the
light-emissive unit which is located on a cathode side of the
charge generation layer and is adjacent thereto, and an electron is
injected into the light-emissive unit which is located on an anode
side of the charge generation layer and is adjacent thereto.
[0028] It is desirable for the charge generation layer to include a
laminated and/or a mixed layer including an organic compound having
an ionization potential of less than 5.7 eV and a hole transporting
property or electron donating property; and an inorganic and/or
organic material capable of forming a charge transfer complex
through the oxidation-reduction reaction thereof with the organic
compound. The charge generation layer contains a charge transfer
complex formed upon the oxidation-reduction reaction between the
organic compound and one of an inorganic and organic material.
[0029] The organic compound can include an arylamine compound,
wherein the arylamine compound is represented by the following
formula (I): 1
[0030] wherein Ar1, Ar2 and Ar3 each independently represents an
aromatic hydrocarbon group which may have substituents.
[0031] It is desirable for the organic compound to include an
arylamine compound having a glass transition temperature of not
lower than 90.degree. C.
[0032] The arylamine can include one of .alpha.-NPD, 2-TNATA,
spiro-TAD, and spiro-NPB.
[0033] The inorganic material can be a metal oxide.
[0034] The inorganic material can be a metal halide.
[0035] The metal oxide can be vanadium pentaoxide or rhenium
heptaoxide.
[0036] The inorganic material can be deposited by one of a
resistive heating vapor deposition method, an electron beam vapor
deposition method and a laser beam vapor deposition method.
[0037] The inorganic material can be deposited by a sputtering
method. A sputtering apparatus used in the sputtering method is a
facing target sputtering system which includes a pair of opposed
targets provided at a certain distance, a reflection electrode
capable of reflecting electrons towards a front peripheral area of
each target, and a magnetic field generation device capable of
forming a parallel magnetic field in the vicinity of the peripheral
portion of each target, the magnetic field having a portion
parallel to the peripheral portion of the target.
[0038] The organic material can include at least one fluorine as a
substituent group, and possess at least one of an electron
injection property and an electron accepting property.
[0039] The organic material can include at least one cyano group as
a substituent group, and possess at least one of an electron
injection property and an electron accepting property.
[0040] The organic material can be
tetrafluoro-tetracyanoquinodimethane (4F-TCNQ).
[0041] The light-emissive unit can include, as a layer located on
an anode side of the charge generation layer and being adjacent
thereto, an electron injection layer having a mixture including an
organic compound and a metal functioning as an electron donating
dopant.
[0042] The electron donating dopant can include at least one metal
selected from a group including an alkaline metal, an alkaline
earth metal and a rare earth metal.
[0043] The metal of the electron donating dopant can be provided in
a molar ratio of 0.1 to 10 with respect to the organic compound in
the electron injection layer.
[0044] The light-emissive unit can include, as a layer located on
an anode side of the charge generation layer and being adjacent
thereto, a metal layer having a thickness of not more than 5 nm
formed from a metal selected from an alkaline metal, an alkaline
earth metal and a rare earth metal. The metal constituting the
layer diffuses in the adjacent electron transporting layer to react
with electron transporting organic material. As a result of the
diffusion, an electron injection layer being composed of a mixture
including the electron transporting organic material and a metal
functioning as an electron donating dopant is formed.
[0045] The light-emissive unit can include, as a layer located on
an anode side of the charge generation layer and being adjacent
thereto, a layer including an organic metal complex compound
including at least one metal ion selected from an alkaline metal
ion, an alkaline earth metal ion and a rare earth metal ion, and a
reaction generating layer which is formed by an in-situ reduction
reaction when a thermally reducible metal, which can reduce a metal
ion in the organic metal complex to a metal in a vacuum is
deposited on the organic metal complex constituting the layer.
[0046] The light-emissive unit can include, as a layer located on
an anode side of the charge generation layer and being adjacent
thereto, a layer including an inorganic compound including at least
one metal ion selected from an alkaline metal ion, an alkaline
earth metal ion and a rare earth metal ion, and a reaction
generating layer which is formed by an in-situ reduction reaction
when a thermally reducible metal, which can reduce a metal ion in
the inorganic compound to a metal in a vacuum is deposited on the
inorganic compound constituting the layer.
[0047] It is desirable for the thermally reducible metal to include
at least one selected from Aluminum, Zirconium, Silicon, Titanium
and Tungsten.
[0048] The light-emissive unit can include a structure, as a layer
located on an anode side of the charge generation layer and being
adjacent thereto, in which a layer of a mixture including an
organic compound and an electron donating dopant is formed,
thereafter, a reaction generating layer is generated by an in-situ
reduction reaction when a thermally reducible metal, which can
reduce an alkaline metal ion, an alkaline earth metal ion or a rare
earth metal ion to a metal in a vacuum, is deposited on an organic
metal complex compound containing at least one metal ion selected
from an alkaline metal ion, an alkaline earth metal ion and a rare
earth metal ion.
[0049] The light-emissive unit can include a structure, as a layer
located on an anode side of the charge generation layer and being
adjacent thereto, in which a layer of a mixture including an
organic compound and an electron donating dopant is formed, a
reaction generating layer is generated by an in-situ reduction
reaction when a thermally reducible metal, which can reduce an
alkaline metal ion, an alkaline earth metal ion or a rare earth
metal ion to a metal in a vacuum, is deposited on an inorganic
compound containing at least one metal ion selected from an
alkaline metal ion, an alkaline earth metal ion and a rare earth
metal ion.
[0050] The light-emissive unit can include, as a layer located on a
cathode side of the charge generation layer and being adjacent
thereto, a hole injection layer including a mixture of an organic
compound and an electron accepting compound having a property
capable of oxidizing the organic compound in terms of Lewis acid
chemistry.
[0051] The electron accepting compound having a property capable of
oxidizing the organic compound in the hole injection layer in terms
of Lewis acid chemistry can be provided in a molar ratio of 0.01 to
10 with respect to the organic compound.
[0052] The light-emissive unit can include, as a layer located on a
cathode side of the charge generation layer and being adjacent
thereto, a hole injection layer including an electron accepting
compound and having a thickness of not more than 30 nm.
[0053] The light-emissive units can each have different emission
spectrums.
[0054] The organic electroluminescent device can emit white light
due to superimposing of different lights from each light-emissive
unit.
[0055] At least one of the light-emissive units can include a
light-emissive layer containing a phosphorescent material.
[0056] In each of the light-emissive units, it is desirable for an
optical path length from a light-emissive site to a
light-reflective metal electrode to be an odd-numbered times a
quarter wavelength of light.
[0057] All the layers including the light-emissive units, the
charge generation layer and the electrode layer can be formed on a
substrate by heating a vaporizable material in a vacuum to deposit
one of a vaporized and sublimed material on the substrate. Upon
depositing the vaporized or sublimed material on the substrate, a
substrate is transported in a direction of a planar surface
thereof, a deposition area being open in a lower surface of the
substrate; a container is provided, in a lower position of the
transporting substrate, including a vaporizable material having a
deposition width which can cover the deposition area extending in a
direction perpendicular to the transportation direction of the
substrate; and the container is heated to thereby one of vaporize
and sublime so as to deposit the vaporizable material provided in
the container.
[0058] It is desirable for a combined thickness of the
light-emissive units and the charge generation layers, sandwiched
between the cathode and the anode, to be greater than 1,000 nm (1
.mu.m).
[0059] It is desirable for the organic electroluminescent device to
be operated at a driving voltage of more than 25 volts.
[0060] It is desirable for light to be able to be passed in only
one direction which is one of an anode electrode direction and a
cathode electrode direction, from a light generation site in the
organic electroluminescent device, wherein light advancing in a
direction opposite to the only one direction is absorbed by a
light-absorbing medium, and wherein, in each of the light-emissive
units, a light interference effect is removed so that an adjustment
of an optical path length from a light-emissive site of the
light-emissive layers to a light-reflective metal electrode is
substantially not necessary.
[0061] It is desirable for light advancing in one direction which
is one of an anode electrode direction and a cathode electrode
direction, from a light generation site in the organic
electroluminescent device to be reflected diffusely by a diffused
reflection medium, and in each of the light-emissive units, a light
interference effect to be removed, so that an adjustment of an
optical path length from a light-emissive site of the
light-emissive layers to a light-reflective metal electrode is
substantially not necessary.
[0062] The present disclosure relates to subject matter contained
in Japanese Patent Application Nos.2002-86599 (filed on Mar. 26,
2002) and 2003-70135 (filed on Mar. 14, 2003) which are expressly
incorporated herein by reference in their entireties.
BRIEF DESCRIPTION OF THE DRAWINGS
[0063] FIG. 1 is a schematic view showing a light emission
mechanism of prior art organic EL device;
[0064] FIG. 2 a schematic view showing a light emission mechanism
of the organic EL device according to the present invention;
[0065] FIG. 3 is a schematic view showing a charge transfer complex
formation and transfer of electrons and holes upon application of
voltage in a charge generation layer having a laminated layer
structure, according to the device of the present invention;
[0066] FIG. 4 is a schematic view showing a charge transfer complex
formation and transfer of electrons and holes upon application of
voltage in a charge generation layer having a mixed layer
structure, according to the device of the present invention;
[0067] FIG. 5 is a graph of the absorption spectrum obtained in a
single layer or mixed layer of an arylamine compound and vanadium
pentaoxide;
[0068] FIG. 6 is a graph of the absorption spectrum obtained in a
single layer or mixed layer of 2-TNATA and 4F-TCNQ;
[0069] FIG. 7 is a graph of the absorption spectrum obtained in a
single layer or mixed layer of .alpha.-NPD and rhenium
heptaoxide;
[0070] FIG. 8 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device according to the
present invention;
[0071] FIG. 9 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Reference
Example 1;
[0072] FIG. 10A shows a glass substrate on which a transparent
anode electrode is coated;
[0073] FIG. 10B shows a construction of a metallic mask for organic
layer formation;
[0074] FIG. 10C shows a construction of a metallic mask for cathode
electrode formation;
[0075] FIG. 10D shows schematic view illustrating a construction of
the organic EL device;
[0076] FIG. 11 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Reference
Example 2;
[0077] FIG. 12 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Reference
Example 3;
[0078] FIG. 13 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
1;
[0079] FIG. 14 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
2;
[0080] FIG. 15 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
3;
[0081] FIG. 16 is a graph of the emission spectrum obtained in
Reference Example 1, and Examples 1 and 4;
[0082] FIG. 17 is a graph of the emission spectrum obtained in
Reference Examples 2 and 3, and Example 3;
[0083] FIG. 18 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
4;
[0084] FIG. 19 is a graph of the emission spectrum of three EL
devices produced in Example 4;
[0085] FIG. 20 is a graph of the emission spectrum of three EL
devices produced in Example 5;
[0086] FIG. 21 is a graph of the luminance-voltage curve of the
organic EL devices produced in Reference Example 1, and Examples 1
and 2;
[0087] FIG. 22 is a graph of the current density-voltage curve of
the EL devices produced in Reference Example 1, and Examples 1 and
2;
[0088] FIG. 23 is a graph of the current efficiency-current density
curve of the EL devices produced in Reference Example 1, and
Examples 1 and 2;
[0089] FIG. 24 is a graph of the luminance-voltage curve of the
organic EL devices produced in Reference Examples 2 and 3, and
Example 3;
[0090] FIG. 25 is a graph of the current density-voltage curve of
the EL devices produced in Reference Examples 2 and 3, and Example
3;
[0091] FIG. 26 is a graph of the current efficiency-current density
curve of the EL devices produced in Reference Examples 2 and 3, and
Example 3;
[0092] FIG. 27 is a graph of the luminance-voltage curve of three
organic EL devices produced in Example 4;
[0093] FIG. 28 is a graph of the current density-voltage curve of
three EL devices produced in Example 4;
[0094] FIG. 29 is a graph of the current efficiency-current density
curve of three EL devices produced in Example 4;
[0095] FIG. 30 is a graph of the luminance-voltage curve of three
organic EL devices produced in Example 5;
[0096] FIG. 31 is a graph of the current density-voltage curve of
three EL devices produced in Example 5;
[0097] FIG. 32 is a graph of the current efficiency-current density
curve of three EL devices produced in Example 5;
[0098] FIG. 33 is a plan view showing a device having a sandwiched
structure used in the evaluation of the resistivity;
[0099] FIG. 34 is a cross-sectional view showing a device having a
sandwiched structure used in the evaluation of the resistivity;
[0100] FIG. 35 is a plan view showing a device having a coplanar
arrangement structure used in the evaluation of the
resistivity;
[0101] FIG. 36 is a cross-sectional view showing a device having a
coplanar arrangement structure used in the evaluation of the
resistivity;
[0102] FIG. 37 is a graph of the electric field-current density
curve for calculating a resistivity determined in a Test
Example;
[0103] FIG. 38A is a photograph showing an emission state in the
organic EL device described in Japanese Patent Application No.
2001-225847;
[0104] FIG. 38B is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device;
[0105] FIG. 39A is a photograph showing an emission state in the
organic EL device produced in Example 3;
[0106] FIG. 39B is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
3;FIG. 40 is a graph showing a relation between mixed ratio (molar
fraction) of the co-deposition layer of V.sub.2O.sub.5 and
.alpha.-NPD, and resistivity;
[0107] FIG. 41 is a schematic cross-sectional view illustrating a
lamination structure of the organic EL device produced in Example
6;
[0108] FIG. 42 is a graph of the luminance-voltage curve of the
organic EL devices produced in Example 6 and a conventional
device;
[0109] FIG. 43 is a graph of the current density-voltage curve of
the EL devices produced in Example 6 and a conventional device;
[0110] FIG. 44 is a graph of the current efficiency-current density
curve of the EL devices produced in Example 6 and a conventional
device; and
[0111] FIG. 45 is a graph of the luminous efficiency-luminance
curve of the organic EL devices produced in Example 6 and a
conventional device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0112] The inventors of the present invention have conducted
intensive studies for solving the above-mentioned problems, and
have found that a solution can be attained if two or more laminated
light-emissive units are sandwiched between a cathode electrode and
an anode electrode opposed to the cathode electrode, and each of
the light-emissive units are partitioned with a charge generation
layer having a resistivity of at least 1.0.times.10.sup.2
.OMEGA.cm, desirably at least 1.0.times.10.sup.5 .OMEGA.cm.
Hereinafter, the property having such a resistivity is abbreviated
as "electrically insulating".
[0113] When a certain level of the voltage was applied between a
cathode and an anode in the EL device having the above structure,
only the two or more light-emissive units located in a crossed area
of the cathode and the anode can be connected as if connected in
series, and thus they can simultaneously emit light. Because of
this simultaneous emission, using the EL device, it becomes
possible to achieve a high quantum efficiency or current efficiency
which cannot be obtained in any conventional EL device.
[0114] As described above, according to the present invention, the
light-emissive units are connected "as if connected in series"
throughout the charge generation layer. Such a series connection of
the light-emissive units means that when a certain level of the
voltage was applied to the EL device, each charge generation layer
can inject holes in a cathode direction of the device, thus playing
a role for injecting electrons in an anode direction, and as a
result of injection of both the electrons and the holes, although
all the layers (light-emissive units and the charge generation
layers) sandwiched between the anode and the cathode are formed
from an electrically insulating layer, the two or more
light-emissive units can act just as they are electrically
connected in series as in an electrical circuit.
[0115] In other words, the organic EL device according to the
present invention resides in an organic EL device including two or
more light-emissive units between a cathode electrode and an anode
electrode opposed to the cathode electrode, each light-emissive
unit having at least one light-emissive layer, in which the
light-emissive units are partitioned from each other by at least
one charge generation layer, and the charge generation layer is an
electrically insulating layer having a resistivity of at least more
than 1.0.times.10.sup.2 .OMEGA.cm, desirably at least
1.0.times.10.sup.5 .OMEGA.cm.
[0116] Furthermore, the material used in the formation of layers
constituting each light-emissive unit corresponds to a component
sandwiched between the anode and the cathode in the conventional EL
devices, and thus all the layers formed therein are electrically
insulating layers having a resistivity of not less than
1.0.times.10.sup.2 .OMEGA.cm.
[0117] The "light-emissive unit" refers to a component of the EL
device having a layer structure including at least one
light-emissive layer including an organic compound, i.e., the
component of the conventional organic EL device from which an anode
and a cathode are omitted.
[0118] Furthermore, the "charge generation layer" refers to an
electrically insulating layer having a resistivity of not less than
1.0.times.10.sup.2 .OMEGA.cm, desirably at least 1.0.times.10.sup.5
.OMEGA.cm, and as described above, represents a layer capable of
injecting an electron for an anode direction of the device as well
as injecting a hole for a cathode direction of the device upon
voltage being applied.
[0119] In the organic EL device of the present invention, the
charge generation layer desirably includes a laminate or a mixed
layer formed from two different materials. A charge transfer
complex having a radical cation and a radical anion is formed upon
an oxidation-reduction reaction between these two materials. When a
voltage is applied to the EL device, a radical cation state (hole)
and a radical anion state (electron) in the charge transfer complex
is transferred to a direction of the cathode and a direction of the
anode, respectively, so that a hole is injected into the
light-emissive unit which is located on a cathode side of the
charge generation layer and is adjacent thereto, and an electron is
injected into the light-emissive unit which is located on an anode
side of the charge generation layer and is adjacent thereto.
[0120] Moreover, in the organic EL device of the present invention,
the charge generation layer desirably includes a laminated or a
mixed layer which has the following components:
[0121] (a) an organic compound having an ionization potential of
less than 5.7 eV and a hole transporting property or electron
donating property; and
[0122] (b) an inorganic or organic material capable of forming a
charge transfer complex through its oxidation-reduction reaction
with the organic compound (a); and
[0123] a charge transfer complex formed upon the
oxidation-reduction reaction between the components (a) and (b)
being contained in the charge generation layer.
[0124] In addition, in order to easily obtain a radical cation
state from an organic compound which generally has an electron
donating property, it is desirable that the organic compound has an
ionization potential of less than 5.7 eV. If the ionization
potential of the organic compound used as the component (a) is 5.7
eV or more, it is difficult to cause an oxidation-reduction between
the organic compound and the compound used as the component (b)
with result of difficulty in producing a charge transfer complex
which is required in when applying the present invention.
[0125] More particularly, the organic compound used as the
component (a) is desirably an arylamine compound, and the arylamine
compound is desirably represented by the following formula (I):
2
[0126] wherein Ar1, Ar2 and Ar3 each independently represent an
aromatic hydrocarbon group which can have substituents.
[0127] tetra-p-tolyl-4,4'-diaminobiphenyl,
bis(4-di-p-tolylaminophenyl)phe- nylmethane,
N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl,
N,N,N',N'-tetraphenyl-4,4'-diaminodiphenylether,
4,4'-bis(diphenylamino)q- uadriphenyl,
4-N,N-diphenylamino-(2-diphenylvinyl)benzene,
3-methoxy-4'-N,N-diphenylaminostilbenzene, N-phenylcarbazole,
1,1-bis(4-di-p-triaminophenyl)cyclohexane,
1,1-bis(4-di-p-triaminophenyl)- -4-phenylcyclohexane,
bis(4-dimethylamino-2-methylphenyl)phenylmethane,
N,N,N-tri(p-tolyl)amine,
4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styry- l]stilbene,
N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl N-phenylcarbazole,
4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl,
4,4"-bis[N-(1-naphthyl)-N- -phenylamino]p-terphenyl,
4,4'-bis[N-(3-acenaphthenyl)-N-phenylamino]biphe- nyl,
1,5-bis[N-(1-naphthyl)-N-phenylamino]naphthalene,
4,4'-bis[N-(9-anthryl)-N-phenylamino]biphenyl,
4,4"-bis[N-(1-anthryl)-N-p- henylamino]p-terphenyl,
4,4'-bis[N-(2-phenanthryl)-N-phenylamino]biphenyl,
4,4'-bis[N-(8-fluoranthenyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(2-pyrenyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(2-perylenyl)-N- -phenylamino]biphenyl,
4,4'-bis[N-(1-coronenyl)-N-phenylamino]biphenyl,
2,6-bis(di-p-tolylamino)naphthalene,
2,6-bis[di-(1-naphthyl)amino]naphtha- lene,
2,6-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]naphthalene,
4,4"-bis[N,N-di(2-naphthyl)amino]terphenyl, 4,4'-bis
{N-phenyl-N-[4-(1-naphthyl)phenyl]amino}biphenyl,
4,4'-bis[N-phenyl-N-(2-- pyrenyl)amino]biphenyl,
2,6-bis[N,N-di(2-naphthyl)amino]fluorene,
4,4"-bis(N,N-di-p-tolylamino)terphenyl,
bis(N-1-naphthyl)(N-2-naphthyl)am- ine,
4,4'-bis[N-(2-naphthyl)-N-phenylamino]biphenyl (.alpha.-NPD),
represented by the following formula: 3
[0128] , spiro-NPD represented by the following formula: 4
[0129] , spiro-TAD represented by the following formula: 5
[0130] , 2-TNATA represented by the following formula: 6
[0131] , and the like.
[0132] Furthermore, any well-known arylamine compound used in the
production of a conventional organic EL devices can be suitably
used.
[0133] Furthermore, in regard to increasing a heat resistance of
the devices, it is desirable that the arylamine compound used
herein is an arylamine compound having a glass transition
temperature of not lower than 90.degree. C.
[0134] Among many arylamine compounds listed above, .alpha.-NPD,
spiro-NPB, spiro-TAD and 2-TNATA are typical examples of a suitable
arylamine compound because they have a glass transition temperature
of not lower than 90.degree. C.
[0135] In the organic EL device of the present invention, if the
charge generation layer is constructed from a laminate including
two different materials, one material constituting the laminate can
be an organic material which constitutes a hole transporting layer
in the light-emissive unit adjacent to the charge generation layer.
Furthermore, in such a case, the hole transporting layer is
desirably constructed from an arylamine compound used as the
component (a).
[0136] The present invention will be further described with
reference to the accompanying drawings.
[0137] As described above, the organic EL device according to the
present invention is characterized in that the device includes an
anode electrode/a plurality of light-emissive units (includes at
least one light-emissive layer, principally consists of an organic
material and generally has a laminated structure of two or more
layers)/a cathode electrode. The plurality of light-emissive units
are provided between the anode and cathode electrodes, and each
light-emissive unit is partitioned with an electrically insulating
charge generation layer having a resistivity or specific resistance
of not less than 1.0.times.10.sup.2 .OMEGA.cm, desirably not less
than 1.0.times.10.sup.5 .OMEGA.cm.
[0138] As shown in FIG. 1, the prior art organic EL device has a
construction in which a single light-emissive unit is sandwiched in
between the electrodes, and an electron (e.sup.-) is injected from
a cathode side into the unit, while a hole (h.sup.+) is injected
from an anode side into the unit so that the electron and the hole
can be recombined inside the unit, thereby an excitation state to
cause light emission.
[0139] Conversely, in the organic EL device according to the
present invention, as shown in FIG. 2, a recombination of the
electron and the hole can be made within the plurality of
light-emissive units, each being partitioned by a charge generation
layer, and thus a plurality of light emissions can be generated
between the electrodes.
[0140] In the organic EL device of the present invention an
electrically insulating material having a resistivity of not less
than 1.0.times.10.sup.2 .OMEGA.cm, desirably not less than
1.0.times.10.sup.5 .OMEGA.cm is used as a material for forming a
charge generation layer. Furthermore, generally, the charge
generation layer is desirably a layer having a visible light
transmittance of not less than 50%. A transmittance of less than
50% will not provide the desired quantum efficiency (current
efficiency) even if the device has a plurality of the
light-emissive units because the light generated in the units is
absorbed during its transmission through the charge generation
layer.
[0141] Furthermore, both an inorganic material and an organic
material can be used as a material for forming a charge generation
layer, providing the material used has a specific resistivity
described above. However, a suitable construction of the charge
generation layer of the present invention, as described above,
includes a laminate or a mixed layer formed from two different
materials. Upon oxidation-reduction reaction between these two
materials, a charge transfer complex including a radical cation and
a radical anion is formed in the charge generation layer. Since a
radical cation state and a radical anion state in the charge
transfer complex are moved to a cathode direction and an anode
direction, respectively, when a voltage is applied, the charge
generation layer can inject a hole in a light-emissive unit
adjacent to the layer on a cathode side and also can inject an
electron in a light-emissive unit adjacent to the layer on an anode
side.
[0142] As described above, the charge generation layer in the
device of the present invention is desirably a laminate or a mixed
layer formed from an arylamine compound such as the component (a)
and a substance, such as the component (b), which may be an
inorganic substance or an organic substance, capable of forming a
charge transfer complex upon the oxidation-reduction reaction with
the arylamine compound.
[0143] FIG. 3 is a schematic view showing a charge transfer complex
formation in a charge generation layer which is a laminate
including the above-described components (a) and (b), and the
transfer of electrons and holes in the charge generation layer upon
application of the voltage.
[0144] Furthermore, FIG. 4 is a schematic view showing a charge
transfer complex formation and transfer of electrons and holes upon
application of voltage in a charge generation layer which is a
mixed layer including the above components (a) and (b).
[0145] Furthermore, whether or not the two compounds constituting
the charge generation layer can form a charge transfer complex can
be confirmed by using a spectroscopic analysis. For example, when
the two compounds are examined, it can be confirmed that in
separate use, the each compound does not exhibit an absorption peak
in a near infrared region of the wavelength of 800 to 2,000 nm,
however, if they are used as a mixed layer, the layer can show an
absorption peak in a near infrared region of the wavelength of 800
to 2,000 nm, i.e., the confirmed absorption peak clearly teaches
the presence (or evidence) of an electron transfer between the two
compounds.
[0146] FIG. 5 shows an absorption spectrum obtained in a sole use
of each of arylamine compounds: 2-TNATA, .alpha.-NPD, spiro-TAD and
spiro-NPB, and V.sub.2O.sub.5 (vanadium pentaoxide), and an
absorption spectrum obtained in a mixed layer of each arylamine
compound and vanadium pentaoxide. As can be appreciated from the
graph of FIG. 5, the arylamine compounds and vanadium pentaoxide
each cannot show a peak in a near IR region of the wavelength of
800 to 2,000 nm when they are used alone, but, if they are used in
the form of a mixed layer including the arylamine compound and
vanadium pentaoxide, the layer can show a prominent peak in a near
IR region of the wavelength of 800 to 2, 000 nm, from which a
charge transfer complex formation can be confirmed.
[0147] FIG. 6 shows an absorption spectrum of each of 2-TNATA and
4F-TCNQ obtained when they are used in the form of a single layer
or a mixed layer, and FIG. 7 shows an absorption spectrum obtained
in a mixed layer of .alpha.-NPD and Re2O7 (di-rhenium
heptaoxide).
[0148] The inventors of the present invention could observe from
the absorption spectrums of each of the mixed layers shown in FIGS.
5 to 7 that a new and third absorption spectrum was produced in a
position of the near IR region (800 to 2,000 nm) upon the reaction
caused with the electron transfer, and the third absorption
spectrum is not a simply piled up spectrum curve obtained as a
result of combination of a spectrum of one single substance with a
spectrum of another single substance. The inventors have studied
and found that a chemical reaction generated in the mixed layer is
an important factor to ensure a charge transfer upon application of
the voltage.
[0149] When two compounds (or layers) are laminated, it is easily
conceived that a chemical reaction can be generated in an
interfacial surface between the two layers. Thus, it is true that
the intended and desired properties can be obtained in a charge
generation layer when the layer is formed by lamination of the two
compounds.
[0150] In the present invention, the terms "light-emissive unit",
as explained above, means a "component of the conventional organic
EL device" excluding an anode and a cathode.
[0151] The "component of the conventional organic EL device"
includes, for example, (anode)/a light-emissive layer/(cathode),
(anode)/a hole-transporting layer/a light-emissive layer/(cathode),
(anode)/a hole-transporting layer/a light-emissive layer/an
electron-transporting layer/(cathode), (anode)/a hole injection
layer/a hole-transporting layer/a light-emissive layer/an
electron-transporting layer/(cathode) and the like.
[0152] In the organic EL device according to the present invention,
the light-emissive units may have any laminate structure, providing
the laminate structure satisfies the requirement that each
light-emissive unit is partitioned with an electrically insulating
charge generation layer and that there are a plurality of
light-emissive units. Furthermore, the materials used in the
formation of a light-emissive layer, a hole-transporting layer, a
hole injection layer, an electron-transporting layer, an electron
injection layer, and the like are not restricted to any specific
material and can be any conventional material used in the formation
of these layers.
[0153] Furthermore, the light-emissive or luminescent materials
which may be added to a light-emissive layer are also not
restricted to a specific material, and can be any well-known
material which includes, for example, a wide variety of fluorescent
materials and phosphorescent materials.
[0154] Generally, a metal having a low work function or a metal
alloy, a metal oxide, and the like, containing such a low work
function metal is mainly used as the cathode material.
Specifically, the cathode material includes, for example, a single
body of a metal, for example, an alkaline metal such as Li, and the
like, an alkaline earth metal such as Mg, Ca, and the like, a rare
earth metal such as Eu, and the like, and a metal alloy of these
metals and Al, Ag, In, and the like. Furthermore, in the device
construction suggested by the inventors in Japanese Laid-open
Patent Application Nos. 10-270171 and 2001-102175, in which a
metal-doped organic layer is used in an interfacial surface between
a cathode and an organic layer, any electrically conducting
material may be used as the cathode material. In this construction,
the selection of the cathode material is not restricted by
properties such as work function of the selected material.
[0155] Moreover, if an organic layer adjacent to a cathode is
constructed from an organic metal complex compound containing at
least one of alkaline metal ions, alkaline earth metal ions and
rare metal ions using the technologies disclosed by the inventors
in their Japanese Laid-open Patent Application Nos. 11-233262 and
2000-182774, a metal capable of reducing a metal ion contained in
the complex compound in vacuum to the corresponding metal, for
example, a thermally reducible metal such as Al, Zr, Ti, Si, and
the like, or an alloy including these metals may be used as the
cathode material. Among these metals, aluminum (Al) which is
generally and widely used as a wiring material is particularly
desired as the cathode material in view of its easy vapor
deposition, high light reflectance and chemical stability.
[0156] Similarly, the anode material is not restricted to a
specific material. For example, a transparent conducting material
such as ITO (indium tin oxide), IZO (indium zinc oxide), and the
like, can be used as the anode material.
[0157] Furthermore, assuming that an ITO coating is formed with a
sputtering method using the process suggested in Japanese Patent
Application No. 2001-142672 to avoid damage in an organic layer, a
transparent conducting material such as above described ITO and IZO
may be used as the cathode material if a metal-doped organic layer
described in Japanese Laid-open Patent Application No. 10-270171 is
used as an electron injection layer in the manner described above.
Accordingly, it becomes possible to produce a transparent
light-emitting device by forming both of the cathode and the anode
as a transparent electrode, because the organic layer and the
charge generation layer are also transparent. Alternatively,
contrary to the structure of the above-described general organic EL
device, if an anode is formed from any metal material and a cathode
is formed as a transparent electrode, it is possible to provide a
device structure in which the emitted light can be projected from a
laminated-layers side of the device, not from a substrate side of
the device.
[0158] In addition, the order of the steps for forming layers is
not restricted to any specific order. Namely, the layer formation
may not always be started from an anode side of the device, and the
layers may be formed from a cathode side of the device.
[0159] In the organic EL device of the present invention, types of
the material used in the formation of cathode and anode electrodes
or the method for forming a charge injection layer adjacent to
these electrodes may be based on well-known technology widely used
in the conventional EL devices, providing that two or more
light-emissive units are contained between the opposed cathode and
anode electrodes and each light-emissive unit is partitioned by a
charge generation layer having a resistivity of not less than
1.0.times.10.sup.2 .OMEGA.cm, desirably not less than
1.0.times.10.sup.5 .OMEGA.cm.
[0160] The organic EL device of the present invention having a
novel device structure is distinguishable from the conventional
organic EL devices in view of the following notably different
characteristics.
[0161] Firstly, in the organic EL device of the present invention,
a theoretical limitation is not applied to the quantum efficiency
of the device, whereas in the conventional EL devices, an upper
limitation of the quantum efficiency which is a ratio of photon
(number)/sec vs. electron (number)/sec, simply determined in an
external circuit, is 1 (=100%) in theory. This is because an
injection of hole (h.sup.+) shown in FIG. 2 means a generation of a
radical cation as a function of withdrawal of electrons from a
valance band (or HOMO, highest occupied molecular orbital) of an
organic layer, and thus the electrons withdrawn from a valance band
of the organic layer constituting a layer adjacent to the charge
generation layer on a cathode side is injected into an electron
conduction band (or LUMO, lowest unoccupied molecular orbital) of
an organic layer constituting a layer adjacent to the layer on an
anode side, thereby producing a light-emissive excitation state.
Namely, the withdrawn electrons are again utilized in the formation
of a light-emissive excitation state.
[0162] Accordingly, in the organic EL device of the present
invention, the quantum efficiency thereof is calculated as a sum of
the quantum efficiency of each light-emissive unit partitioned with
a charge generation layer wherein the quantum efficiency is defined
as a ratio of electrons (apparent number) passing thorough each
light-emissive unit/sec vs. photons (number), emitted from each
light-emissive unit/sec, and therefore the quantum efficiency has
no upper limit.
[0163] Namely, the organic EL device of the present invention can
still be operated as a planar and thin film-shaped light-emissive
device capable of emitting light only from a crossed area of the
cathode and the anode as in the conventional organic EL devices,
although it has a circuit structure the same as that of the
conventional devices in which plural EL devices are connected in
series with a metal wiring, because the present device has a charge
generation layer having a very thin and transparent layer structure
and the charge generation layer is constructed from an
(electrically) insulating layer having a resistivity which is
substantially the same as that of the organic layer.
[0164] Although the organic EL device of the present invention is
only constructed from an insulating material having a resistivity
of not less than 1.0.times.10.sup.2 .OMEGA.cm, desirably not less
than 1.0.times.10.sup.5 .OMEGA.cm, except for the electrodes, the
organic EL device can be operated at a driving voltage which is a
sum of the potential reduction amount (Vn) consumed in each of the
light-emissive units, i.e., V=V1+V2+ . . . +Vn, because the present
device is consequently operated just as if the plurality (n) of the
conventional EL devices were connected in series. Accordingly, an
advantage obtained in conventional devices, i.e., a low voltage
driving at 10 volts or less, cannot be obtained in the present
device with increase of the number (n) of the light-emissive
units.
[0165] However, the organic EL device of the present invention
still has some advantages over conventional organic EL devices. In
conventional devices, since the luminance is substantially
proportional to a current density, it was essentially required to
apply a higher current density to obtain an increased luminance. On
the other hand, since, as previously mentioned, the operational
life-time of the device was inversely proportional to the current
density (not to a driving voltage), a high luminance emission
results in a shortened operational life-time of the device.
[0166] Contrary to the drawbacks of conventional devices, in the
organic EL device of the present invention, if it is desired to
obtain an n-times increased luminance at a desired current density,
such a increase of the luminance can be attained by increasing the
number of the light-emissive units (each having the same
construction) used between the electrodes by n-times, without
increasing the current density.
[0167] In this method, the driving voltage will be also increased
to a level of n-times or more. However, it should be noted that an
unexpected and important advantage is that an n-times increased
luminance can be achieved without sacrificing the operational
life-time.
[0168] Furthermore, in the organic EL device of the present
invention, a layer thickness between the cathode and the anode can
be naturally increased by increasing the number of the
light-emissive units used therein. For example, assuming that the
number of the light-emissive units between the electrodes is "n", a
layer thickness of the present device is increased to about n-times
of that of the conventional EL devices. In addition, since the
number of the light-emissive units in the present device is not
restrictive, a layer thickness between the electrodes is also not
restrictive. In view of the fact that in conventional EL devices, a
layer thickness between the electrodes of not exceeding 1 .mu.m
(practically, not more than 2000 .ANG. (not more than 200 nm)) and
that a driving voltage of 25 volts or less must be applied, the
present EL device has an essentially different characteristics
which cannot be found in the conventional EL devices (above
mentioned Kodak Patent, Japanese Laid-open Patent Application
Nos.59-194393, 63-264692 and 2-15595, U.S. Pat. Nos. 4,539,507,
4,769,292, and 4,885,211).
[0169] Namely, in the organic EL device of the present invention,
there is no necessity to define an upper limit of the layer
thickness between the electrodes, an upper limit of the driving
voltage and an upper limit of the quantum efficiency (current
efficiency).
[0170] On the other hand, in conventional organic EL devices, an
increase of the driving voltage results only in a reduction of the
power conversion efficiency (w/w). Conversely, according to the
organic EL device of the present invention, in principle, the
conversion efficiency (w/w) can be maintained without any change,
because if "n" of the light-emissive units are introduced between
the electrodes, the light-emission starting voltage (turn on
voltage), and the like, are increased by about n-times, and
accordingly the voltage for obtaining the desired luminance is
increased by about n-times, and in addition to the increase of
these voltages, the quantum efficiency (current efficiency) can be
also increased by about n-times.
[0171] Moreover, the organic EL device of the present invention
containing a plurality of the light-emissive units has a secondary
advantage of being able to reduce the risk of short circuiting in
the device. In conventional EL devices containing only one
light-emissive unit, if an electrical short circuit is caused
between a cathode and an anode due to presence of pin-holes, etc.,
in the layer of the unit, the EL devices could immediately change
to a state of emitting no light. Conversely, in the organic EL
device of the present invention, since the layer thickness between
the electrodes is thick, a risk of short circuiting can be reduced,
and at the same time, even if short circuiting is caused in some
light-emissive units, the worst scenario result such as non-light
emission can be avoided because the remaining light-emissive units
can still emit light. Specifically, when the EL device is designed
to be driven at a constant current, a driving voltage is only
reduced by an amount corresponding to the short circuited units,
and the remaining non-short circuited units can emit light
normally.
[0172] In addition to the above advantages, for example, when the
organic EL device of the present invention is applied to an EL
display device having a simple matrix structure, a reduction of the
current density means that a voltage reduction due to the wiring
resistance and a temperature increase in the substrate can be
largely reduced in comparison with a conventional display device.
Furthermore, a higher driving voltage between the electrodes, which
sandwich the light-emissive element portion, in comparison with the
conventional devices means that a voltage reduction due to the
wiring resistance does not largely cause a reduction of the
luminance (the effect due the higher driving voltage can be
sufficiently understood just from considering the influence of the
possible potential reduction of 1 volt due to the wiring resistance
to a reduction of the luminance in comparison with an EL device
capable of providing a luminance of 1,000 cd/m.sup.2 at 5 volts and
an EL device capable of providing a luminance of 1,000 cd/m.sup.2
at 50 volts). This effect, in combination with another
characteristic of the EL device of the present invention where the
device naturally has a low voltage reduction in the wiring portion
thereof, enables to achieve a display device controllable at a
constant voltage which can not be provided using a conventional
device.
[0173] Furthermore, the above-described characteristics
advantageously affect other uses for obtaining an uniform light
emission in a large surface area, in particular, for use as an
illumination apparatus. In conventional organic EL devices, since
an electrode material used therein, especially a transparent
electrode material, typically ITO, etc., has a resistivity of up to
10.sup.-4 .OMEGA.cm, which is about 100 .OMEGA. cm higher than a
resistivity of metal (up to 10.sup.-6 .OMEGA.cm), a voltage (V) or
electric field E (V/cm) applied to the light-emissive unit reduces
with an increase of the distance from a contact point of electric
power, so that unevenness (difference of luminance) in the
luminance occurs between a near portion to and a far portion from a
contact point of electric power. Conversely, according to the
organic EL device of the present invention, since an electric
current in obtaining the desired luminance can be largely reduced
in comparison with conventional EL devices, the potential reduction
can be diminished with the result that substantially uniform light
emission can be obtained in a large surface illumination
apparatus.
[0174] Furthermore, in the formation of the charge generation
layer, since the present invention is characterized by
intentionally using a material having a considerably increased
resistivity (of not less than 1.0.times.10.sup.2 .OMEGA.cm,
desirably not less than 1.0.times.10 .OMEGA.cm) than that of an ITO
and other electrically conductive materials (about 10.sup.-4
.OMEGA.cm), a shadow mask for defining a vapor deposition area,
which is with the same as that used in the formation of the
patterned organic layer, can be used in the layer formation process
of the charge generation layer, and thus the frequent change and
precise positioning of the shadow mask can be excluded from the
production process except for the formation of the electrodes.
Namely, according to the present invention, it becomes possible to
achieve a remarkably increased productivity.
[0175] FIG. 8 is a schematic cross-sectional view illustrating a
laminated structure of the organic EL device according to an
embodiment of the present invention. A glass substrate (transparent
substrate) 1 includes, laminated in sequence thereon, a transparent
electrode 2 constituting an anode electrode, a light-emissive unit
3-1, a charge generation layer 4-1, a light-emissive unit 3-2, a
charge generation layer 4-2, . . . , a charge generation layer
4-(n-1), a light-emissive unit (3-n) wherein the n=1, 2, 3, . . . ,
and finally a cathode electrode (metal electrode) 5. In these
elements (layers), the glass substrate (transparent substrate) 1,
the transparent anode electrode 2, the light-emissive unit (3-n)
wherein n is 1, 2, 3, . . . , and the cathode electrode 5 each is a
well-known element (layer). The new feature in the EL device of the
present invention resides in that a plurality of light-emissive
units (3-n, wherein n is 1, 2, 3, . . . ) are contained between
both electrodes and are partitioned with an electrically insulating
charge generation layer (4-n, wherein n is 1, 2, 3, . . . ) having
a resistivity of not less than 1.0.times.10.sup.2 .OMEGA.cm.
[0176] Furthermore, in regard to organic EL devices, it is known
that the characteristics thereof such as driving voltage, etc., can
be varied depending upon the work function; the work function being
one property of the electrode material. Referring to the organic EL
device of the present invention, the charge generation layer 4-n
used therein is not acting as an electrode. However, since an
electron is injected into a direction of the anode electrode and a
hole is injected in a direction of the cathode electrode, in the
formation of the above-described components of the light-emissive
unit, particularly the method for forming a electron injection
(transporting) layer and a hole injection (transporting) layer,
both being adjacent to a charge generation layer, is essential for
reducing an energy barrier in the injection of the charge (electron
and hole) into each light-emissive unit.
[0177] For example, if it is intended to inject an electron from
each charge generation layer 4-n to a direction of the anode
electrode, it is desirable that, as is disclosed in Japanese
Laid-open Patent Application Nos. 10-270171 and 2001-102175, an
electron injection layer having a mixed layer of an organic
compound and a metal functioning as an electron donating (donor)
dopant, is formed as a layer adjacent to the charge generation
layer in anode side. The donor dopant desirably includes at least
one metal selected from alkaline metals, alkaline earth metals and
rare earth metals.
[0178] Furthermore, in the electron injection layer, a molar ratio
of the metal as the donor dopant is desirably in the range of 0.1
to 10 with respect to the organic compound. A molar ratio of less
than 0.1 results in a reduction of the doping effect because a
concentration of the molecule reduced with the dopant (hereinafter,
referred to as a "reduced molecule") is reduced excessively. A
molar ratio above 10 also results in a reduction of the doping
effects because a concentration of the dopant in the layer is
significantly increased in comparison with concentration of the
organic compound, thus causing an excessive reduction of the
reduced molecule in the layer.
[0179] The application of the above-described electron injection
layer-containing structure to a light-emissive unit of the organic
EL device achieves an energy barrier-free electron injection to
each of the light-emissive units regardless of the work function of
the material constituting a charge generation layer.
[0180] Furthermore, the light-emissive unit may have a structure in
which an electron injection layer including a metal selected from
alkaline metals, alkaline earth metals and rare earth metals, and
having a layer thickness of up to 5 nm (desirably 0.2 to 5 nm) is
disposed as a layer adjacent to the charge generation layer on an
anode side. A layer thickness of above 5 nm is not desirable
because it reduces a light transmittance, and at the same time,
makes the device unstable because the content of the metal which
has a high reactivity and is unstable in air is excessively
increased in the layer. Moreover, in this metal layer having a
layer thickness of up to 5 nm, it is considered that a substantial
amount of the metal layer can be diffused into an organic layer to
result in a layer having a composition which is substantially the
same as that of the above-described metal doping layer. The
resulting layer at least has no form of the metal layer having an
electrical conductivity.
[0181] For example, if the electron is injected from each charge
generation layer 4-n in the anode direction, it is also desirable
that the electron injection layer, which is disclosed in Japanese
Laid-open Patent Application Nos. 11-233262 and 2000-182774
(corresponding U.S. Pat. No. 6,396,209) (J. Endo, T.Matsumoto, and
J. Kido, Jpn. J. Appl. Phys. Vol. 41 (2002) pp.L800-L803), is
provided on the anode side of the charge generation layer. The
electron injection layer of this type is explained as an "in-situ
reaction generating layer" which is generated by depositing a
thermally reducible metal such as aluminum on a compound containing
an alkaline metal ion, an alkaline earth metal ion and a rare earth
metal ion to reduce the metal ions into a metal condition. In the
device of the present invention, it is desirable to supply the very
thin thermally reducible metal on the compound by a minimum amount
required for the reduction reaction. If the metal ion in the
compound is reduced, the supplied thermally reducible metal itself
is oxidized to be a insulative compound having a resistivity not
less than 1.0.times.10.sup.2 .OMEGA.cm. The very thin thermally
reducible metal has a layer thickness not more than 10 nm. If the
layer thickness of the thermally reducible metal is more than 10
nm, a metal atom, which does not contribute to the reduction
reaction, remains so that the transparency and insulation property
are lost.
[0182] In addition to an organic metal complex compound described
in the above mentioned patent document (Japanese Laid-open Patent
Application Nos.11-233262 and 2000-182774), an inorganic compound
can be used as the compound including the alkaline metal ion,
alkaline earth metal ion and rare earth metal ion, which are used
for the above mentioned "in-situ reaction generating layer". An
oxide and halide including the alkaline metal ion, alkaline earth
metal ion and rare earth metal ion can be used as the compound for
the in-situ reaction generating layer, and further, any inorganic
compound including the alkaline metal ion, alkaline earth metal ion
and rare earth metal ion can be used as the compound.
[0183] Furthermore, it is also desirable to use different types of
electron injection (transporting) layers in above mentioned
Japanese Laid-open Patent Application Nos. 10-270171, 2001-102175,
11-233262 and 2000-182774 (corresponding to U.S. Pat. No.
6,396,209) in a superposed condition. The metal doping layer in the
Japanese Laid-open Patent Application No. 10-270171 or 2001-102175
is desirably deposited on the organic layer (including
light-emissive layer), by a predetermined thickness, as a low
resistance electron transporting layer, then the in-situ reaction
generating layer described in the Japanese Laid-open Patent
Application Nos. 11-233262 and 2000-182774 is superposed on the
metal doping layer. As mentioned above, a technical idea in which
an electron injection layer contacting the cathode electrode of the
conventional electroluminescent device is formed by using
superposed different types of electron injection (transporting)
layers is described in the Japanese Patent Application No.
2002-273656 by the inventors of the present invention.
[0184] In this case, the in-situ reaction generating layer contacts
the charge generation layer on an anode side. According to the
present invention, an interaction between a material used for the
charge generation layer and a reactive metal such as alkaline metal
can be avoided. As a result, it is found that such method is a
desirable for forming an electron injection layer on a point that
the electron injection barrier from the charge generation layer to
the light emissive unit can be lowered.
[0185] Furthermore, for example in the injection of holes from each
charge generation layer 4-n to a direction of the cathode
electrode, a hole injection layer, suggested by the inventors in
Japanese Laid-open Patent Application Nos. 11-251067 and
2001-244079, which contains a doped electron-accepting compound
(Lewis acid compound) having a property of oxidizing an organic
compound in terms of Lewis acid chemistry may be formed as a layer
adjacent to the charge generation layer in a cathode side.
Regardless of the work function of the material constituting the
charge generation layer 4-n, hole injection in the absence of an
energy barrier can be achieved.
[0186] Moreover, a layer of the electron-accepting compound (Lewis
acid compound) which is very thin and thus ensures a transparency
may be formed as a hole injection layer. In this method, a layer
thickness of the hole injection layer is desirably 30 nm or less,
more desirably in the range of 0.5 to 30 nm. The layer thickness
above 30 nm causes a reduction of the light transmittance, and at
the same time, makes the device unstable because a content of the
Lewis acid compound which has a high reactiveness and is unstable
in air is excessively included in the layer.
[0187] The electron-accepting compound (Lewis acid compound) used
herein is not restricted to a specific compound. For example,
electron-accepting compound includes an inorganic compound such as
ferric chloride, ferric bromide, ferric iodide, aluminum chloride,
aluminum bromide, aluminum iodide, gallium chloride, gallium
bromide, gallium iodide, indium chloride, indium bromide, indium
iodide, antimony pentachloride, arsenic pentafluoride, boron
trifluoride, and the like, and an organic compound such as DDQ
(dicyanodichloroquinone), TNF (trinitrofluorenone), TCNQ
(tetracyanoquinodimethane), 4F-TCNQ
(tetrafluoro-tetracyanoquinodimethane- ), and the like.
[0188] In the hole injection layer, a molar ratio of the organic
compound and the electron-accepting compound (dopant compound) is
desirably in the range of 0.01 to 10 with respect to the organic
compound. A molar ratio of less than 0.01 results in a reduction of
the doping effects because a concentration of the molecule oxidized
with the dopant (hereinafter, referred also to an "oxidized
molecule") is excessively reduced. A molar ratio above 10 also
results in a reduction of the doping effects because a
concentration of the dopant in the layer is remarkably increased in
comparison with concentration of the organic compound, thus causing
an excessive reduction of a concentration of the oxidized molecule
in the layer.
[0189] Further, if the material forming a charge generation layer
has a work function of not less than 4.5 eV, it may be sometimes
possible to inject holes to each light-emissive unit without
specially using an electron-accepting compound (Lewis acid
compound).
[0190] Conversely, as shown in Example 2 described hereinafter, the
Lewis acid compound itself may sometimes act as a component of the
charge generation layer.
[0191] In the light-emissive units used in the present invention,
the layers which are formed in direct contact with the cathode or
anode may have the same composition as that of the layer adjacent
to the charge generation layer on an anode side or the layer
adjacent to the charge generation layer on a cathode side,
respectively, or the electron injection layer and the hole
injection layer each may have some other compositions. Of course,
the electron injection layer and the hole injection layer used in
the conventional EL devices may be suitably used.
[0192] In comparison with conventional organic EL devices, the
amount of time it takes for the layer to be formed in the
production of the organic EL device of the present invention is
necessarily longer. Furthermore, since the present method is
characterized in that the substantially same processes are
repeatedly carried out, conventional batch system-based vapor
deposition apparatuses which are currently widely used for layer
formation require an excessively long processing time. Moreover, an
increase of the production costs is of concern because a large
amount of expensive organic materials must be used, compared to
conventional organic EL devices.
[0193] In such a case, it is suggested by the inventors in Japanese
Patent Application No. 2001-153367 to use an in line-line
system-based continuous layer formation apparatus. Using this
apparatus, the time required for layer formation can be largely
shortened and the efficiency of materials use can be increased so
as to approach 100%.
[0194] Furthermore, in the formation of the organic layer, the
charge generation layer and the electrode layer which constitute
the organic EL device of the present invention, any well-known
deposition method which is conventionally used such as a resistive
heating vapor deposition method, an electron beam vapor deposition
method, a laser beam vapor deposition method, a sputtering method,
and the like, can be used.
[0195] In particular, when an inorganic substance or compound such
as metal oxide is used as an element for forming a charge
generation layer, a vapor deposition method must be carried out
with care, because there is a tendency that a deposited layer may
have a composition which is outside of the desired stoichiometric
composition due to separation, etc., of oxygen atoms from the
compound.
[0196] Furthermore, when an inorganic substance or compound is
deposited using a sputtering method, it is important to use a
method in which a substrate having the formed organic layer is
disposed separately from the plasma generated during the deposition
process to thereby avoid damage of the organic layer. At the same
time, it is also important that the molecules of the sputtered
inorganic compounds are softly deposited on the organic layer with
a kinetic energy up to a predetermined level in order to reduce
damage in the device.
[0197] For example, the facing target sputtering apparatus in which
a pair of opposed targets arranged separately from each other at a
certain distance have a reflection electrode for reflecting
electrons against a front peripheral portion of each of the
targets, and a -magnetic field generating device which is included
to form a parallel magnetic field having a portion parallel to a
surface of the target in the vicinity of the peripheral portion of
each target (see, Japanese Patent Application No. 2001-142672) can
be suitably used in the formation of the charge generation layer of
the present invention, too.
[0198] In addition, all the layers to be formed on a substrate can
be formed by the vapor deposition method in which all layers are
formed on a substrate by heating a vaporizable material in a vacuum
to deposit a vaporized or sublimed material on the substrate, and
includes transporting a substrate in a direction of a planar
surface thereof, a deposition area being open in a lower surface of
the substrate; providing a container, in a lower position of the
transporting substrate, including a vaporizable material having a
deposition width which can cover the deposition area extending in a
direction perpendicular to the transportation direction of the
substrate; and heating the container, thereby vaporizing or
subliming and thus depositing the vaporizable material in the
container (Japanese Patent Application No.2001-153367).
[0199] Furthermore, contrary to conventional EL devices, using the
organic EL device of the present invention, the highest light
emission efficiency can be obtained when an optical path length
from light-emissive site to light-reflective electrode is almost an
odd-numbered times greater than a quarter wavelength of light,
i.e., .lambda..times.(2n-1)/4 wherein n is 1, 2, 3, . . . , since
an important feature in the present invention is that two or more
light-emissive site are provided at intervals.
[0200] In conventional EL devices, a structure is adopted wherein
an optical path length from light-emissive site to light-reflective
electrode is adjusted to approximately an odd-numbered times a
quarter wavelength of light. In such devices, even if the organic
layer is formed at a larger thickness above the quarter wavelength
of light, the result is only an undesirable increase of the driving
voltage.
[0201] However, as disclosed in above mentioned Japanese Laid-open
Patent Application No. 2001-102175, if a combination of the
electron transporting organic compound and the alkaline metal (both
constituting an electron injection layer adjacent to a
light-reflective cathode) are appropriately selected, it becomes
possible to inhibit an increase of the driving voltage at a larger
layer thickness of about 1 .mu.m, and a color hue (namely, a
profile of the emission spectrum) can be largely changed because an
interference effect can be remarkably increased with an increase of
the layer thickness.
[0202] For example, assuming that an optical path length of the
electron injection layer is adjusted to be approximately an
odd-numbered times a quarter wavelength of light, i.e.,
.lambda..times.(2n-1)/4 wherein n is 1, 2, 3, . . . , a profile of
the resulting emission spectrum is narrowed by an increase of n. On
the other hand, if an optical path length of the electron injection
layer is adjusted to be approximately an even-numbered times a
quarter wavelength of light, i.e., .lambda..times.(2n)/4 wherein n
is 1, 2, 3, . . . , there arises a notable interference effect with
an increase of n, with the result that the emission efficiency is
largely deteriorated because an emission in the original
light-emitting peak is offset with the notable interference
effect.
[0203] Accordingly, when the organic EL device has the resultant
structure in which n is large and a plurality of light-emissive
site are contained as in the EL device of the present invention, it
is essential to exactly control the layer thickness from each
light-emissive site to a light-reflective electrode.
[0204] To be free from such troublesome fine adjustment of layer
thickness, it is desirable to construct the cathode electrode,
which was light reflective electrode conventionally when the anode
electrode is a transparent electrode, a non-reflective black
electrode, or to construct at least one layer existed in the
cathode electrode direction so as to function as a light absorbing
layer. Accordingly, problems with light interference can be
avoided.
[0205] Conversely, if the anode electrode is the light reflective
electrode, it is desirable that the anode electrode itself or at
least one layer existing in the anode electrode direction have a
light absorbing function.
[0206] If a light diffuse reflection surface is provided on one of
the electrodes when the other electrode is the transparent
electrode, problems with light interference can be avoided in
theory.
[0207] Furthermore, as is shown in the appended examples, another
feature of the present invention is that the light-emissive units
each have different emission colors so that a desired mixed
(superimposed) color emission can be obtained. In this case, it is
also necessary to optimize the optical path length from
light-emissive site to light-reflective electrode in the manner
described above. The necessity for the optimization of the layer
thickness will depend on the emission color in each light-emissive
unit.
EXAMPLES
[0208] The present invention will be further described with
reference to the examples below. Note, however, that the present
invention is not restricted to these examples.
[0209] In the following examples, the vapor deposition of the
organic compound and the metal, as well as formation of the charge
generation layer, was carried out by using a vapor deposition
apparatus commercially available from VIEETECH JAPAN. The control
of the deposition rate of the vapor deposition material and of the
thickness of the deposited layers is carried out by using a
thickness monitor, provided with a quartz oscillator and attached
to the vapor deposition apparatus, "CRTM-8000" commercially
available from ULVAC. Furthermore, to determine an actual layer
thickness after the layer formation, a stylus step meter "P10"
commercially available from Tencor, Co., was used. Furthermore, the
characteristics of the organic EL device were evaluated with the
source meter "2400", commercially available from KEITHLEY, and the
luminance meter "BM-8", commercially available from TOPCON. A DC
voltage was stepwise applied at an increasing rate of 0.2 volts per
2 seconds to the EL device having an ITO anode and an aluminum (Al)
cathode, and the luminance and the electric current were determined
after a lapse of one second from the completion of each increase of
the voltage. The EL spectrum was determined by using the optical
multi-channel analyzer, "PMA-11" commercially available from
HAMAMATSU PHOTONICS, driven at a constant electric current.
REFERENCE EXAMPLE 1
[0210] (Example for the Production of the Conventional Organic EL
Device-Green Light-Emitting Device)
[0211] The conventional organic EL device having a laminate
structure shown in FIG. 9 was produced as follows.
[0212] A glass substrate 1 used herein includes, coated in the
predetermined pattern on a surface thereof, a transparent anode
electrode 2 including an ITO (indium-tin oxide, sputtered product
commercially available from ASAHI GLASS, or ion plating product
commercially available from Nippon Sheet Glass Co., Ltd.) having a
sheet resistance of about 20 .OMEGA./.quadrature. (.OMEGA./sq.)
(see, FIG. 10A). Alpha(A)-NPD having a hole transporting property
was deposited, through a metal mask (shadow mask) 40 for organic
layer formation (see FIG. 10B), onto the ITO-coated glass substrate
1 under vacuum of about 10.sup.-6 Torr and at a deposition rate of
about 2 .ANG./sec to form a hole transportation layer 6 having a
thickness of about 700 .ANG..
[0213] An organic-metal complex of tris(8-quinolinolato) aluminum
(hereinafter, briefly referred to as "Alq") is represented by the
following formula: 7
[0214] and a coumarin derivative which is a green light-emissive
fluorescent dye, "C545T" (trade name) commercially available from
KODAK, were deposited onto the hole transportation layer 6 under
vacuum vapor deposition conditions to form a light-emissive layer 7
having a thickness of about 400 .ANG.. Each deposition rate was
adjusted so that the resulting light-emissive layer 7 contains a
fluorescent dye in a concentration of about 1% by weight.
[0215] Thereafter, bathocuproine represented by the following
formula: 8
[0216] and metal cesium (Cs) in a molar ratio of about 1:1 were
co-deposited under vacuum vapor deposition conditions to form a
metal (Cs)-doped electron injection layer 8 having a thickness of
about 200 .ANG. on the light-emissive layer 7. Each deposition rate
was adjusted to obtain the molar ratio of about 1:1.
[0217] Finally, aluminum (Al) was deposited through a metal mask
(shadow mask) 41 for cathode layer formation (see, FIG. 10C) at a
deposition rate of about 10 .ANG./sec onto the electron injection
layer 8 to form a cathode electrode 5 having a thickness of about
1,000 .ANG.. An organic EL device having a square light-emissive
area of 0.2 cm (length) by 0.2 cm (width) was thus obtained (see,
FIG. 10D).
[0218] FIG. 16 shows an emission spectrum of the resultant organic
EL device.
[0219] In this organic EL device, a DC voltage was applied between
the anode electrode (ITO) and the cathode electrode (Al), and the
characteristics of the green light emitted from the light-emissive
layer (co-deposited layer of Alq and C545T) 7 were measured to
obtain the results plotted in FIGS. 21, 22 and 23.
[0220] In FIGS. 21, 22 and 23, the circle symbols (O) designate the
luminance (cd/m.sup.2)-voltage (v) characteristic curve, a graph of
current density (mA/cm.sup.2)-voltage (v) characteristic curve and
a graph of current efficiency (cd/A)-current density (mA/cm.sup.2)
characteristic curve, respectively, of the EL device of Reference
Example 1.
[0221] In the EL device of Reference Example 1, a voltage at which
the emission was started was 2.2 volts.
Reference Example 2
[0222] (Example for the Production of the Conventional Organic EL
Device-Blue Light-Emitting Device)
[0223] A conventional organic EL device having a laminate structure
shown in FIG. 11 was produced in accordance with the manner similar
to Reference Example 1 as follows.
[0224] A glass substrate 1 used herein includes, coated in the
predetermined pattern on a surface thereof, a transparent anode
electrode 2 including an ITO (indium-tin oxide, sputtered product
commercially available from ASAHI GLASS) having a sheet resistance
of about 20 .OMEGA./.quadrature. (see, FIG. 10A). Spiro-NPB having
a hole transporting property was deposited, through a metal mask 40
for organic layer formation (see, FIG. 10B), onto the ITO-coated
glass substrate 1 under vacuum of about 10.sup.-6 Torr and at a
deposition rate of about 2 .ANG./sec to form a hole transportation
layer 9 having a thickness of about 800 .ANG..
[0225] Spiro-DPVBi represented by the following formula: 9
[0226] was deposited onto the hole transportation layer 9 under
vacuum vapor deposition conditions to form a light-emissive layer
10 having a thickness of about 400 .ANG..
[0227] Thereafter, as in Reference Example 1, bathocuproine and
metal cesium (Cs) in a molar ratio of about 1:1 were co-deposited
under the controlled vacuum vapor deposition conditions to form a
metal (Cs)-doped electron injection layer 11 having a thickness of
about 200 .ANG. on the light-emissive layer 10.
[0228] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the electron injection layer 11 to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. An
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D) In
FIG. 17, an emission spectrum of the resultant organic EL device
(Reference Example 2) is shown as a dotted line.
[0229] In this organic EL device, a DC voltage was applied to
between the anode electrode (ITO) and the cathode electrode (Al),
and the characteristics of the blue light emitted from the
light-emissive layer (spiro-DPVBi) 10 were measured to obtain the
results plotted in FIGS. 24, 25 and 26.
[0230] In FIGS. 24, 25 and 26, white circle symbols (O) represent a
graph of luminance (cd/m.sup.2)-voltage (v) characteristic curve, a
graph of current density (mA/cm.sup.2)-voltage (v) characteristic
curve and a graph of current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of the EL device
of Reference Example 2.
[0231] In the EL device of Reference Example 2, the voltage at
which the emission was started was 2.6 volts.
Reference Example 3
[0232] (Example for the Production of the Conventional Organic EL
Device-Red Light-Emitting Device)
[0233] A conventional organic EL device having a laminate structure
shown in FIG. 12 was produced in a manner similar to Reference
Example 1 as follows.
[0234] A glass substrate 1 used herein includes, coated in the
predetermined pattern on a surface thereof, a transparent anode
electrode 2 including an ITO (indium-tin oxide, sputtered product
commercially available from ASAHI GLASS) having a sheet resistance
of about 20 .OMEGA./F (see, FIG. 10A). .alpha.-NPD having a hole
transporting property was deposited, through a metal mask 40 for
organic layer formation (see, FIG. 10B), onto the ITO-coated glass
substrate 1 under vacuum of about 10.sup.-6 Torr and at a
deposition rate of about 2 .ANG./sec to form a hole transportation
layer 12 having a thickness of about 700 .ANG..
[0235] Alq and a red light-emissive fluorescent dye, "DCJTB" (trade
name) commercially available from KODAK, were deposited onto the
hole transportation layer 12 under the vacuum vapor deposition
conditions to form a light-emissive layer 13 having a thickness of
about 400 .ANG.. Each deposition rate was adjusted so that the
resulting light-emissive layer 13 contains the fluorescent dye in a
concentration of about 1% by weight.
[0236] Thereafter, as in Reference Example 1, bathocuproine and
metal cesium (Cs) in a molar ratio of about 1:1 were co-deposited
under the controlled vacuum vapor deposition conditions to form a
metal (Cs)-doped electron injection layer 14 having a thickness of
about 200 .ANG. on the light-emissive layer 13.
[0237] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the electron injection layer 11 to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. An
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0238] In FIG. 17, an emission spectrum of the resultant organic EL
device (Reference Example 3) is shown with a chain line.
[0239] In this organic EL device, a DC voltage was applied to
between the anode electrode (ITO) and the cathode electrode (Al),
and the characteristics of the red light emitted from the
light-emissive layer (co-deposited layer of Alq and DCJTB) 13 were
measured to obtain the results plotted in FIGS. 24, 25 and 26.
[0240] In FIGS. 24, 25 and 26, plus symbols (+) represent a graph
of luminance (cd/m.sup.2)-voltage (v) characteristic curve, a graph
of current density (mA/cm.sup.2)-voltage (v) characteristic curve
and a graph of current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of the EL device
(Reference Example 3).
[0241] In the EL device of Reference Example 3, a voltage at which
the emission was started was 2.2 volts.
Example 1
[0242] (Example for the Production of the Organic EL Device having
a Charge Generation Layer Including V.sub.2O.sub.5, Vanadium
Pentaoxide)
[0243] The organic EL device according to the present invention
having a laminate structure shown in FIG. 13 was produced as
follows.
[0244] In accordance with the manner and order described in
Reference Example 1, a light-emissive unit 3-1 was deposited
through a metal mask 40 for organic layer formation (see, FIG. 10B)
on an ITO pattern-coated glass substrate 1 shown in FIG. 10A.
Namely, a 600 .ANG.-thick .alpha.-NPD, a 400 .ANG.-thick layer
including Alq:C545T=100:1 (weight ratio), and a 200 .ANG.-thick
mixed layer including bathocuproine and metal cesium (Cs) were
sequentially deposited.
[0245] Subsequently, V.sub.2O.sub.5 (vanadium pentaoxide) was
deposited onto the metal-doped layer at a deposition rate of about
2 .ANG./sec to form a charge generation layer 4-1 having a
thickness of about 100 .ANG.. The formation of the charge
generation layer 4-1 was also carried out in the presence of the
metal mask 40 for organic layer formation (see, FIG. 10B).
[0246] Thereafter, while the metal mask 40 for organic layer
formation (FIG. 10B) is still on the glass substrate 1, the
above-described step was again repeated to form a light-emissive
unit 3-2. Namely, a 600 .ANG.-thick .alpha.-NPD, a 400 .ANG.-thick
layer including Alq:C545T=100:1 (weight ratio), and a 200
.ANG.-thick mixed layer including bathocuproine and a metal cesium
(Cs) were sequentially deposited.
[0247] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the light-emissive unit 3-2 to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. An
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0248] In this organic EL device, a DC voltage was applied to
between the anode electrode (ITO) and the cathode electrode (Al),
and the characteristics of the green light emitted from the
light-emissive layer (co-deposited layer of Alq and C545T) were
measured to obtain the results plotted in FIGS. 21, 22 and 23. In
FIGS. 21, 22 and 23, white square symbols (.quadrature.) represent
a graph of luminance (cd/m.sup.2)-voltage (v) characteristic curve,
a graph of current density (mA/cm.sup.2)-voltage (v) characteristic
curve, and a graph of current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of the EL device
of Example 1.
[0249] In this EL device, a voltage at which the emission was
started was 4.4 volts, i.e., exactly 2 times of the voltage
observed in Reference Example 1.
[0250] As can appreciated from the above results, the organic EL
device which includes two light-emissive units, each partitioned
with a charge generation layer, achieves an increased maximum
current efficiency (and thus the quantum efficiency) by about 2
times in comparison with the organic EL device of Reference Example
1.
[0251] In the EL device of Example 1, it is considered that an
oxidation-reduction reaction was induced between the molecules of
vanadium pentaoxide (V.sub.2O.sub.5) and .alpha.-NPD, an arylamine
compound which acts as a hole transporting molecule, to form a
charge transfer complex (V.sub.2O.sub.5.sup.-+.alpha.-NPD.sup.+).
Namely, an interfacial surface between the vanadium pentaoxide
(V.sub.2O.sub.5) layer and the .alpha.-NPD layer acts as a charge
generation layer.
[0252] In FIG. 16, an emission spectrum of the resultant organic EL
device is shown by a chain line. Referring to the plotted emission
spectrum, it is observed that the spectrum is substantially the
same as that of Reference Example 1, however, a full width at half
maximum of the spectrum is slightly narrowed in comparison with
that of Reference Example 1. It therefore can be concluded that
this is due to the generated interference effect. Namely, an
interference effect was generated in the two light-emissive units
because a light emitted from the firstly formed light-emissive unit
3-1 was reflected on the cathode, and the reflected light had a
phase which substantially corresponds to a phase of the light
directly projected in the direction of the substrate from the
emissive site.
Example 2
[0253] (Example for the Production of the Organic EL Device Having
a Charge Generation Layer Consisting Only of an Organic
Compound)
[0254] The organic EL device according to the present invention
having a laminate structure shown in FIG. 14 was produced as
follows.
[0255] In accordance with the manner which is substantially the
same as that described in Reference Example 1, a light-emissive
unit 3-1 was deposited through a metal mask 40 for organic layer
formation (see, FIG. 10B) on an ITO pattern-coated glass substrate
1 shown in FIG. 10A. Namely, a 700 .ANG.-thick .alpha.-NPD, a 400
.ANG.-thick layer including Alq:C545T=100:1 (weight ratio), and a
200 .ANG.-thick mixed layer including bathocuproine and metal
cesium (Cs) were sequentially deposited. 4F-TCNQ represented by the
following formula: 10
[0256] was deposited onto the metal-doped layer at a deposition
rate of about 1 .ANG./sec to form a charge generation layer 4-1
having a thickness of about 20 .ANG.. 2-TNATA (product of BANDO
CHEMICAL) was deposited onto the charge generation layer 4-1 at a
deposition rate of about 1 .ANG./sec to obtain a layer thickness of
about 50 .ANG..
[0257] The formation of the charge generation layer 4-1 was also
carried out in the presence of the metal mask 40 for organic layer
formation (see, FIG. 10B).
[0258] Thereafter, while the metal mask 40 for organic layer
formation (FIG. 10B) is still on the glass substrate 1, the
above-described step was again repeated to form a light-emissive
unit 3-2. Namely, a 700 .ANG.-thick .alpha.-NPD, a 400 .ANG.-thick
layer including Ala:C545T=100:1 (weight ratio), and a 200
.ANG.-thick mixed layer including bathocuproine and a metal cesium
(Cs) were sequentially deposited.
[0259] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the light-emissive unit 3-2 to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. The
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0260] In this organic EL device, a DC voltage was applied between
the anode electrode (ITO) and the cathode electrode (Al), and the
characteristics of the green light emitted from the light-emissive
layer (co-deposited layer of Alq and C545T) were measured to obtain
the results plotted in FIGS. 21, 22 and 23.
[0261] In FIGS. 21, 22 and 23, the plus symbols (+) represent a
graph of luminance (cd/m.sup.2)-voltage (v) characteristic curve, a
graph of current density (mA/cm.sup.2)-voltage (v) characteristic
curve and a graph of current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of the EL device
of Example 2.
[0262] In the EL device of Example 2, it is considered that a
charge transfer complex (4F-TCNQ-+2-TNATA+) was formed between the
two organic molecules, i.e., 4F-TCNQ which is a Lewis acid and
2-TNATA which is a hole transporting arylamine molecule. Namely, an
interfacial surface between the 4F-TCNQ layer and the 2-TNATA layer
acts as a charge generation layer.
[0263] Furthermore, in this EL device, it was observed that the
current efficiency was gradually reduced from a luminance of about
30 cd/M.sup.2 (current density=0.12 mA/cm.sup.2), but the maximum
current efficiency of about 25.6 cd/A was obtained at a current
density range of up to about 0.1 MA/cm.sup.2. The maximum current
efficiency of about 25.6 cd/A is a value which could not be
obtained in the conventional organic EL devices having only one
light-emissive unit, and proves that the charge generation layer
can be formed by using only an organic compound.
Example 3
[0264] (Example for the Production of the Organic EL Device Having
Two Light-Emissive Units Having Different Emission Spectrums)
[0265] The organic EL device according to the present invention
having a laminate structure shown in FIG. 15 was produced as
follows.
[0266] As in Reference Example 1, a glass substrate 1 includes,
coated in a predetermined pattern on a surface thereof, a
transparent anode electrode 2 including an ITO (indium-tin oxide,
sputtered product commercially available from ASAHI GLASS) having a
sheet resistance of about 20 .OMEGA./.quadrature. (see, FIG. 10A).
On the ITO pattern-coated glass substrate 1, in the same order as
in Reference Example 2, spiro-NPB having a hole transporting
property (product of COVION) was deposited through a metal mask 40
for organic layer formation (see, FIG. 10B) onto the ITO-coated
glass substrate 1 under vacuum of about 10.sup.-6 Torr and at a
deposition rate of about 2 .ANG./sec to form a hole transportation
layer of the light-emissive unit 3-1 having a thickness of about
800 .ANG..
[0267] Subsequently, spiro-DPVBi (product of COVION) was deposited
onto the hole transportation layer at a deposition rate of about 2
.ANG./sec to form a blue light-emissive layer of the light-emissive
unit 3-1 having a thickness of about 400 .ANG., followed by
depositing a 200 .ANG.-thick mixed layer including bathocuproine
and a metal cesium (Cs).
[0268] Subsequently, as in Example 1, V.sub.2O.sub.5 (vanadium
pentaoxide) was deposited onto the mixed layer including
bathocuproine and Cs at a deposition rate of about 2 .ANG./sec to
form a charge generation layer 4-1 having a thickness of about 100
.ANG.. The formation of the charge generation layer 4-1 was also
carried out in the presence of the metal mask 40 for organic layer
formation (see, FIG. 10B).
[0269] Thereafter, as in Reference Example 3, .alpha.-NPD was
deposited at a layer thickness of about 700 .ANG. to form a hole
transportation layer of the light-emissive unit 3-2. Subsequently,
Alq and a red light-emissive fluorescent dye, "DCJTB" (KODAK), were
deposited onto the hole transportation layer to form a red
light-emissive layer having a thickness of about 400 .ANG.. Each
deposition rate was adjusted so that the resulting red
light-emissive layer contains the fluorescent dye in a
concentration of about 1% by weight. Subsequently, as in the manner
described above, a 200 .ANG.-thick mixed layer including
bathocuproine and Cs was deposited.
[0270] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the mixed layer of bathocuproine and Cs to
form a cathode electrode 5 having a thickness of about 1,000 .ANG..
The organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0271] In FIG. 17, an emission spectrum of the organic EL device
obtained in Example 3 is shown with a solid line. In this organic
EL device, a DC voltage was applied to between the anode electrode
(ITO) and the cathode electrode (Al). As a result, a light emission
of the mixed color of blue and red (pink-colored emission) could be
obtained from the two light-emissive layers. FIG. 39A is a
photograph showing an emission state in this device (FIG. 39B).
[0272] Subsequently, the characteristics of the device were
measured to obtain the results plotted in FIGS. 24, 25 and 26. In
these drawings, white square symbols (.quadrature.) represent a
graph of luminance (cd/m.sup.2)-voltage (v) characteristic curve, a
graph of current density (mA/cm.sup.2)-voltage (v) characteristic
curve, and a graph of current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of the EL device
of Example 3.
[0273] In the EL device of Example 3, a voltage at which the
emission was started was about 4.8 volts. Namely, the starting
voltage of about 4.8 volts is a sum of the starting voltage (2.6
volts) of the device of Reference Example 2 and the starting
voltage (2.2 volts) of the device of Reference Example 3.
[0274] Furthermore, in the EL device of Example 3, as in Example 1,
it is considered that an oxidation-reduction reaction was induced
between the molecules of vanadium pentaoxide (V.sub.2O.sub.5) and
.alpha.-NPD, an arylamine compound which acts as a hole
transporting molecule, to form a charge transfer complex
(V.sub.2O.sub.5.sup.-+.alpha.-NPD.sup.+). Namely, an interfacial
surface between the vanadium pentaoxide (V.sub.2O.sub.5) layer and
the .alpha.-NPD layer acts as a charge generation layer.
Example 4
[0275] (Example for the Production of the Organic EL Device Having
Three Light-Emissive Units; Experiments for Optimizing the Optical
Path Length, a Distance from Each Light-Emissive Site to a
Reflective Cathode.)
[0276] The organic EL device according to the present invention
having a laminate structure shown in FIG. 18 was produced as
follows.
[0277] Three sheets of the ITO pattern-coated glass substrate 1
were provided. In accordance with the manner and order described in
Reference Example 1, a light-emissive unit 3-1 was deposited
through a metal mask 40 for organic layer formation (see, FIG. 10B)
on the ITO pattern-coated glass substrate 1 shown in FIG. 10A.
Namely, a 700 .ANG.-thick .alpha.-NPD, a 600 .ANG.-thick layer
including Alq:C545T=100:1 (weight ratio), and a 100 .ANG.-thick
mixed layer including bathocuproine and a metal cesium (Cs) were
sequentially deposited on each ITO pattern-coated glass substrate
1.
[0278] Subsequently, V.sub.2O.sub.5 (vanadium pentaoxide) was
deposited onto the metal-doped layer at a deposition rate of about
2 .ANG./sec to form a charge generation layer 4-1 having a
thickness of about 300 .ANG.. The formation of the charge
generation layer 4-1 was also carried out in the presence of the
metal mask 40 for organic layer formation (see, FIG. 10B).
[0279] Thereafter, while the metal mask 40 for organic layer
formation (FIG. 10B) is still on the glass substrate 1, the
above-described step was again repeated to form a light-emissive
unit 3-2 and a light-emissive layer 3-3. Note, in this example,
that to ascertain the optimum conditions for an optical path length
from each light-emissive site to a reflective cathode, a layer
thickness of the hole transportation layer including .alpha.-NPD
was varied with intention to obtain three different cells having
the hole transportation layer of the thickness of about 300, 500 or
700 .ANG..
[0280] Namely, a 300, 500 or 700 .ANG.-thick .alpha.-NPD, a 600
.ANG.-thick layer including Alq C545T=100:1 (weight ratio), and a
100 .ANG.-thick mixed layer including bathocuproine and a metal
cesium (Cs) were sequentially deposited on each substrate to form a
light-emissive unit 3-2. Subsequently, V.sub.2O.sub.5 (vanadium
pentaoxide) was deposited at a deposition rate of about 2 .ANG./sec
to form a charge generation layer 4-2 having a thickness of about
300 .ANG..
[0281] After formation of the charge generation layer 4-2, the
above-described process was again repeated. That is, a 300, 500 or
700 .ANG.-thick .alpha.-NPD, a 600 .ANG.-thick layer including
Alq:C545T=100:1 (weight ratio), and a 100 .ANG.-thick mixed layer
including bathocuproine and a metal cesium (Cs) were sequentially
deposited on the charge generation layer 4-2 to form a
light-emissive unit 3-3.
[0282] Finally, aluminum (Al) was deposited through a metal mask 41
for cathode layer formation (see, FIG. 10C) at a deposition rate of
about 10 .ANG./sec onto the light-emissive unit 3-3 to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. The
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0283] In the resulting organic EL device, a DC voltage was applied
to between the anode electrode (ITO) and the cathode electrode (Al)
to measure the characteristics of the green light emitted from the
light-emissive layer (co-deposited layer of Alq and C545T). The
results plotted in FIGS. 27, 28 and 29 were obtained. In these
figures, the symbols .smallcircle., .quadrature. and + each
represents a graph of the luminance (cd/m.sup.2)-voltage (v)
characteristic curve, a graph of the current density
(mA/cm.sup.2)-voltage (v) characteristic curve, and a graph of the
current efficiency (cd/A)-current density (mA/cm.sup.2)
characteristic curve, respectively, of each of the EL devices
having the three different thickness described above.
[0284] As shown in FIG. 29, the EL devices having the three
different thickness each have a largely varied current efficiency
(cd/A). In the devices having the light-emissive units 3-2 and 3-3
having a thickness of about 700 .ANG. in the hole transportation
layer, a maximum current density exceeding about 48 cd/A was
obtained, while in the devices including the light-emissive units
3-2 and 3-3 having a thickness of about 300 or 500 .ANG. in the
hole transportation layer, the current density obtained was only
about 18 or 28 cd/A.
[0285] The EL device including the light-emissive units 3-2 and 3-3
having a thickness of about 700 .ANG. in the hole transportation
layer show that they have a current efficiency of about 16 cd/A
(48/3 cd/A) per a light-emissive unit, and thus they represent the
optimized examples in which in all of the three light-emissive
sites, an optical path length (product of a real layer thickness
and an index of refraction) from the light-emissive site to the Al
cathode (light reflective cathode) is always approximately an
odd-numbered times a quarter wavelength of light, i.e., in this
example, the layer thickness is 1/4 wavelength, 3/4 wavelength and
{fraction (5/4)} wavelength of the emission wavelength,
respectively, from an Al cathode side of the device.
[0286] An emission spectrum of each of the three organic EL devices
obtained in Example 4 is shown in FIG. 19. Furthermore, the
emission spectrum of the device showing the maximum current
efficiency (48 cd/A), selected from all the emission spectrums of
the devices of Example 4, is also plotted in FIG. 16 for the
comparison with the spectrum of the device (one light-emissive
unit) of Reference Example 1 and the spectrum of the device (two
light-emissive units) of Example 1.
Example 5
[0287] (Example for the Production of the Organic EL Device
Including Two Light-Emissive Units Having Different Emission
Spectrums; Experiments for Optimizing the Optical Path Length, a
Distance from Each Light-Emissive Site to a Reflective
Electrode.)
[0288] Three sheets of the ITO pattern-coated glass substrate were
provided, and in accordance with the process which is substantially
the same as that of Example 3, a blue light-emissive unit and a red
light-emissive unit were deposited through a V.sub.2O.sub.5
(vanadium pentaoxide) of the charge-generation layer 4-1 with the
proviso that, in this example, for the purpose of ascertaining the
optimum conditions for an optical path length of from a blue
light-emissive site of the light-emissive unit 3-1 to the light
reflective electrode, a layer thickness of the hole transportation
layer including .alpha.-NPD of the light-emissive unit 3-2 was
varied with intention to obtain three different cells having the
hole transportation layer of the thickness of about 300, 500 or 700
.ANG.. Other layer deposition conditions and measurement conditions
are with the same as those of Example 3.
[0289] In FIGS. 30, 31 and 32, the symbols .quadrature., + and
.smallcircle. each represents a graph of the luminance
(cd/m.sup.2)-voltage (v) characteristic curve, a graph of the
current density (mA/cm.sup.2)-voltage (v) characteristic curve, and
a graph of the current efficiency (cd/A)-current density
(mA/cm.sup.2) characteristic curve, respectively, of each of the EL
devices having the three different thickness obtained in this
example.
[0290] Furthermore, an emission spectrum of each of the three
organic EL devices obtained in this example (Example 5) is shown in
FIG. 20.
[0291] As shown in FIG. 32, the EL devices having the three
different thicknesses each had a largely varied current efficiency
(cd/A). In the devices including the light-emissive unit 3-2 having
a thickness of about 700 .ANG. in the hole transportation layer, a
maximum current density exceeding about 8 cd/A was obtained, while
in the devices including the light-emissive unit 3-2 having a
thickness of about 300 or 500 .ANG. in the hole transportation
layer, the current density obtained was only about 6.5 or 4
cd/A.
[0292] The EL device including the light-emissive unit 3-2 having a
thickness of about 700 .ANG. had an optical path length (product of
a real layer thickness and an index of refraction) from the
light-emissive site of spiro-DPVBi (blue light-emissive material)
to the Al cathode (light reflective electrode) of about three times
a quarter wavelength of light. Namely, the EL device is an example
of an optimized device.
Example 6
[0293] (Example for the Production of the Organic EL Device in
Which a Layer Contacting a Charge Generation Layer on an Anode Side
is an In-Situ Reaction Generating Layer, and Having a Charge
Generation Layer Consisting of the Mixture of V.sub.2O.sub.5 and
Arylamine Compound.)
[0294] The organic EL device according to the present invention
having a laminate structure shown in FIG. 41 was produced as
follows.
[0295] In accordance with the manner which is substantially the
same as that described in Reference Example 1, a light-emissive
unit 3-1 was deposited through a metal mask 40 for organic layer
formation (see, FIG. 10B) on an ITO pattern-coated glass substrate
1 shown in FIG. 10A. Namely, a 600 .ANG.-thick .alpha.-NPD and a
700 .ANG.-thick layer including Alq:C545T=100:1 (weight ratio) were
sequentially deposited. Thereafter the in-situ reaction generating
layer was formed thereon.
[0296] Namely, a metal-organic complex of 8-quinolinolato lithium
(hereinafter, briefly referred to as "Liq") represented by the
following formula 11
[0297] was deposited by 10 .ANG.. Thereafter Al was deposited a as
a thermally reducible metal at a deposition rate of about 1
.ANG./sec to form an in-situ reaction generating layer having a
thickness of 15 .ANG..
[0298] Subsequently, V.sub.2O.sub.5 (vanadium pentaoxide) and
.alpha.-NPD was co-deposited at a molar ratio
(V.sub.2O.sub.5:.alpha.-NPD=4:1) on the in-situ reaction generating
layer at a deposition rate of 2 .ANG./sec to form the charge
generation layer 4-1 having a thickness of 200 .ANG.. The charge
generation layer was also deposited via the metal mask 40 for
organic layer formation (see, FIG. 10B).
[0299] Thereafter, while the metal mask 40 for organic layer
formation (FIG. 10B) is still on the glass substrate 1, the
above-described step was again repeated to form a light-emissive
unit 3-2. Namely, a 600 .ANG.-thick .alpha.-NPD, a 700 .ANG.-thick
layer including Alq:C545T 100:1 (weight ratio), and a 10
.ANG.-thick Liq were sequentially deposited. Finally, aluminum (Al)
was deposited through a metal mask 41 for cathode layer formation
(see, FIG. 10C) at a deposition rate of 10 .ANG./sec to form a
cathode electrode 5 having a thickness of about 1,000 .ANG.. The
organic EL device having a square light-emissive area of 0.2 cm
(length) by 0.2 cm (width) was thus obtained (see, FIG. 10D).
[0300] In this organic EL device, a DC voltage was applied between
the anode electrode (ITO) and the cathode electrode (Al), and the
characteristics of the green light emitted from the light-emissive
layer (co-deposited layer of Alq and C545T) were measured to obtain
the results in FIGS. 42, 43, 44 and 45. In FIGS. 42, 43, 44 and 45,
the circle symbols (.circle-solid.) represent a graph of luminance
(cd/m.sup.2)-voltage (v) characteristic curve, a graph of current
density (mA/cm2)-voltage (v) characteristic curve, a graph of
current efficiency (cd/A)-current density (mA/cm.sup.2)
characteristic curve and a graph of luminous efficiency
(lm/W)-luminance (cd/m.sup.2) characteristic curve, respectively,
of the EL device of Example 6.
[0301] For comparison, a result of a reference device
(ITO/.alpha.-NPD, 600 .ANG./Alq:C545T=100:1, 700 .ANG./Liq, 10
.ANG./Al) having a conventional structure was plotted in FIGS. 42,
43, 44 and 45, using the circle symbols (.smallcircle.)
[0302] As shown in the drawings, in the organic EL device in which
the light-emissive unit was partitioned into 2 units, a maximum
current efficiency (and quantum efficiency) is improved to twice as
the organic EL device in the above reference device.
[0303] In the EL device of Example 6, it is considered, like in
Example 1, that a charge transfer complex
(V.sub.2O.sub.5.sup.-+.alpha.-NPD.sup.+) was formed between
molecules of the V.sub.2O.sub.5 and the .alpha.-NPD, a hole
transporting arylamine molecule, by an oxidation reduction
reaction. A mixed layer of the V.sub.2O.sub.5 and the .alpha.-NPD
is functioned as the charge generation layer.
[0304] Furthermore, in this EL device, a material constituting the
in-situ reaction generating layer includes only the organic metal
complex having an alkaline metal ion (Lithium ion in the EXAMPLE
6). The material can be, however, a mixed layer of the electron
transporting compound such as bathocuproine and Alq and the organic
metal complex (see Japanese Laid-open Patent Application
No.2000-182774) or a layer including the organic metal complex
containing one of said metal ion.
[0305] The in-situ reaction using inorganic compound containing one
of said metal ion can also be adopted for the layer contacting the
charge generation layer on an anode side, because such in-situ
reaction has been observed conventionally also in using an
inorganic alkaline metal compound as a contacting material to Al
cathode and so on (see a reference document "J. Endo, T. Matsumoto,
and J. Kido, Jpn. J. Appl. Phys. Vol. 41 (2002) pp.L800-L803").
Test Example
[0306] (Measurement of Resistivity in the Charge Generation Layer
and the Like)
[0307] In this example, the resistivity (.OMEGA.cm) was measured
with two different methods depending on the range of the
resistivity of the test sample.
[0308] The first measuring method can be suitably applied to a test
samples having a relatively large resistivity. The measurement is
carried out by sandwiching a vapor deposition layer of the test
sample with electrodes (see FIGS. 33 and 34). The resistivity of
the test sample is then calculated from a ratio of the electric
field E(V/cm), obtained from an applied voltage (V) and a layer
thickness (cm) of the deposition layer of the sample, i.e.,
distance between the electrodes, and a current density (A/cm.sup.2)
obtained from an observed current value (A) and a cross-sectional
area (cm.sup.2) of the current flowing region, i.e., resistivity
(.OMEGA.cm)=(V/cm)/(A/cm.sup.2)
[0309] The resistivity evaluation device for use in this measuring
method can be produced in accordance with the following method.
FIG. 33 is a plan view of the evaluation device, and FIG. 34 is a
cross-sectional view thereof.
[0310] As in the Examples and the Reference Examples described
above, a metal mask 40 shown in FIG. 10B is used. A test sample
(material, a resistivity of which is intended to be measured) 18 is
deposited, through a shadow mask for forming both an organic layer
and a charge generation layer, at a desired thickness on an ITO
electrode 16 having a width of about 2 mm or, alternatively, an
aluminum electrode having a width of about 2 mm. Finally, an
aluminum electrode 17 having a width of about 2 mm is deposited in
such a manner that it is crossed with the ITO electrode 16. A
desired evaluation device is thus obtained.
[0311] The second measuring method can be suitably applied to the
test samples having a relatively small resistivity. The measurement
is carried out by using a resistivity evaluation device having a
coplanar arrangement structure. Namely, as shown in FIGS. 35 and
36, a substrate 19 is provided, and on the same plane surface of
the substrate 19, electrodes which are used as an anode 20 and a
cathode 21 are previously deposited at a certain distance of L cm.
A test material 22 is deposited through a metal mask for defining a
deposition area having an opening with the certain width (W cm) on
the electrodes-deposited substrate 19 to obtain a deposited layer
having a desired thickness (t cm). In this measuring method, an
electric field E(V/cm) of the test sample is calculated by dividing
an applied voltage (V) with a distance (L cm) between the
electrodes, and a current density (A/cm.sup.2) is calculated by
dividing an observed current value (A) by a cross-sectional area of
the current flowing region (in this example, W.times.t cm.sup.2).
The resistivity (.OMEGA.cm) of the test sample can be calculated
from the equation described above with regard to the first
measuring method (sandwich method).
[0312] FIG. 37 is a graph showing the measurement results of the
resistivity. The test samples used herein are ITO (transparent
electrode material), V.sub.2O.sub.5 (a charge generation layer
according to the present invention), a co-deposition layer of
V.sub.2O.sub.5 and .alpha.-NPD (three kinds of molar ratios of
V.sub.2O.sub.5:.alpha.-NPD=4:- 1, 1:1, 1:2) (a charge generation
layer according to the present invention), a co-deposition layer of
V.sub.2O.sub.5 and 2-TNATA [V.sub.2O.sub.5:2-TNATA=4:1 (molar
ratio) (a charge generation layer according to the present
invention)], a co-deposition layer of .alpha.-NPD, Cs and
bathocuproine [Cs bathocuproine 1:1 (molar ratio) (electron
injecting layer in the light-emissive unit)], and Alq (light
emitting material).
[0313] For the ITO, the co-deposition layer of V.sub.2O.sub.5 and
.alpha.-NPD, and the co-deposition layer of V.sub.2O.sub.5 and
2-TNATA, the resistivity was measured using a measuring device
having a coplanar arrangement structure (coplanar arrangement
method), and for the .alpha.-NPD, the co-deposition layer of Cs and
bathocuproine, and Alq.sub.3, the resistivity was measured using a
measuring device having a sandwich structure (sandwich method).
Furthermore, the .alpha.-NPD having a thickness of 1000 .ANG. was
measured by a measuring device having the sandwich structure
wherein the mixed layer of V.sub.2O.sub.5 and .alpha.-NPD (the
composition of the charge generation layer according to the present
invention) was formed thinly by 50 .ANG. on a portion contacting
both electrodes to make the charge injection from the electrode
ohmic.
[0314] Furthermore, with regard to V.sub.2O.sub.5, the resistivity
thereof was measured by using both of the coplanar arrangement
method and the sandwich method with the result that a substantially
same resistivity can be measured regardless of the difference of
the applied methods.
[0315] Coplanar Arrangement Method:
1 .largecircle. ITO 4.6 .times. 10.sup.-4 .OMEGA. cm .circle-solid.
V.sub.2O.sub.5 7.2 .times. 10.sup.$ .OMEGA. cm .tangle-solidup.
co-deposition layer of V.sub.2O.sub.5 and .alpha. -NPD
(V.sub.2O.sub.5: .alpha. - NPD = 4:1) 2.0 .times. 10.sup.3 .OMEGA.
cm .diamond. co-deposition layer of V.sub.2O.sub.5 and .alpha. -NPD
(V.sub.2O.sub.5: .alpha. - NPD = 1:1) 3.6 .times. 10.sup.4 .OMEGA.
cm + co-deposition layer of V.sub.2O.sub.5 and .alpha. -NPD
(V.sub.2O.sub.5: .alpha. - NPD = 1:2) 2.9 .times. 10.sup.5 .OMEGA.
cm .quadrature. co-deposition layer of V.sub.2O.sub.5 and 2-TNATA
(V.sub.2O.sub.5: 2-TNATA = 4:1) 5.8 .times. 10.sup.3 .OMEGA. cm
[0316] Sandwich Method:
2 .DELTA. ITO/V.sub.2O.sub.5/Al 2.8 .times. 10.sup.5 .OMEGA. cm
.tangle-soliddn. ITO/ .alpha. -NPD/Al 1.5 .times. 10.sup.13 .OMEGA.
cm .box-solid. ITO/V.sub.2O.sub.5: .alpha. -NPD(50.ANG.)/ .alpha.
-NPD(1000.ANG.)/V.sub.2O.sub.5: .alpha. -NPD (50.ANG.) /Al 8.0
.times. 10.sup.8 .OMEGA. cm X Al/ Alq.sub.3/Al 6 .times. 10.sup.13
.OMEGA. cm .vertline. ITO/Cs: bathocuproine/Al 2 .times. 10.sup.5
.OMEGA. cm
[0317] FIG. 40 shows a relationship between a mixed ratio (molar
fraction) of the co-deposition layer of V.sub.2O.sub.5 and
.alpha.-NPD, and resistivity. As shown in FIG. 40, due to the
mixing of both materials, the charge generation layer according to
the present invention indicates a resistivity lower than that of
each material. This result suggests a presence of oxidation
reduction reaction caused by the transfer of electrons, i.e.
formation of the charge transfer complex. Accordingly, it was found
that the resistivity of the charge generation layer can be varied
depending the way of contacting the electron accepting material
such as V.sub.2O.sub.5 with the hole transporting material, using
an appropriate method such as laminating or mixing.
[0318] As described above, since the EL device of the present
invention has a structure wherein two or more light-emissive units
were arranged between the electrodes while the light-emissive units
are partitioned with an electrically insulating charge generation
layer, an EL device having a long operational lifetime and a high
luminance region can be achieved without increasing a current
density so much. Furthermore, it is not necessary to frequently
change and to precisely position shadow masks for defining a vapor
deposition area during production, especially during the formation
of two or more light-emissive units and a charge generation layer.
Furthermore, in the production of simple matrix-type display
devices, it is not required to perform an operation which may cause
a risk of disconnection in formation of a cathode line, thus
enabling to retain high productivity, and effectively and stably
produce an organic EL device with a high luminance and long
operational lifetime.
[0319] Moreover, when the EL device was applied to the production
of an illumination apparatus, since a voltage reduction due to the
resistance of the electrode material can be diminished, it becomes
possible to achieve an uniform light emission over a large surface
area. Similarly, if the EL device was applied to the production of
a display device having a simple matrix structure, since a voltage
reduction due to the wiring resistance and an increase of the
substrate temperature can be largely diminished, it becomes
possible to achieve a large surface area simple matrix display
device which could not be obtained using the conventional EL
devices.
[0320] Obvious changes may be made in the specific embodiments of
the present invention described herein, such modifications being
within the spirit and scope of the invention claimed. It is
indicated that all matter contained herein is illustrative and does
not limit the scope of the present invention.
* * * * *