U.S. patent application number 09/162322 was filed with the patent office on 2001-12-13 for organic electroluminescent element.
Invention is credited to FURUKAWA, KEIICHI, TERASAKA, YOSHIHISA, UEDA, HIDEAKI.
Application Number | 20010051284 09/162322 |
Document ID | / |
Family ID | 27329968 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051284 |
Kind Code |
A1 |
UEDA, HIDEAKI ; et
al. |
December 13, 2001 |
ORGANIC ELECTROLUMINESCENT ELEMENT
Abstract
The present invention relates to an organic electroluminescence
element comprising an anode, an organic luminous layer, an
electron-injection layer and a cathode, in which the
electron-injection layer comprises a metal oxide or a metal halide,
and a different material therefrom.
Inventors: |
UEDA, HIDEAKI;
(KISHIWADA-SHI, JP) ; FURUKAWA, KEIICHI;
(SUITA-SHI, JP) ; TERASAKA, YOSHIHISA; (SUITA-SHI,
JP) |
Correspondence
Address: |
MORRISON & FOERSTER LLP
2000 PENNSYLVANIA AVENUE, N.W.
WASHINGTON
DC
20006-1888
US
|
Family ID: |
27329968 |
Appl. No.: |
09/162322 |
Filed: |
September 28, 1998 |
Current U.S.
Class: |
428/690 ;
313/504; 313/506; 428/917 |
Current CPC
Class: |
H01L 51/5092
20130101 |
Class at
Publication: |
428/690 ;
428/917; 313/504; 313/506 |
International
Class: |
H05B 033/12 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 1997 |
JP |
09/264102 |
Sep 30, 1997 |
JP |
09/267037 |
Jul 31, 1998 |
JP |
10/217039 |
Claims
What is claimed is:
1. An organic electroluminescence element comprising an anode, an
organic luminous layer, an electron-injection layer comprising a
metal oxide or a metal halide, and a different material therefrom
and a cathode.
2. The organic electroluminescence element according to claim 1,
wherein the different material is metal.
3. The organic electroluminescence element according to claim 2,
wherein the metal has a work function of more than 4.2 eV
4. The organic electroluminescence element according to claim 2,
wherein a mixing ratio of the metal oxide to the metal halide is
1:100 to 100:1.
5. The organic electroluminescence element according to claim 2,
wherein a mixing ratio of the metal oxide to the metal halide is
1:20 to 20:1.
6. The organic electroluminescence element according to claim 1,
wherein the different material is an electron transporting
material.
7. The organic electroluminescence element according to claim 6,
wherein the electron transporting material is an organic
compound.
8. The organic electroluminescence element according to claim 7,
wherein a mixing ratio of the electron transporting material to the
metal oxide or matal halide (electron transporting material metal
oxide and/or metal halide) is 100:1 to 1:1.2.
9. The organic electroluminescence element according to claim 7,
wherein a mixing ratio of the electron transporting material to the
metal oxide or matal halide (electron transporting material metal
oxide and/or metal halide) is 20:1 to 1:1.
10. The organic electroluminescence element according to claim 1,
wherein the electron-injection layer has a thickness of 0.1 to 20
nm.
11. The organic electroluminescence element according to claim 1,
wherein the metal oxide or the metal halide to be mixed in the
electron-injection layer have a work function of less than 4.2
eV.
12. The electroluminescence element of claim 1, in which the metal
halide is selected from the group consisting of magnesium fluoride,
calcium fluoride, yttrium fluoride, lithium fluoride and lithium
bromide.
13. The electroluminescence element of claim 1, in which the metal
oxide is selected from the group consisting of magnesium oxide,
yttrium oxide and lithium oxide.
14. The electroluminescence element of claim 1, in which the
electron-injection layer is formed by co-deposition of a metal
oxide or a metal halide, and a different material therefrom.
15. The electroluminescence element of claim 1, in which an
electron-transporting layer is formed between the
electron-injection layer and the organic luminous layer.
16. The electroluminescence element of claim 1, in which the
cathode is formed of a metal selected from the group consisting of
aluminum, silver and indium.
17. The electroluminescence element of claim 1, in which a sealing
layer is formed on the cathode.
18. The electroluminescence element of claim 1, further comprising
a hole-injection transporting layer.
19. The electroluminescence element of claim 1, further comprising
a hole-injection layer and a hole-transporting layer.
20. The electroluminescence element of claim 1, in which the same
charge transporting materila is contained in both the
electron-injection layer and the luminous layer.
Description
[0001] This application is based on Japanese Patent Application
Nos. Hei 9-264102, Hei 9-267037 and Hei 10-217039, respectively
filed in Japan Sep. 29, 1997, Sep. 30, 1997 and Jul. 31, 1998, the
contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an organic
electroluminescence element.
[0004] 2. Description of the Prior Art
[0005] The organic electroluminescence element emit light in
accordance with electric signals and is constituted of an organic
compound as a luminous material.
[0006] The organic electroluminescence element is basically
constituted of an organic luminous layer and a pair of electrodes
with the luminous layer sandwiched between the electrodes.
Luminescence is a phenomenon in which electrons are injected from
one electrode and holes are injected from the other electrode so
that the luminous material in the luminous layer is excited to a
higher energy level and then the excited luminous material goes
down to a ground state to emit extra energy as light.
[0007] In addition to the above basic structure, a hole-injection
layer for injecting holes is formed on the hole-injection electrode
or an electron-injection layer is formed on the electron-injection
electrode in order to improve luminous efficiency.
[0008] U.S. Pat. No. 3,530,325 discloses an example of
electroluminescence elements in which single crystal anthracene is
contained as a luminous material. Japanese Patent Laid-Open No. Sho
59-194,393 proposes the combination of a hole-injection layer with
an organic luminous layer. Japanese Patent Laid-Open No. Sho 63-
295,695 proposes the combination of an organic hole-injection
transporting layer with an organic electron-injection tranporting
layer.
[0009] Those laminated electroluminescence element has a structure
in which an organic fluorescent material, a charge-transporting
organic compound (charge-transporting material) and electrodes are
laminated. Holes and electrons injected from respective electrode
move in the charge-transporting material and are recombined to emit
light. An organic pigments which can emit fluorescenct light, such
as 8-qunolinol aluminum complex and cumarin, are used as the
organic fluorescent material. The electron-transporting material
is, for example, exemplified by amino compounds, such as
N,N'-di(m-tolyl)N,N'-diphenyl benzidine and
1,1-bis[N,N-di(p-tolyl)aminophenyl]cyclohexane, and
4-(N,N-diphenyl)aminobenzaldehyde-N,N-diphenyl hydrazone. In
addition, porphyrin, such as cupper phthalocyanine, is
proposed.
[0010] By the way, organic electroluminescence element has a high
luminous properties. Stability at light-emitting time and
preserving stability, however, are not sufficient for the
electroluminescence element to be put into practical use. The
stability of charge-transporting material is pointed out as one of
problems with respect to the light-emitting stability and
preserving stability of the element. A layer constituted by an
organic material in the electroluminescence element is several tens
of nm to several hundred of nm in thickness, being very thin. A
voltage applied to the layer in unit of thickness is very high. As
heat is emitted at light-emitting time or in electriferous
conditions, the charge-transporting material is required to have
electrical stability, thermal stability or chemical stability.
[0011] Japanese Patent Laid-Open Nos. Hei 2-15,595, Hei 3-37, 994,
Hei 4-132, 191 and Hei 5-121, 172 disclose that materials other
than aluminum is used as cathode in order to lower light
luminescence-starting voltage of an electroluminescence
element.
[0012] Japanese Patent Laid-Open Nos. Hei 4-132, 189 and Hei 7-268,
317 disclose that a layer constituted of a mixture of an electron
transporting material and metal is used as an electron-injection
layer.
[0013] The handling of the material other than aluminum is
difficult in layer-forming conditions and the material is liable to
be oxidized. The same problem arises when the mixture of the
electron transporting material and metal.
[0014] When metal used for formation of an electron-injection layer
is oxidized at vapor deposition time, powdery ones are formed. A
uniform layer can not be formed. White haze occurs. Metallic layer
is not formed. The formed one can not be used as an electrode.
[0015] A layer having excellent properties as an electron-injection
layer has not been obtained yet as things are.
SUMMARY OF THE INVENTION
[0016] The present invention is to provide an electroluminescence
element having high luminous strength and displaying stable
performance even if used repeatedly.
[0017] The present invention relates to an organic
electroluminescence element comprising an anode, an organic
luminous layer, an electron-injection layer and a cathode, in which
the electron-injection layer comprises a metal oxide or a metal
halide, and a different material therefrom.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a schematic sectional view illustrating one
embodiment of organic electroluminescence elements.
[0019] FIG. 2 is a schematic sectional view illustrating one
embodiment of organic electroluminescence elements.
[0020] FIG. 3 is a schematic sectional view illustrating one
embodiment of organic electroluminescence elements.
[0021] FIG. 4 is a schematic sectional view illustrating one
embodiment of organic electroluminescence elements.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] The present invention relates to an organic
electroluminescence element comprising an anode, an organic
luminous layer, an electron-injection layer and a cathode, in which
the electron-injection layer comprises a metal oxide or a metal
halide, and a different material therefrom.
[0023] The electroluminescence element of the present invention has
at least a luminous layer and an electron-injection layer between a
pair of an anode and a cathode. The present invention is basically
characterized in that the electron-injection layer is a composite
layer comprising a metal oxide, a metal halide and a different
material therefrom.
[0024] The present invention is further explained by referring to
FIG. 1. In FIG. 1, the reference number 1 is an anode. On the
anode, a hole-injection transporting layer 2, an organic luminous
layer 3, an electron-injection layer 4 and a cathode 5 are
laminated in the order.
[0025] It is preferred that an electrically conductive substance to
be used for an anode 1 of the organic electroluminescence element
has a work function of more than 4 eV. Conductive substances such
as carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc,
tungsten, silver, tin, gold, etc., and an alloy thereof, tin oxide,
indium oxide, antimony oxide, zinc oxide or zirconium oxide are
used.
[0026] It is preferred that a metal forming a cathode 5 has a work
function of less than 4 eV. Magnesium, calcium, titanium, yttrium,
lithium, gadolinium, ytterbium, ruthenium, manganese, indium and an
alloy thereof are used.
[0027] In the organic electroluminescence element, it is necessary
that at least the anode 1 or the cathode 5 is a transparent
electrode so that emission is observed. In this case, if the
transparent electrode is used for the cathode, the transparency is
easily deteriorated. Therefore, it is preferred that the
transparent electrode is used for the anode.
[0028] When the transparent electrode is formed, it may be formed
using the above-mentioned conductive substances, by means of vapor
deposition, spattering, sol-gel method, or applying resin in which
the above conductive substance is dispersed, etc., so that the
desired transparency and conductivity are secured.
[0029] The transparent substrate is not specifically limited as
long as it has suitable strength, is not affected by heat due to
deposition, etc. at the time of preparing an organic
electroluminescence element, and is transparent. Examples thereof
include glass substrate, transparent resin such as polyethylene,
polypropylene, polyethersulfon or polyetherketone. As the
transparent electrode formed on the glass substrate, commercially
available ITO, NESA, etc., are known. They may also be used.
[0030] FIG. 1 shows a construction with the hole-injection
transporting layer 2 formed on the anode 1. The hole-injection
transporting layer 2 can be formed by means of a vapor deposition
of a compound, a dip coating or spin coating of the compound.
[0031] When the hole-injection transporting layer is formed by a
deposition method, the thickness thereof is normally 1 to 200 nm,
preferably 5 to 100 nm. When the hole-injection transporting layer
is formed by the coating method, the thickness thereof is normally
about 5 to 500 nm. The thicker the thickness of the layer, the
higher the applied voltage is required, which results in the
degradation of luminous efficiency. The deterioration of an
electroluminescence element is liable to occur. If the thickness of
the layer is smaller, the luminous efficiency is improved, however,
the electroluminescence element easily causes breakdown, which
shortens its life.
[0032] Examples of the hole-transporting material to be used for
the hole-injection transporting layer include known compounds such
as
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine,
N,N'-diphenyl-N,N'-bis(4-methylphenyl)-1,1'-diphenyl-4,4'-diamine,
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-diphenyl-4,4'-diamine,
N,N'-diphenyl-N,N'-bis(2-naphthyl)-1,1'-diphenyl-4,4'-diamine,
N,N'-tetra(4-methylphenyl)-1,1'-diphenyl-4,4'-diamine,
N,N'-tetra(4-methylphenyl)-1,1'-bis(3-methylphenyl)- 4,4'-diamine,
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diamine,
N,N'-bis(N-carbazolyl)-1,1'-diphenyl-4,4'-diamine, 4,4',
4"-tris(N-carbazolyl)triphenylamine,
N,N',N"-triphenyl-N,N',N"-tris(3-met-
hylphenyl)-1,3,5-tri(4-aminophenyl)benzene,
4,4',4"-tris[N,N',N"-triphenyl- -N,N',
N"-tris(3-methylphenyl)]triphenylamine and the like. They may be
used in a mixture of more than one compounds.
[0033] organic luminous layer 3 is formed on the hole-injection
transporting layer 2. Examples of an organic luminous material to
be used for the organic luminous layer 3 include those which are
known to the art. For example, epidorisin,
2,5-bis[5,7-di-t-pentyl-2-benzoxazolyl]-thi- ophene,
2,2'-(1,4-phenylenedivinylene)bisbenzothiazole,
2,2'-(4,4'-biphenylene)bisbenzothiazole,
5-methyl-2-{2-[4-(5-methyl-2-ben-
zoxazolyl)phenyl]vinyl}benzoxazole,
2,5-bis(5-methyl-2-benzoxazolyl)thioph- ene, anthracene,
naphthalene, phenanthrene, pyrene, chrysene, perylene, perynone,
1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin, acridine,
stilbene, 2-(4-biphenyl)-6-phenylbenzoxazole, aluminum trisoxine,
magnesium bisoxine, bis(benzo-8-quinolinol)zinc,
bis(2-methyl-8-quinolinol)-aluminum oxide, indium trisoxine,
aluminum tris(5-methyloxine), lithium oxine, gallium trisoxine,
calcium bis(5-chloroxine), poly(zinc-bis(8-hydroxy-5-quinolinolyl)
methane), dilithium epindolision, zinc bisoxine,
1,2-phthaloperynone, 1,2-naphthaloperynone and the like.
[0034] Further, conventional fluorescent dyes such as fluorescent
coumarine dye, fluorescent perylene dye, fluorescent pyran dye,
fluorescent thiopyran dye, fluorescent polymethine dye, fluorescent
mecyanin dye, fluorescent imidazole dye, etc. can be used. Among
them, chelating oxynoid compounds are particularly preferred.
[0035] The organic luminous layer may be composed of a single layer
construction of the above-mentioned luminous substance. It may also
be composed of a multi-layer construction in order to adjust the
properties such as luminous color or luminous intensity. Further,
the luminous layer may be formed with two or more luminous
substances or doped with luminous substances.
[0036] When the luminous layer is formed by a deposition method,
the thickness thereof is normally 1 to 200 nm, preferably 1 to 100
nm. When the luminous layer is formed by a coating method, the
thickness thereof is normally about 5 to 500 nm. The thicker the
thickness of the layer, the higher the applied voltage is required,
which results in the degradation of luminous efficiency. The
deterioration of an electroluminescence element is liable to occur.
If the thickness of the layer is smaller, the luminous efficiency
is improved, however, the electroluminescence element easily causes
breakdown, which shortens its life.
[0037] On the luminous layer 3, a composite layer comprising a
metal oxide, a metal halide and a different material therefrom is
formed as the electron-injection layer 4.
[0038] It is preferred that metal oxides or metal halides to be
mixed in the electron-injection layer have a work function of less
than 4.2 eV. As such, magnesium oxide, magnesium fluoride, calcium
fluoride, strontium fluoride, yttrium oxide, strontium oxide,
yttrium fluoride, lithium fluoride, lithium bromide, lithium oxide,
magnesium bromide may be used. Magnesium fluoride, calcium
fluoride, lithium fluoride, yttrium fluoride, lithium oxide,
magnesium oxide, lithium bromide and yttrium oxide are preferred
from the viewpoint of luminous properties and layer-forming
properties.
[0039] As the metals to be mixed in the electron-injection layer,
aluminum, indium, silver, magnesium, and gold are used. Among those
metals, aluminum, indium, silver and gold are preferable each of
which has a work function of more than 4.2 eV.
[0040] The different material therefrom to be mixed and contained
in the electron-injection layer is a charge-transporting material
or a metal.
[0041] The charge-transporting material contained in the
electron-injection layer 4 may be exemplified by nitro-substituted
fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide,
oxadiazole, triazole, thiadiazole, cumarin, chelated oxynoid
compound, and a derivative thereof. Among those, the chelated
oxynoid compound are particularly preferred from the viewpoint of
heat resistance.
[0042] When the organic luminous materials have charge-transporting
ability, such the organic luminous materials may be used as an
electron-transporting material of the electron-injection layer. In
this case, it is preferable that the organic luminous material and
the electron transporting material in the electron-injection layer
are same. Such material may be exemplified by chelated oxynoid
compound, benzoxazole complex, benzothiazole complex. Among those
compounds, chelated oxynoid compound is preferable.
[0043] When the electron transporting material is mixed, its mixing
ratio to metal oxide or matal halide (electron transporting
material:metal oxide and/or metal halide) is 100:1 to 1:1.2,
preferably 20:1 to 1:1.
[0044] When metal is mixed, its mixing ratio to metal oxide or
metal halide (metal oxide and/or metal halide:metal) is 1:100 to
100:1, preferably 1:20 to 20:1.
[0045] The electron-injection layer may be formed by a vacuum vapor
deposition method to have a layer thickness of 0.1 to 20 nm. The
thicker the thickness of the layer, the higher the applied voltage
is required to emit light, which results in the degradation of
luminous efficiency. The deterioration of an electroluminescence
element is liable to occur. If the thickness of the layer is
smaller, it becomes difficult to form a uniform layer. Defects in
the layer are liable to be formed. The luminous efficiency is also
deteriorated. The life of electroluminescence element is shortened.
The layer thickness of, for example, the electron-injection layer
can be measured by means of a layer-thickness measuring apparatus
of crystal oscillator type.
[0046] The mixture of a metal oxide, a metal halide and a different
material therefrom can be deposited to form a layer by many known
methods, such as an electrical resistance heating method, an EB
vapor deposition method, an ion plating method and an ionizing
vapor deposition method.
[0047] Different constitutions of electroluminescence element are
shown in FIG. 2 to FIG. 4.
[0048] In FIG. 2, the reference number 1 is an anode. On the anode,
a hole-injection transporting layer 2, an organic luminous layer 3,
an electron transporting layer 6, an electron-injection layer 4 and
a cathode 5 are laminated in the order. The above-mentioned
electron-injection layer is a composite layer comprising a metal
oxide, a metal halide and a different material therefrom.
[0049] In FIG. 3, the reference number 1 is an anode. On the anode,
a hole-injection layer 7, a hole-transporting layer 8, an organic
luminous layer 3, an electron-transporting layer 6, an
electron-injection layer 4 and a cathode 5 are laminated in the
order. The above-mentioned electron-injection layer is a composite
layer comprising a metal oxide, a metal halide and a different
material therefrom.
[0050] In FIG. 4, the reference number 1 is an anode. On the anode,
a hole-injection layer 7, a hole-transporting layer 8, an organic
luminous layer 3, an electron-injection layer 4, a cathode 5 and a
sealing layer 9 are laminated in the order. The above-mentioned
electron-injection layer is a composite layer comprising a metal
oxide, a metal halide and a different material therefrom.
[0051] When the electron-transporting layer is formed as shown in
FIG. 2 or FIG. 3, a layer thickness thereof is about 1 to 200 nm,
preferably 1 to 100 nm. The same electron-transporting material as
described in the elecrton-injection layer may be used as an
electron-transporting material. When the luminous material has
electron-transporting ability, the electron-transporting layer 6
may be formed with such a luminous material. In this case, it is
preferable that the same material as that used in the
electron-transporting layer is used in the luminous layer with the
material doped. For example, when the electron-transporting layer
may be formed with aluminum trisoxine, it is preferable that the
luminous layer is formed with aluminum trisoxine doped with a
luminant. The electron-transporting layer may be formed by means of
a vapor deposition method, a coating method and other known method
in a manner similar to the luminous layer formation.
[0052] In the organic electroluminescence element as shown in FIG.
3 or FIG. 4, the hole-injection transporting layer is divided
functionally into two layers of the hole-injection layer 7 and the
hole-transporting layer 8. Such the hole-injection layer 7 may be
formed with a phthalocyanine compound, an electrically conductive
polymer compound, an arylamine compound etc. by a vapor deposition
method etc. to have a layer thickness of 1 to 30 nm. The
hole-transporting layer 8 may be formed with a benzidine compound,
an arylamine compound and a styryl compound etc. by a vapor
deposition method etc. to have a layer thickness of 10 to 200
nm.
[0053] When the sealing layer 9 is formed as shown in FIG. 9,
silicon oxide, zinc oxide, magnesium fluoride and magnesium oxide
etc. are vapor-deposited to form a thin layer having a thickness of
5 to 1000 nm.
[0054] In a pair of transparent electrodes (i.e., the cathode 5 and
the anode 1), a suitable leading wire (10) such as nichrome wire,
gold wire, copper wire or platinum wire is connected to the
electrodes. An organic electroluminescence element emits light by
applying appropriate voltage to both electrodes.
[0055] When the electron-injection layer is formed of a composite
layer comprising a metal oxide, a metal halide and a different
material therefrom according to the present invention,
electron-injecting properties are improved. It is thought that when
its layer is formed to have a thin thickness of 0.1 to 20 nm, the
flow of electrons is made smooth under a high electrical field, so
that light luminescence-starting voltage necessary for an organic
electroluminescence element to emit light may be low and that
stable light emission may achieved a long period of time.
[0056] The organic electroluminescence element of the present
invention is applicable to various indicator devices or display
devices, etc.
[0057] The following are Examples to explain the present invention.
Further, the organic electroluminescence element achieves the
improvement in luminous efficiency and luminance, and long life. It
should not be construed that the present invention is limited to a
luminous substance, an auxiliary luminous material, a
charge-transporting material, a sensitizer, resin, a material for
electrodes, etc., and a method of preparing an element, which are
used in Examples below.
EXAMPLE 1
[0058]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm
[0059] A thin layer having a thickness of 60 nm was formed by means
of vacuum deposition with aluminum trisoxine serving as an organic
luminous layer.
[0060] Lithium fluoride and aluminum trisoxine were co-deposited at
a ratio of 1:10 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 5 nm. A thin layer having a thickness of 200 nm was
formed by means of vapor deposition with aluminum to give a
cathode.
[0061] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 2
[0062]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium in oxide. The obtained
layer had a thickness of 60 nm
[0063] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0064] Lithium fluoride and aluminum trisoxine were co-deposited at
a ratio of 1:10 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 2 nm.
[0065] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0066] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 3
[0067]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm
[0068] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0069] Lithium fluoride and aluminum trisoxine were co-deposited at
a ratio of 1:5 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 1 nm.
[0070] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0071] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 4
[0072]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm.
[0073] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0074] Lithium fluoride and aluminum trisoxine were co-deposited at
a ratio of 1:1 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 0.5 nm.
[0075] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0076] In this way, an organic electroluminescence element was
prepared.
Comparative Example 1
[0077] An organic electroluminescence element was prepared in a
manner similar to Example 1, except that an electron-injection
layer was not formed.
EXAMPLE 5
[0078] N,N'-diphenyl-N,N'-bis (1-naphtyl)
-1,1'-diphenyl-4,4'-diamine was vapor-deposited as an organic
hole-injection transporting layer on a glass substrate coated with
indium tin oxide. The obtained layer had a thickness of 55 nm
[0079] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight serving as an organic luminous layer.
[0080] Aluminum trisoxine was vapor-deposited to form a thin
electron transporting layer having a thickness of 45 nm.
[0081] Magnesium fluoride and aluminum trisoxine were co-deposited
at a ratio of 1:5 (volume ratio) by means of an electrical
resistance heating method to form an electron-injection layer
having a layer thickness of 2 nm.
[0082] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0083] In this way, an organic electroluminescence element was
prepared.
Comparative Example 2
[0084] An organic electroluminescence element was prepared in a
manner similar to Example 5, except that magnesium was
vapor-deposited by means of an electrical resistance heating method
to form an electron-injection layer having 2 nm thickness.
Comparative Example 3
[0085] In example 5, magnesium and aluminum trisoxine were
co-deposited at a ratio of 1:5 (volume ratio) by means of an
electrical resistance heating method to form an electron-injection
layer having a layer thickness of 2 nm. Then, a thin layer having a
thickness of 200 nm was formed by means of vapor deposition with
aluminum to give a cathode. In this way, an organic
electroluminescence element was prepared.
Comparative Example 4
[0086] In example 5, an oxadiazole compound (A) represented by the
formula below was vapor-deposited by means of an electrical
resistance heating method to form an electron-injection layer
having a layer thickness of 2 nm. Then, a thin layer having a
thickness of 200 nm was formed by means of vapor deposition with
aluminum to give a cathode. In this way, an organic
electroluminescence element was prepared. 1
EXAMPLE 6
[0087] N,N'-diphenyl-N,N'-bis(1-naphtyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 55 nm .
[0088] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0089] Aluminum trisoxine was vapor-deposited to form a thin
electron transporting layer having a thickness of 45 nm.
[0090] Yttrium fluoride and aluminum trisoxine were co-deposited at
a ratio of 1:1 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 1 nm.
[0091] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0092] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 7
[0093] 4,4',4"-tris[N,N',N"-triphenyl-N,N',N"-tris(3-methylphenyl)]
triphenylamine was vapor-deposited as a hole-injection layer on a
glass substrate coated with indium tin oxide. The obtained layer
had a thickness of 15 nm
[0094]
N,N'-diphenyl-N,N'-bis(4-methylphenyl)-1,1'-bis(3-methylphenyl)-4,4-
'-diamine was vapor-deposited as a hole-transporting layer on the
hole-injection layer. The obtained layer had a thickness of 45
nm
[0095] A thin layer having a thickness of 30 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0096] Aluminum trisoxine was vapor-deposited to form a thin
electron-transporting layer having a thickness of 30 nm.
[0097] Magnesium fluoride and aluminum trisoxine were co-deposited
at a ratio of 1:3 (volume ratio) by means of an electrical
resistance heating method to form an electron-injection layer
having a layer thickness of 2 nm.
[0098] A layer having a thickness of 200 nm was formed by means of
vapor deposition with Mg and Ag, the atomic ratio of which was
10:1, to give a cathode.
[0099] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 8
[0100] N,N'-diphenyl-N,N'-bis(1-naphtyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 55 nm.
[0101] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0102] Aluminum trisoxine was vapor-deposited to form a thin
electron-transporting layer having a thickness of 45 nm.
[0103] Lithium bromide and aluminum trisoxine were co-deposited at
a ratio of 1:1 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 2 nm.
[0104] A layer having a thickness of 200 nm was formed by means of
vapor deposition with aluminum to give a cathode.
[0105] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 9
[0106] N,N'-diphenyl-N,N'-bis(1-naphtyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 55 nm .
[0107] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0108] Aluminum trisoxine was vapor-deposited to form a thin
electron-transporting layer having a thickness of 45 nm.
[0109] Lithium oxide and aluminum trisoxine were co-deposited at a
ratio of 1:1 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 2 nm.
[0110] A layer having a thickness of 200 nm was formed by means of
vapor deposition with aluminum to give a cathode.
[0111] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 10
[0112] N,N'-diphenyl-N,N'-bis(1-naphtyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 55 nm
[0113] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0114] Aluminum trisoxine was vapor-deposited to form a thin
electron-transporting layer having a thickness of 45 nm.
[0115] Yttrium oxide and aluminum trisoxine were co-deposited at a
ratio of 1:3 (volume ratio) by means of an electrical resistance
heating method to form an electron-injection layer having a layer
thickness of 1 nm.
[0116] A layer having a thickness of 200 nm was formed by means of
vapor deposition with aluminum to give a cathode.
[0117] In this way, an organic electroluminescence element was
prepared.
Comparative Example 5
[0118] An organic electroluminescence element was prepared in a
manner similar to Example 7, except that an electron-injection
layer was not formed.
EXAMPLE 11
[0119]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm
[0120] A thin layer having a thickness of 60 nm was formed by means
of vacuum deposition with aluminum trisoxine serving as an organic
luminous layer.
[0121] Lithium fluoride and aluminum were co-deposited at a ratio
of 1:1 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 1 nm.
[0122] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0123] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 12
[0124]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'1-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm .
[0125] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0126] Lithium fluoride and aluminum were co-deposited at a ratio
of 1:2 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 3 nm.
[0127] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0128] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 13
[0129] N,N'-diphenyl-N,N'-bis (3-methylphenyl)
-1,1'-diphenyl-4,4'-diamine was vapor-deposited as an organic
hole-injection transporting layer on a glass substrate coated with
indium tin oxide. The obtained layer had a thickness of 60 nm .
[0130] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0131] Lithium fluoride and indium were co-deposited at a ratio of
1:5 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 1 nm.
[0132] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0133] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 14
[0134]
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 60 nm
[0135] A thin layer having a thickness of 60 nm was formed by means
of vapor deposition with aluminum trisoxine serving as an organic
luminous layer.
[0136] Magnesium fluoride and aluminum were co-deposited at a ratio
of 1:1 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 1 nm.
[0137] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0138] In this way, an organic electroluminescence element was
prepared.
Comparative Example 6
[0139] In example 11, indium was deposited by means of an
electrical resistance heating method to form an electron-injection
layer having a layer thickness of 1 nm.
[0140] Then, a thin layer having a thickness of 200 nm was formed
by means of vapor deposition with aluminum to give a cathode. In
this way, an organic electroluminescence element was prepared.
Comparative Example 7
[0141] In example 13, magnesium and aluminum trisoxine were
co-deposited at a ratio of 2:1 (volume ratio) by means of an
electrical resistance heating method to form an electron-injection
layer having a layer thickness of 3 nm.
[0142] Then, a thin layer having a thickness of 200 nm was formed
by means of vapor deposition with aluminum to give a cathode.
[0143] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 15
[0144] N,N'-diphenyl-N,N'-bis (1-naphtyl)
-1,1'-diphenyl-4,4'-diamine was vapor-deposited as an organic
hole-injection transporting layer on a glass substrate coated with
indium tin oxide. The obtained layer had a thickness of 55 nm
[0145] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight serving as an organic luminous layer.
[0146] Aluminum trisoxine was vapor-deposited to form a thin
electron transporting layer having a thickness of 45 nm.
[0147] Magnesium fluoride and indium were co-deposited at a ratio
of 1:5 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 2 nm.
[0148] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with indium to give a cathode.
[0149] In this way, an organic electroluminescence element was
prepared.
Comparative Example 8
[0150] An organic electroluminescence element was prepared in a
manner similar to Example 15, except that an electron-injection
layer was not formed.
Comparative Example 9
[0151] In example 15, magnesium fluoride was deposited by means of
an electrical resistance heating method to form an
electron-injection layer having a layer thickness of 2 nm.
[0152] Then, a thin layer having a thickness of 200 nm was formed
by means of vapor deposition with indium to give a cathode.
[0153] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 16
[0154] N,N'-diphenyl-N,N'-bis(1-naphtyl)-1,'-diphenyl-4,4'-diamine
was vapor-deposited as an organic hole-injection transporting layer
on a glass substrate coated with indium tin oxide. The obtained
layer had a thickness of 55 nm .
[0155] A thin layer having a thickness of 10 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0156] Aluminum trisoxine was vapor-deposited to form a thin
electron transporting layer having a thickness of 45 nm.
[0157] Yttrium fluoride and aluminum were co-deposited at a ratio
of 1:1 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 1 nm.
[0158] A thin layer having a thickness of 200 nm was formed by
means of vapor deposition with aluminum to give a cathode.
[0159] In this way, an organic electroluminescence element was
prepared.
EXAMPLE 17
[0160] 4,4',4"-tris [N,N',N"-triphenyl-N,N', N"-tris
(3-methylphenyl)] triphenylamine was vapor-deposited as a
hole-injection layer on a glass substrate coated with indium tin
oxide. The obtained layer had a thickness of 15 nm.
[0161] N,N'-diphenyl-N,N'-bis (4-methylphenyl)-1,1'-bis
(3-methylphenyl)-4,4'-diamine was vapor-deposited as a
hole-transporting layer on the hole-injection layer. The obtained
layer had a thickness of 45 nm
[0162] A thin layer having a thickness of 30 nm was formed by means
of co-deposition with aluminum trisoxine doped with rubrene at 5%
by weight as an organic luminous layer.
[0163] An oxadiazole compound represented by the formula (A) below
was vapor-deposited to form an electron-transporting layer having a
layer thickness of 30 nm. 2
[0164] Magnesium oxide and indium were co-deposited at a ratio of
1:3 (volume ratio) by means of an electrical resistance heating
method to form an electron-injection layer having a layer thickness
of 2 nm.
[0165] A layer having a thickness of 200 nm was formed by means of
vapor deposition with magnesium to give a cathode.
[0166] In this way, an organic electroluminescence element was
prepared.
Comparative Example 10
[0167] An organic electroluminescence element was prepared in a
manner similar to Example 17, except that an electron-injection
layer was not formed.
Evaluation
[0168] A direct voltage was gradually applied to the organic
electroluminescence elements obtained in Examples 1 to 17 and
Comparative Examples 1 to 10 with the glass electrode as an anode.
Luminescence-starting voltage (V), luminous brightness at 5V
(cd/cm.sup.2), and luminous brightness at 10V (cd/cm.sup.2) were
measured.
[0169] Each electroluminescence element was driven at current
density of 5 mA/cm.sup.2 for 5 hours. Then, maintaining ratio of
initial output power (%) was measured as follows;
maintaining ratio of initial output power (%)=(output power
(mW/cm.sup.2)after 5 hours)/(initial output power
(mW/cm.sup.2)).times.10- 0
[0170] The result are summarized in Table 1 and Table 2.
1 TABLE 1 Luminous Luminous Maintaining Luminescence Brightness
Brightness Ratio of Starting at 5 V at 10 V initial output Voltage
(V) (cd/m.sup.2) (cd/m.sup.2) power (%) Example 1 3.5 12 410 90
Example 2 3.0 51 5240 95 Example 3 3.0 62 7440 93 Example 4 3.0 82
14530 94 Comparative 9.0 0 20 43 Example 1 Example 5 3.0 70 10160
91 Comparative 4.0 25 3942 77 Example 2 Comparative 3.5 34 4590 80
Example 3 Comparative 8.0 0 50 57 Example 4 Example 6 3.0 80 12940
92 Example 7 3.0 90 14970 93 Example 8 3.5 55 6100 90 Example 9 3.0
75 10350 92 Example 10 3.5 18 1700 89 Comparative 3.5 37 4725 83
Example 5
[0171]
2 TABLE 2 Luminous Luminous Maintaining Luminescence Brightness
Brightness Ratio of Starting at 5 V at 10 V initial output Voltage
(V) (cd/m.sup.2) (cd/m.sup.2) Power (%) Example 11 3.0 85 15310 95
Example 12 3.0 71 12440 94 Example 13 3.0 68 11750 94 Example 14
3.0 75 13930 94 Comparative 5.0 2 530 66 Example 6 Comparative 3.5
39 4650 80 Example 7 Example 15 3.0 65 9260 93 Comparative 5.0 1
420 64 Example 8 Comparative 6.0 0 370 65 Example 9 Example 16 3.0
50 7950 92 Example 17 3.5 39 6570 90 Comparative 8.5 0 25 51
Example 10
[0172] As is apparent from Tables and 2, and organic
electroluminescece element of the present invention can start to
emit light at a low voltage and shows good luminous brightness.
[0173] An organic electrouminescence element of the present
invention can keep initial-emission for a long preriod of time
stably
* * * * *