U.S. patent application number 16/367924 was filed with the patent office on 2019-07-25 for compound for organic electronic element, organic electronic element using the same, and electronic device thereof.
This patent application is currently assigned to DUK SAN NEOLUX CO., LTD.. The applicant listed for this patent is DUK SAN NEOLUX CO., LTD.. Invention is credited to Yun-sun BYUN, Daesung KIM, Jae-Taek KWON, Bum Sung LEE, Sun Hee LEE, Soung Yun MUN, Nam Jin PARK, Jin Ho YUN.
Application Number | 20190229273 16/367924 |
Document ID | / |
Family ID | 55081966 |
Filed Date | 2019-07-25 |
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United States Patent
Application |
20190229273 |
Kind Code |
A1 |
YUN; Jin Ho ; et
al. |
July 25, 2019 |
COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT
USING THE SAME, AND ELECTRONIC DEVICE THEREOF
Abstract
The present invention provides a novel compound for an EBL
capable of improving the light emitting efficiency, stability and
life span of a device, and an organic electric element and an
electronic device using the same.
Inventors: |
YUN; Jin Ho; (Cheonan-si,
KR) ; LEE; Sun Hee; (Hwaseong-si, KR) ; PARK;
Nam Jin; (Cheonan-si, KR) ; BYUN; Yun-sun;
(Daegu, KR) ; KIM; Daesung; (Yongin-si, KR)
; MUN; Soung Yun; (Cheonan-si, KR) ; LEE; Bum
Sung; (Hwaseong-si, KR) ; KWON; Jae-Taek;
(Cheonan-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DUK SAN NEOLUX CO., LTD. |
Cheonan-si |
|
KR |
|
|
Assignee: |
DUK SAN NEOLUX CO., LTD.
Cheonan-si
KR
|
Family ID: |
55081966 |
Appl. No.: |
16/367924 |
Filed: |
March 28, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15162835 |
May 24, 2016 |
10305043 |
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16367924 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/0061 20130101;
H01L 51/0052 20130101; H01L 51/5096 20130101; C07D 307/91 20130101;
H01L 27/3244 20130101; H01L 51/0073 20130101; H01L 51/0058
20130101; H01L 51/006 20130101; H01L 51/0059 20130101; Y02E 10/549
20130101; H01L 51/0081 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07D 307/91 20060101 C07D307/91 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 17, 2015 |
KR |
10-2015-0131326 |
Claims
1. A compound of Formula (1): ##STR00044## wherein: n is an integer
of 0 to 4, m is an integer of 0 to 3, R.sup.1 and R.sup.2 are each
independently selected from the group consisting of: deuterium;
halogen; a C.sub.6-C.sub.60 aryl group; a fluorenyl group; a
C.sub.2-C.sub.60 heterocyclic group including at least one
heteroatom of O, N, S, Si or P; a fused ring group of a
C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic
ring; a C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl
group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxy
group; a C.sub.6-C.sub.30 aryloxy group; and
-L'-N(R.sub.a)(R.sub.b) wherein L' is selected from the group
consisting of a single bond, a C.sub.6-C.sub.60 arylene group, a
fluorenylene group, a fused ring group of a C.sub.3-C.sub.60
aliphatic ring and a C.sub.6-C.sub.60 aromatic ring, and a
C.sub.2-C.sub.60 heterocyclic group, and R.sub.a and R.sub.b are
each independently selected from the group consisting of a
C.sub.6-C.sub.60 aryl group, a fluorenyl group, a fused ring group
of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60
aromatic ring, and a C.sub.2-C.sub.60 heterocyclic group including
at least one heteroatom of O, N, S, Si and P, in the case where m
and n are 2 or more, a plurality of R.sup.1 or a plurality of
R.sup.2 may combine to each other to form a ring, and Ar.sup.1 and
Ar.sup.2 are each a C.sub.12-20 aryl group unsubstituted or
substituted with deuterium.
2. The compound of claim 1, represented by Formula (2):
##STR00045## wherein: o and p are each an integer of 1 to 5,
R.sup.3 and R.sup.4 are each independently a C.sub.6-C.sub.10 aryl
group unsubstituted or substituted with deuterium, and R.sup.1,
R.sup.2, m and n are the same as defined in claim 1.
3. The compound of claim 1, represented by one of Formula (3) to
(5): ##STR00046## wherein R.sup.1, R.sup.2, m and n are the same as
defined in claim 1.
4. The compound of claim 2, represented by Formula (6):
##STR00047## wherein R.sup.1 to R.sup.4, m and n are the same as
defined in claim 2.
5. The compound of claim 2, represented by Formula (7) or (8):
##STR00048## Wherein: R.sup.1 and R.sup.2 are each independently
selected from the group consisting of: halogen; a C.sub.11-C.sub.60
aryl group; a C.sub.2-C.sub.60 heterocyclic group including at
least one heteroatom of O, N, S, Si or P; a fused ring group of a
C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic
ring; a C.sub.16-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl
group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxy
group; a C.sub.6-C.sub.30 aryloxy group; and
-L'-N(R.sub.a)(R.sub.b) wherein L' is selected from the group
consisting of a single bond, a C.sub.6-C.sub.60 arylene group, a
fluorenylene group, a fused ring group of a C.sub.3-C.sub.60
aliphatic ring and a C.sub.6-C.sub.60 aromatic ring, and a
C.sub.2-C.sub.60 heterocyclic group, and R.sub.a and R.sub.b are
each independently selected from the group consisting of a
C.sub.6-C.sub.60 aryl group, a fluorenyl group, a fused ring group
of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60
aromatic ring, and a C.sub.2-C.sub.60 heterocyclic group including
at least one heteroatom of O, N, S, Si and P, in the case where m
and n are 2 or more, a plurality of R.sup.1 or a plurality of
R.sup.2 may combine to each other to form a ring, and R.sup.3,
R.sup.4 m and n are the same as defined in claim 2.
6. The compound of claim 1, represented by one of the following
compounds: ##STR00049## ##STR00050## ##STR00051##
7. An organic electric element comprising: a first electrode; a
second electrode; and an organic layer positioned between the first
electrode and the second electrode, the organic layer comprising an
electron blocking layer (EBL) formed with the compound claim 1.
8. The organic electric element of claim 7, wherein the organic
layer further comprises a hole injection layer, a hole transport
layer, a light emitting layer, an electron transport layer, an
electron injection layer, or a mixture thereof, and wherein the EBL
is formed between the electron transport layer and the hole
transport layer.
9. The organic electric element of claim 8, wherein the organic
layer further comprises a hole blocking layer, an
emission-auxiliary layer, a buffer layer, or a mixture thereof
formed between the electron transport layer and the hole transport
layer.
10. The organic electric element of claim 7, wherein the organic
material layer is formed by one of a spin coating process, a nozzle
printing process, an inkjet printing process, a slot coating
process, a dip coating process, and a roll-to-roll process.
11. The organic electric element of claim 7, further comprising a
light efficiency enhancing layer formed on one side of the first
electrode and/or one side of the second electrode.
12. An electronic device comprising a display apparatus comprising
the organic electric element according to claim 7; and a driving
part configured to drive the display apparatus.
13. The electronic device of claim 12, wherein the organic electric
element is an organic light emitting diode (OLED), an organic solar
cell, an organic photo conductor, an organic transistor, or a
device for monochromic or white illumination.
14. An organic electric element comprising: a first electrode; a
second electrode; an organic layer between the first electrode and
the second electrode; and a light efficiency enhancing layer formed
on one side of the first electrode and/or one side of the second
electrode, the side being opposite to the organic layer, wherein
light efficiency enhancing layer comprises the compound of claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 15/162,835, filed May 24, 2016, which claims
the benefit of priority from Korean Patent Application No.
10-2015-0131326, filed Sep. 17, 2015, the contents of each of which
are incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to compound for organic
electronic element, organic electronic element using the same, and
an electronic device thereof.
DESCRIPTION OF THE RELATED ART
[0003] Recently, in an organic light emitting diode (OLED),
researches on adding an electron blocking layer (EBL) between a
hole transport layer and an emission layer are continuously
conducted to solve defects on light emission at the interface of
the hole transport layer and on the decrease of efficiency due to
charge unbalance in the emission layer. Particularly, developments
on different electron blocking materials (EBM) according to
respective emission layer (R, G, B) are conducted.
[0004] However, in the case where different EBLs are used for
respective emission layer (R, G, B) as described above, various
limitations are generated at the point where an OLED panel is being
gradually large-sized. Particularly, each of the EBLs is required
to be patterned according to emission regions (R, G, B), and the
patterning time increases (the number of masks used increases),
consuming time for processing increases (exchange time of masks
increases), and processing issues accompanied with the mask
exchange is generated.
[0005] In order to solve the defects generated due to the use of
different EBLs according to the emission regions (R, G, B) as
described above, developments on EBMs commonly used in the emission
regions (R, G, B) are desperately in need. However, due to
luminescent materials used in each emission region of an OLED panel
currently produced, the development on a common EBM is difficult.
The luminescent material used in the OLED panel is largely
classified as a phosphorescent luminescent material and a
fluorescent luminescent material. For green and red color, the
manufacture of a panel having high efficiency and long life may be
easy through using the phosphorescent luminescent material,
however, for blue color, the development of the phosphorescent
luminescent material having high efficiency and long life is
difficult, and the fluorescent luminescent material is used
now.
SUMMARY OF THE INVENTION
[0006] Accordingly, developments on an EBM having both electrical
and physical properties required for each of the fluorescent
luminescent material and the phosphorescent luminescent material
are desperately in need in order to use a common EBL for each
emission region (R, G, B).
[0007] An object of the present invention is to provide a compound
for EBL which is commonly used in each of the emission regions to
improve high luminous efficiency, a low driving voltage, a high
heat resistance, color purity and life, and an organic electric
element and an electronic device using the same.
[0008] The present invention provides a compound represented by
Formula below.
##STR00001##
[0009] In another aspect of the present invention, the present
invention provides organic electric elements using the compound
represented by the formula above and electronic devices
thereof.
[0010] By using the compound according to the present invention to
an electron blocking layer (EBL), an organic electric element
according to one or more embodiments of the present invention not
only has high luminous efficiency, low driving voltage and high
heat resistance and, but can also be significantly improved in
color purity and life span.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The patent or application file contains at least one drawing
executed in color. Copies of this patent or patent application
publication with color drawing(s) will be provided by the Office
upon request and payment of the necessary fee.
[0012] FIG. 1 illustrates one embodiment of the organic light
emitting diode according to the present invention.
[0013] FIG. 2 illustrates chemical structures of Compound 1-1 and
Comparative Compound 2 and electron cloud thereof (LUMO and
G-HOMO).
DETAILED DESCRIPTION OF THE INVENTION
[0014] Hereinafter, some embodiments of the present invention will
be described in detail with reference to the accompanying
illustrative drawings.
[0015] In designation of reference numerals to components in
respective drawings, it should be noted that the same elements will
be designated by the same reference numerals although they are
shown in different drawings. Further, in the following description
of the present invention, a detailed description of known functions
and configurations incorporated herein will be omitted when it may
make the subject matter of the present invention rather
unclear.
[0016] In addition, terms, such as first, second, A, B, (a), (b) or
the like may be used herein when describing components of the
present invention. Each of these terminologies is not used to
define an essence, order or sequence of a corresponding component
but used merely to distinguish the corresponding component from
other component(s). It should be noted that if it is described in
the specification that one component is "connected," "coupled" or
"joined" to another component, a third component may be
"connected," "coupled," and "joined" between the first and second
components, although the first component may be directly connected,
coupled or joined to the second component. In addition, it will be
understood that when an element such as a layer, film, region or
substrate is referred to as being "on" or "over" another element,
it can be directly on the other element or intervening elements may
also be present. In contrast, when an element is referred to as
being "directly on" another element, there are no intervening
elements present.
[0017] As used in the specification and the accompanying claims,
unless otherwise stated, the following is the meaning of the term
as follows.
[0018] Unless otherwise stated, the term "halo" or "halogen" as
used herein includes fluorine, bromine, chlorine, or iodine.
[0019] Unless otherwise stated, the term "alkyl" or "alkyl group"
as used herein has a single bond of 1 to 60 carbon atoms, and means
saturated aliphatic functional radicals including a linear alkyl
group, a branched chain alkyl group, a cycloalkyl group
(alicyclic), an cycloalkyl group substituted with a alkyl or an
alkyl group substituted with a cycloalkyl.
[0020] Unless otherwise stated, the term "haloalkyl" or "halogen
alkyl" as used herein means an alkyl group substituted with a
halogen.
[0021] Unless otherwise stated, the term "alkenyl" or "alkynyl" as
used herein has, but not limited to, double or triple bonds of 2 to
60 carbon atoms, and includes a linear or a branched chain
group.
[0022] Unless otherwise stated, the term "cycloalkyl" as used
herein means, but not limited to, alkyl forming a ring having 3 to
60 carbon atoms.
[0023] Unless otherwise stated, the term "alkoxy group" or
"alkyloxy group" as used herein means an oxygen radical attached to
an alkyl group, but not limited to, and has 1 to 60 carbon
atoms.
[0024] Unless otherwise stated, the term "aryloxyl group" or
"aryloxy group" as used herein means an oxygen radical attached to
an aryl group, but not limited to, and has 6 to 60 carbon
atoms.
[0025] Unless otherwise stated, the term "fluorenyl group" or
"fluorenylene group" as used herein means a monovalent or divalent
functional group in the following structure in which all R, R' and
R'' are hydrogen, and the term "substituted fluorenyl group" or
"substituted fluorenylene group" means that at least one of R, R'
and R'' is a substituent other than hydrogen and includes a case of
combining R and R' to each other and forming a spiro compound along
with a carbon atom making the combination.
##STR00002##
[0026] Unless otherwise stated, the term "aryl group" or "arylene
group" as used herein has, but not limited to, 6 to 60 carbon
atoms. In the present invention, aryl or arylene includes a
monocycle, ring assemblies, a fused ring system, a spiro compound,
etc.
[0027] Unless otherwise stated, the term "heterocyclic group" as
used herein includes a non-aromatic ring as well as an aromatic
ring such as "heteroaryl group" and "heteroarylene group" and each
means, but not limited to, a ring having 2 to 60 carbon atoms
including at least one heteroatom. Unless otherwise stated, the
term "heteroatom" used in the present disclosure means N, O, S, P
or Si, and the heterocyclic group means a monocycle, ring
assemblies, a fused ring system, a spiro compound, etc. including
the heteroatom.
[0028] Also, the term "heterocyclic group" may include SO.sup.2
instead of carbon consisting of cycle. For example, "heterocyclic
group" includes compound below.
##STR00003##
[0029] The term "ring" as used herein includes a monocyclic and
polycyclic group, a heterocyclic group including at least one
heteroatom as well as a hydrocarbon ring, and an aromatic and
non-aromatic ring.
[0030] The term "polycyclic group" as used herein includes ring
assemblies such as biphenyl and terphenyl, a fused ring system and
a spiro compound, aromatic and non-aromatic group, and a
heterocycle including at least one heteroatom as well as a
hydrocarbon ring.
[0031] The term "ring assemblies" as used herein is obtained by
directly connecting two or more rings (monocyclic group or fused
ring system) via a direct linkage or a double bond, where the
number of the direct connection is less by one than the total
number of the rings included in a compound. In the ring assemblies,
the same or different ring systems may be directly connected via a
direct linkage or a double bond.
[0032] The term "fused ring system" as used herein means a fused
ring shape sharing at least two atoms and includes a fused shape of
at least two hydrocarbon ring systems and a fused shape of at least
one heterocycle including at least one heteroatom. The fused ring
system may be an aromatic ring, a heteroaromatic ring, an aliphatic
ring, or the combination thereof.
[0033] The term "spiro compound" as used herein has "spiro union",
and the spiro union means a connection of two rings by sharing only
one atom. In this case, the atom shared by the two rings is
referred to as "spiro atom". According to the number of the spiro
atom included in a compound, the compound is referred to as
"monospiro-", "dispiro-", or "trispiro-" compound.
[0034] In addition, if a compound is named with continuous
prefixes, substituents are listed in the order. For example, an
arylalkoxy group means an alkoxy group substituted with an aryl
group, an alkoxycarbonyl group means a carbonyl group substituted
with an alkoxy group, and an arylcarbonylalkenyl group means an
alkenyl group substituted with an arylcarbonyl group, where
arylcarbonyl group is a carbonyl group substituted with an aryl
group.
[0035] Unless otherwise stated, the term "substituted or
unsubstituted" as used herein means that substitution is carried
out by at least one substituent selected from the group consisting
of, but not limited to, deuterium, halogen, an amino group, a
nitrile group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy
group, a C1-C20 alkylamine group, a C1-C20 alkylthiophene group, a
C6-C20 arylthiophene group, a C2-C20 alkenyl group, a C2-C20
alkynyl group, a C3-C20 cycloalkyl group, a C6-C60 aryl group, a
C6-C20 aryl group, a C6-C20 aryl group substituted by deuterium, a
C8-C20 arylalkenyl group, a silane group, a boron group, a
germanium group and a C2-C60 heterocyclic group including at least
one heteroatom of O, N, S, Si or P.
[0036] Unless otherwise stated, the Formulas used in the present
invention are as defined in the index definition of the substituent
of the following Formula:
##STR00004##
[0037] wherein, when a is an integer of zero, the substituent
R.sup.1 is absent, when a is an integer of 1, the sole substituent
R.sup.1 is linked to any one of the carbon atoms constituting the
benzene ring, when a is an integer of 2 or 3, the substituent
R.sup.1 s may be the same and different, and are linked as follows:
and when a is an integer of 4 to 6, the substituents R.sup.1 s may
be linked to the carbon of the benzene ring in a similar manner,
whereas hydrogen atoms linked to carbon constituents of the benzene
ring are not represented as usual.
##STR00005##
[0038] FIG. 1 illustrates an example of an organic electric element
according to an embodiment of the present invention.
[0039] Referring to FIG. 1, an organic electric element 100
according to the present invention includes a first electrode 120
formed on a substrate 110, a second electrode 180, and an organic
material layer between the first electrode 120 and the second
electrode 180, which contains the compound according to the present
invention. Here, the first electrode 120 may be an anode (positive
electrode), and the second electrode 180 may be a cathode (negative
electrode). In the case of an inverted organic electric element,
the first electrode may be a cathode, and the second electrode may
be an anode.
[0040] The organic material layer may include a hole injection
layer 130, a hole transport layer 140, a light emitting layer 150,
an electron transport layer 160, and an electron injection layer
170 formed in sequence on the first electrode 120. Here, at least
one of the layers may further include a hole blocking layer, an
electron blocking layer, an emission-auxiliary layer 151, a buffer
layer 141, etc., and the electron transport layer 160 and the like
may serve as the hole blocking layer.
[0041] Although not shown, the organic electric element according
to the present invention may further include at least one
protective layer or one capping layer formed on at least one of the
sides the first and second electrodes, which is a side opposite to
the organic material layer.
[0042] The organic light emitting diode according to an embodiment
of the present invention may be manufactured using various
deposition methods. The organic light emitting diode according to
an embodiment of the present invention may be manufactured using a
PVD (physical vapor deposition) method or CVD (chemical vapor
deposition) method. For example, the organic light emitting diode
may be manufactured by depositing a metal, a conductive metal
oxide, or a mixture thereof on the substrate 110 to form the anode
120, forming the organic material layer including the hole
injection layer 130, the hole transport layer 140, the light
emitting layer 150, the electron transport layer 160, and the
electron injection layer 170 thereon, and then depositing a
material, which can be used as the cathode 180, thereon. Also, the
emission-auxiliary layer 151 may be further formed between the hole
transport layer 140 and the light emitting layer 150.
[0043] Also, the organic material layer may be manufactured in such
a manner that a smaller number of layers are formed using various
polymer materials by a soluble process or solvent process, for
example, spin coating, nozzle printing, inkjet printing, slot
coating, dip coating, roll-to-roll, doctor blading, screen
printing, or thermal transfer etc. Since the organic material layer
according to the present invention may be formed in various ways,
the scope of protection of the present invention is not limited by
a method of forming the organic material layer.
[0044] The organic electric element according to the present
invention may be of a top emission type, a bottom emission type, or
a dual emission type according to the material used. A WOLED (White
Organic Light Emitting Device) readily allows for the formation of
ultra-high definition images, and is of excellent processability as
well as enjoying the advantage of being produced using conventional
color filter technologies for LCDs. In this regard, various
structures for WOLEDs, used as back light units, have been, in the
most part, suggested and patented. Representative among the
structures are a parallel side-by-side arrangement of R (Red), G
(Green), B (Blue) light-emitting units, a vertical stack
arrangement of RGB light-emitting units, and a CCM (color
conversion material) structure in which electroluminescence from a
blue (B) organic light emitting layer, and photo-luminescence from
an inorganic luminescent using the electroluminescence are
combined. The present invention is applicable to these WOLEDs.
[0045] Further, the organic electric element according to the
present invention may be any one of an organic light emitting diode
(OLED), an organic solar cell, an organic photo conductor (OPC), an
organic transistor (organic TFT), and an element for monochromatic
or white illumination.
[0046] Another embodiment of the present invention may include an
electronic device including a display device, which includes the
above described organic electric element, and a control unit for
controlling the display device. Here, the electronic device may be
a wired/wireless communication terminal which is currently used or
will be used in the future, and covers all kinds of electronic
devices including a mobile communication terminal such as a
cellular phone, a personal digital assistant (PDA), an electronic
dictionary, a point-to-multipoint (PMP), a remote controller, a
navigation unit, a game player, various kinds of TVs, and various
kinds of computers.
[0047] Hereinafter, a compound according to an aspect of the
present invention will be described.
[0048] The compound according to an aspect of the present invention
is represented by the following Formula 1 below.
##STR00006##
[0049] {In the Formula (1) above,
1) n is an integer of 0 to 4, m is an integer of 0 to 3, R.sup.1, 2
are each independently selected from the group consisting of
deuterium; halogen; a C6-C60 aryl group; a fluorenyl group; a
C.sub.2-C.sub.60 heterocyclic group including at least one
heteroatom of O, N, S, Si or P; a fused ring group of a
C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic
ring; a C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl
group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxy
group; a C.sub.6-C.sub.30 aryloxy group; and
-L'-N(R.sub.a)(R.sub.b) (where L' above may be selected from the
group consisting of a single bond; a C.sub.6-C.sub.60 arylene
group; a fluorenylene group; a fused ring group of a
C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic
ring; and a C.sub.2-C.sub.60 heterocyclic group, R.sub.a and
R.sub.b above are each independently selected from the group
consisting of a C.sub.6-C.sub.60 aryl group; a fluorenyl group; a
fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a
C.sub.6-C.sub.60 aromatic ring; and a C.sub.2-C.sub.60 heterocyclic
group including at least one heteroatom of O, N, S, Si or P), or in
the case where m and n are 2 or more, m and n are each in plural
and the same or different, and a plurality of R.sup.1 or a
plurality of R.sup.2 may combine to each other to form a ring, and
2) Ar.sup.1, 2 are a C.sub.12-20 aryl group substituted or
unsubstituted with deuterium.
[0050] Specially, according to the present invention, the compound
represented by Formula 1 above provides a compound of Formula 2
below.
##STR00007##
{In the Formula (2) above, 1) o and p are an integer of 1 to 5, and
R.sup.3,4 are each independently a C.sub.6-C.sub.10 aryl group
substituted or unsubstituted with deuterium. 2) R.sup.1-2, m and n
are as defined in Formula 1 above.}
[0051] In an aspect of the present invention, the compound
represented by Formula 1 above provides any one of compounds of
Formula 3 to Formula 5 below.
##STR00008##
[0052] {In Formula 3 to Formula 5 above, R.sup.1-2, m and n are as
defined in Formula 1 above.}
[0053] In addition, according to the present invention, the
compound represented by the Formula 1 above provides a compound of
the following Formula 6 to 8.
##STR00009##
[0054] {In Formula 6 to Formula 8 above, R.sup.1-4, m, n, o and p
are as defined above.}
[0055] More specially, according to the present invention, the
compound represented by Formula 1 above includes compounds
below
##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014##
##STR00015## ##STR00016## ##STR00017## ##STR00018##
##STR00019##
[0056] In another aspect of the present invention, there is
provided a compound for an organic electric element represented by
Formula 1 above
[0057] In another aspect of the present invention, there is
provided an organic electric element comprising the compound
represented by Formula 1 above.
[0058] The organic electric element can comprise a first electrode,
a second electrode, and an organic material layer disposed between
the first electrode and the second electrode. The organic material
layer can comprise the compound represented by Formula 1. In
addition, a light efficiency enhancing layer formed on at least one
of the opposite side to the organic layer, or on the opposite side
to the organic layer among one side of the second electrode may be
further included.
[0059] In addition, the present invention provides an organic
electric device in which the compound is included in an organic
material layer formed between the first electrode and an light
emitting layer. The organic layer including the compound forms an
EBL, and the compound may be included in the EBL as a mixture of
one or two kinds of the compounds.
[0060] Further, the organic material layer of the present invention
is formed by any one of the spin coating, nozzle printing process,
inkjet printing process, slot coating process, dip coating and
roll-to-roll process, and the present invention also provides an
organic electric element including the compound as the material of
the EBL in the organic material layer.
[0061] The present invention also provides an electronic device
including a display device including the organic electric element;
and a control part driving the display apparatus.
[0062] According to another aspect, the present invention provides
an electronic device characterized in that the organic electric
element is at least one of an OLED, an organic solar cell, an
organic photo conductor, an organic transistor and an element for
monochromic or white illumination. Here, the electronic device may
be a wired/wireless communication terminal which is currently used
or will be used in the future, and covers all kinds of electronic
devices including a mobile communication terminal such as a
cellular phone, a personal digital assistant (PDA), an electronic
dictionary, a point-to-multipoint (PMP), a remote controller, a
navigation unit, a game player, various kinds of TVs, and various
kinds of computers.
[0063] Hereinafter, Synthesis Examples of the compound represented
by Formula according to the present invention and Preparation
Examples of an organic electric element will be described in detail
by way of example. However, the following examples are only for
illustrative purposes and are not intended to limit the scope of
the invention.
SYNTHESIS EXAMPLE
[0064] The final product represented by Formula 1 according to the
present invention can be synthesized by reaction between Sub 1 and
Sub 2 as illustrated in the following Reaction Scheme 1.
##STR00020##
Synthesis Examples of Sub 1
[0065] Sub 1 of Reaction Scheme 1 can be synthesized according to,
but not limited to, the reaction path of the following Reaction
Scheme 2.
##STR00021##
Synthesis Examples of Sub 1 (1)
##STR00022##
[0067] Sub 1-1-1 (23.3 g, 0.11 mol),
4'-bromo-3-iodo-1,1'-biphenyl(46.7 g, 0.13 mol), K.sub.2CO.sub.3
(46.03 g, 0.33 mol), Pd(PPh.sub.3).sub.4 (5.13 g, 4 mol %) were
dissolved in anhydrous THE and a small amount of water, followed by
reflux at 80.degree. C. for 12 hours. Upon completion of the
reaction, the temperature of the reaction product was lowered to
room temperature, the reaction product was extracted with
CH.sub.2Cl.sub.2, and was washed with water. The extracted organic
layer was dried with MgSO.sub.4 and concentrated, and then the
produced organic material was seperated by silicgel column to
obtain desired Sub1 (1) (36.5 g, yield 81%).
Synthesis Examples of Sub 1(2)
##STR00023##
[0069] Using Sub 1-1-2 (31.7 g, 0.11 mol),
3-bromo-3'-iodo-1,1'-biphenyl(46.7 g, 0.13 mol) as the starting
material, the same procedure as described in the synthesis method
of Sub 1(1) above was carried out to obtain desired Sub 1(2) (40.8
g, yield 81%).
Synthesis Examples of Sub 1(3)
##STR00024##
[0071] Using Sub 1-1-3 (34.3 g, 0.11 mol),
2-bromo-3'-iodo-1,1'-biphenyl(46.7 g, 0.13 mol) as the starting
material, the same procedure as described in the synthesis method
of Sub 1(1) above was carried out to obtain desired Sub 1(3) (43.4
g, yield 81%).
[0072] The examples of Sub 1 include, but are not limited to, the
following compounds.
##STR00025## ##STR00026## ##STR00027##
TABLE-US-00001 TABLE 1 compound FD-MS compound FD-MS Sub 1(1) m/z =
398.03(C.sub.24H.sub.15BrO = 399.28) Sub 1(2) m/z =
474.06(C.sub.30H.sub.19BrO = 475.38) Sub 1(3) m/z =
498.06(C.sub.32H.sub.19BrO = 499.40) Sub 1(4) m/z =
474.06(C.sub.30H.sub.19BrO = 475.38) Sub 1(5) m/z =
448.05(C.sub.28H.sub.17BrO = 449.34) Sub 1(6) m/z =
498.06(C.sub.32H.sub.19BrO = 499.40) Sub 1(7) m/z =
448.05(C.sub.28H.sub.17BrO = 449.34) Sub 1(8) m/z =
398.03(C.sub.24H.sub.15BrO = 399.28) Sub 1(9) m/z =
498.06(C.sub.32H.sub.19BrO = 499.40) Sub 1(10) m/z =
474.06(C.sub.30H.sub.19BrO = 475.38) Sub 1(11) m/z =
448.05(C.sub.28H.sub.17BrO = 449.34) Sub 1(12) m/z =
398.03(C.sub.24H.sub.15BrO = 399.28)
[0073] Sub 2 of Reaction Scheme 1 can be synthesized according to,
but not limited to, the reaction path of the following Reaction
Scheme 2.
##STR00028##
Synthesis Examples of Sub 2(1)
##STR00029##
[0075] After 4-bromo-1,1'-biphenyl (5.6 g, 24 mmol) was dissolved
in toluene, followed by being added [1,1'-biphenyl]-4-amine (3.4 g,
20 mmol), Pd.sub.2(dba).sub.3 (0.5 g, 0.6 mmol), P(t-Bu).sub.3 (0.2
g, 2 mmol), NaOt-Bu (5.8 g, 60 mmol), toluene (300 mL), followed by
reflux at 100.degree. C. for 24 hours. Upon completion of the
reaction, the reaction product was extracted with ether and water.
The organic layer was dried with MgSO.sub.4 and concentrated, and
then the produced organic material was purified by silicagel column
and recrystallized to obtain desired Sub 2(1) 6.2 g, (yield
80%).
[0076] The examples of Sub 2 include, but not limited to, the
following compounds.
##STR00030## ##STR00031## ##STR00032## ##STR00033##
TABLE-US-00002 TABLE 2 compound FD-MS compound FD-MS Sub 2(1) m/z =
321.15(C.sub.24H.sub.19N = 321.41) Sub 2(2) m/z =
371.17(C.sub.28H.sub.21N = 371.47) Sub 2(3) m/z =
371.17(C.sub.28H.sub.21N = 371.47) Sub 2(4) m/z =
421.18(C.sub.32H.sub.23N = 421.53) Sub 2(5) m/z =
321.15(C.sub.24H.sub.19N = 321.41) Sub 2(6) m/z =
371.17(C.sub.28H.sub.21N = 371.47) Sub 2(7) m/z =
371.17(C.sub.28H.sub.21N = 371.47) Sub 2(8) m/z =
421.18(C.sub.32H.sub.23N = 421.53) Sub 2(9) m/z =
321.15(C.sub.24H.sub.19N = 321.41) Sub 2(10) m/z =
371.17(C.sub.28H.sub.21N = 371.47) Sub 2(11) m/z =
321.15(C.sub.24H.sub.19N = 321.41) Sub 2(12) m/z =
321.15(C.sub.24H.sub.19N = 321.41)
Synthesis Examples of Final Products
Synthesis Examples of 1-1
##STR00034##
[0078] After Sub 1(1)(9.6 g, 24 mmol) was dissolved in toluene,
followed by being adding Sub 2(1) (6.4 g, 20 mmol) and added with
Pd.sub.2(dba).sub.3 (0.5 g, 0.6 mmol), P(t-Bu).sub.3 (0.2 g, 2
mmol), NaOt-Bu (5.8 g, 60 mmol), toluene (300 mL), followed by
reflux at 100.degree. C. for 24 hours. After the reaction was
completed, the reaction product was extracted with ether and water.
The organic layer was dried with MgSO.sub.4 and concentrated. Then,
the produced organic layer was purified by silicagel column and
recrystallized to obtain a final compound 13.1 g (yield 85%).
Synthesis Examples of 1-6
##STR00035##
[0080] After Sub 1(1)(9.6 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(6) (7.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 13.1 g (yield 79%)
Synthesis Examples of 1-11
##STR00036##
[0082] After Sub 1(1)(9.6 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(11) (6.4 g, 20 mmol), the same procedure
as described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 12.7 g (yield 83%)
Synthesis Examples of 2-4
##STR00037##
[0084] After Sub 1(8)(9.6 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(4) (8.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 14.9 g (yield 84%)
Synthesis Examples of 2-5
##STR00038##
[0086] After Sub 1(8)(9.6 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(5) (6.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 13.2 g (yield 86%)
Synthesis Examples of 2-10
##STR00039##
[0088] After Sub 1(7)(10.8 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(10) (7.4 g, 20 mmol), the same procedure
as described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 13.9 g (yield 78%)
Synthesis Examples of 3-3
##STR00040##
[0090] After Sub 1(12)(9.6 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(3) (7.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 12.4 g (yield 75%)
Synthesis Examples of 3-8
##STR00041##
[0092] Sub 1(12)(9.6 g, 24 mmol) was dissolved in toluene, followed
by adding Sub 2(8) (8.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 12.8 g (yield 85%)
Synthesis Examples of 3-9
##STR00042##
[0094] After Sub 1(10)(11.4 g, 24 mmol) was dissolved in toluene,
followed by adding Sub 2(9) (6.4 g, 20 mmol), the same procedure as
described in Synthesis Method of 1-1 was carried out to obtain
desired final compound 13.1 g (yield 76%)
TABLE-US-00003 TABLE 3 compound FD-MS compound FD-MS 1-1 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 1-2 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 1-3 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 1-4 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 1-5 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 1-6 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 1-7 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 1-8 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 1-9 m/z =
715.29(C.sub.54H.sub.37NO = 715.88) 1-10 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 1-11 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 1-12 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 2-1 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 2-2 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 2-3 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 2-4 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 2-5 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 2-6 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 2-7 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 2-8 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 2-9 m/z =
715.29(C.sub.54H.sub.37NO = 715.88) 2-10 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 2-11 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 2-12 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 3-1 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 3-2 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 3-3 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 3-4 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 3-5 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 3-6 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 3-7 m/z =
689.27(C.sub.52H.sub.35NO = 689.84) 3-8 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 3-9 m/z =
715.29(C.sub.54H.sub.37NO = 715.88) 3-10 m/z =
739.29(C.sub.56H.sub.37NO = 739.90) 3-11 m/z =
639.26(C.sub.48H.sub.33NO = 639.78) 3-12 m/z =
739.29(C.sub.56H.sub.37NO = 739.90)
[0095] Manufacture and Evaluation of Organic Electric Element
Example 1) Manufacture and Test of Blue OLED (EBL)
[0096] On an ITO layer (anode) formed on a glass substrate, 2-TNATA
was vacuum deposited to form a hole injection layer with a
thickness of 60 nm, and
N,N'-bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-dia-
mine (hereinafter will be abbreviated as NPB) was vacuum deposited
on the hole injection layer to form a hole transport layer with a
thickness of 60 nm. Then, the compound of the present invention was
vacuum deposited on the hole transport layer to form an EBL with a
thickness of 20 nm. On the EBL, an light emitting layer with a
thickness of 30 nm was deposited using
9,10-di(naphthalen-2-yl)anthracene as a host doped with BD-052X
(Idemitsukosan) as a dopant in a weight ratio of 96:4.
(1,1'-bisphenyl)-4-olato)bis(2-methyl-8-quinolinolato)aluminum
(hereinafter will be abbreviated as BAlq) was vacuum deposited to
form a hole blocking layer with a thickness of 40 nm, and an
electron transport layer was formed using
tris(8-quinolinol)aluminum (hereinafter will be abbreviated as
Alq3) to a thickness of 40 nm. After that, an alkali metal halide,
LiF was deposited as an electron injection layer to a thickness of
0.2 nm, and Al was deposited as a cathode to a thickness of 150 nm
to manufacture an OLED.
[0097] To the OLEDs which were manufactured in examples and
comparative examples, a forward bias direct current voltage was
applied, and electroluminescent (EL) properties were measured using
PR-650 of Photoresearch Co., and T95 life was measured using a life
measuring apparatus manufactured by McScience Inc. with a reference
luminance of 500 cd/m.sup.2. In the following table, the results on
the manufacture of a device and evaluation are shown.
Comparative Example 1
[0098] Except for not using EBL, an OLED was manufactured in the
same manner as described in the embodiment 1 above.
Comparative Example 2 to Comparative Example 3
[0099] Except that EBL was formed in using the Comparative Example
1 to 2, an OLED was manufactured in the same manner as described in
the embodiment 1 above, instead of the inventive compound.
##STR00043##
TABLE-US-00004 TABLE 4 Current Brightness Lifetime CIE compound
Voltage Density (cd/m2) Efficiency T(95) (x, y) Comparative -- 6.0
13.5 500.0 3.7 61.8 (0.15, example (1) 0.13) Comparative
Comparative 6.1 11.1 500.0 4.5 83.5 (0.14, example (2) compound 1
0.14) Comparative Comparative 5.8 9.8 500.0 5.1 95.6 (0.15, example
(3) compound 2 0.14) Example(1) compound(1-1) 5.2 7.9 500.0 6.3
111.3 (0.14, 0.14) Example(2) compound(1-2) 5.3 7.8 500.0 6.4 111.7
(0.15, 0.13) Example (3) compound(1-3) 5.2 7.9 500.0 6.4 111.6
(0.15, 0.16) Example(4) compound(1-4) 5.2 7.8 500.0 6.4 110.3
(0.15, 0.14) example (5) compound(1-5) 5.3 7.8 500.0 6.4 118.5
(0.15, 0.13) example (6) compound(1-6) 5.3 7.9 500.0 6.4 112.6
(0.14, 0.14) example (7) compound(1-7) 5.3 7.8 500.0 6.4 118.7
(0.15, 0.14) example (8) compound(1-8) 5.3 7.7 500.0 6.5 110.3
(0.15, 0.13) example (9) compound(2-1) 5.3 8.1 500.0 6.2 114.5
(0.15, 0.14) example (10) compound(2-2) 5.4 8.2 500.0 6.1 114.8
(0.15, 0.13) example (11) compound(2-3) 5.3 8.2 500.0 6.1 119.6
(0.14, 0.14) example (12) compound(2-4) 5.4 8.3 500.0 6.0 113.8
(0.14, 0.14) example (13) compound(2-5) 5.3 8.2 500.0 6.1 117.5
(0.14, 0.14) example (14) compound(2-6) 5.4 8.1 500.0 6.2 117.1
(0.15, 0.13) example (15) compound(2-7) 5.4 8.1 500.0 6.2 112.6
(0.15, 0.14) example (16) compound(2-8) 5.3 8.1 500.0 6.2 114.1
(0.15, 0.14) example (17) compound(3-1) 5.4 8.4 500.0 5.9 112.0
(0.15, 0.13) example (18) compound(3-2) 5.5 8.6 500.0 5.8 116.9
(0.15, 0.13) example (19) compound(3-3) 5.4 8.3 500.0 6.0 112.7
(0.14, 0.14) example (20) compound(3-4) 5.4 8.5 500.0 5.9 113.3
(0.15, 0.14) example (21) compound(3-5) 5.4 8.5 500.0 5.9 113.5
(0.15, 0.14) example (22) compound(3-6) 5.4 8.5 500.0 5.9 114.8
(0.14, 0.14) example (23) compound(3-7) 5.4 8.4 500.0 6.0 119.0
(0.15, 0.13) example (24) compound(3-8) 5.5 8.5 500.0 5.9 110.4
(0.15, 0.16)
[0100] As is apparent from data of Table 4 above, in case that the
organic electroluminescent device using the material of the present
invention, the main substituent were found to be low driving
voltage, significantly high luminous efficiency and high life span,
compared to that of not using EBL or that of Comparative Example
using Comparative compound 1 and 2.
[0101] In other words, the results for Comparative Examples 1 and 2
and Examples 1-24 using the EBL are better when compared to those
for Comparative example 1 not using the EBL, and the driving
voltage and life of Comparative Compound 2 and the inventive
compounds having a non-linear linker are improved, and
particularly, efficiency is markedly improved when compared to
those for Comparative Compound 1 which is similar to the inventive
compounds, however in which, a linker-amine group is linearly
substituted at position 4 of dibenzofuran. The results are
considered to be obtainable, because Comparative Compound 2 and the
inventive compounds having the non-linear linker have a decreased
bonding angle than Comparative Compound 1 having a linear linker,
and so, has a high T1 value and improved electron blocking
ability.
[0102] When comparing Comparative Compound 2 having the same
non-linear linker as the inventive compounds with the inventive
compound, it may be confirmed that even though the cores are the
same, the physical properties of compounds are markedly changed
according to the kind of substituents.
[0103] As shown in FIG. 2 In Inventive Compound 1-1 of which
substituent is bis-biphenyl, HOMO electron cloud is formed except
for dibenzofuran, however in Comparative Compound 2 of which
substituent is terphenyl, the electron cloud is not formed to the
terminal of terphenyl. When examining LUMO electron cloud,
difference may be clearly shown. The LUMO electron cloud is formed
for dibenzofuran in Inventive Compound 1-1 and is formed for
bis-terphenyl in Comparative Compound 2. Accordingly, the energy
level values of HOMO and LUMO become different, and the inventive
compounds may have a higher LUMO value and a wider band gap. Due to
such chemical difference, holes and electrons make charge balance
owing to an appropriate EBL role while measuring a device, and
light emission is attained not at the interface of a hole transport
layer but in the light emitting layer, thereby decreasing a driving
voltage and maximizing efficiency and life span.
[0104] As described in the results, even though the same core is
used, the linker (linear or non-linear) and the kind of the
substituent (terphenyl or the substituent of the inventive
compound) act as a main factor of the performance improvement of
the device of the EBL, different results may be obtained.
[0105] Although exemplary embodiments of the present invention have
been described for illustrative purposes, those skilled in the art
will appreciate that various modifications, additions and
substitutions are possible, without departing from the scope and
spirit of the invention as disclosed in the accompanying claims.
Therefore, the embodiment disclosed in the present invention is
intended to illustrate the scope of the technical idea of the
present invention, and the scope of the present invention is not
limited by the embodiment. The scope of the present invention shall
be construed on the basis of the accompanying claims, and it shall
be construed that all of the technical ideas included within the
scope equivalent to the claims belong to the present invention.
* * * * *