U.S. patent application number 14/903197 was filed with the patent office on 2016-05-19 for organic alloy for organic optoelectronic device, organic optoelectronic device, and display device.
The applicant listed for this patent is SAMSUNG SDI CO., LTD. Invention is credited to Eui-Su KANG, Gi-Wook KANG, Hun KIM, Han-Ill LEE, Sang-Shin LEE, Soo-Hyun MIN, Jae-Jin OH, Min-Jee PARK, Sun-Ha PARK, Dong-Kyu RYU, Eun-Sun YU.
Application Number | 20160141505 14/903197 |
Document ID | / |
Family ID | 52813259 |
Filed Date | 2016-05-19 |
United States Patent
Application |
20160141505 |
Kind Code |
A1 |
PARK; Sun-Ha ; et
al. |
May 19, 2016 |
ORGANIC ALLOY FOR ORGANIC OPTOELECTRONIC DEVICE, ORGANIC
OPTOELECTRONIC DEVICE, AND DISPLAY DEVICE
Abstract
Disclosed are an organic alloy for an organic optoelectric
device that is an organic alloy of at least two kinds of organic
compounds, the at least two kinds of organic compounds includes a
first organic compound and a second organic compound, a difference
between evaporation temperatures of the first organic compound and
the second organic compound is less than or equal to about
20.degree. C. at less than or equal to about 10.sup.-3 torr, and a
light emitting wavelength of the organic alloy is different from
light emitting wavelengths of the first organic compound, the
second organic compound, and a simple mixture of the first organic
compound and the second organic compound, and an organic
optoelectric device and a display device including the organic
alloy.
Inventors: |
PARK; Sun-Ha; (Suwon-si,
Gyeonggi-do, KR) ; KANG; Gi-Wook; (Suwon-si,
Gyeonggi-do, KR) ; KANG; Eui-Su; (Suwon-si,
Gyeonggi-do, KR) ; KIM; Hun; (Suwon-si, Gyeonggi-do,
KR) ; OH; Jae-Jin; (Suwon-si, Gyeonggi-do, KR)
; RYU; Dong-Kyu; (Suwon-si, Gyeonggi-do, KR) ;
LEE; Sang-Shin; (Suwon-si, Gyeonggi-do, KR) ; LEE;
Han-Ill; (Suwon-si, Gyeonggi-do, KR) ; MIN;
Soo-Hyun; (Suwon-si, Gyeonggi-do, KR) ; PARK;
Min-Jee; (Suwon-si, Gyeonggi-do, KR) ; YU;
Eun-Sun; (Suwon-si, Gyeonggi-do, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG SDI CO., LTD |
Yongin-si Gyeonggi-do |
|
KR |
|
|
Family ID: |
52813259 |
Appl. No.: |
14/903197 |
Filed: |
June 17, 2014 |
PCT Filed: |
June 17, 2014 |
PCT NO: |
PCT/KR2014/005306 |
371 Date: |
January 6, 2016 |
Current U.S.
Class: |
257/40 ;
252/301.16; 252/500 |
Current CPC
Class: |
H01L 51/0054 20130101;
C09K 2211/1092 20130101; C09K 2211/1088 20130101; C09K 2211/1007
20130101; C09K 2211/1029 20130101; C09K 2211/1011 20130101; C09K
11/02 20130101; H01L 51/5012 20130101; C09K 11/06 20130101; H01L
51/0067 20130101; H01L 51/0072 20130101; Y02E 10/549 20130101; C09K
2211/1044 20130101; C09K 2211/1059 20130101; H01L 51/5016 20130101;
H01L 51/0052 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C09K 11/02 20060101 C09K011/02; C09K 11/06 20060101
C09K011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 11, 2013 |
KR |
10-2013-0121569 |
Claims
1. An organic alloy for an organic optoelectric device, which is an
organic alloy of at least two kinds of organic compounds, the at
least two kinds of organic compounds includes a first organic
compound and a second organic compound, a difference between
evaporation temperatures of the first organic compound and the
second organic compound is less than or equal to 20.degree. C. at
less than or equal to 10.sup.-3 torr, and a light emitting
wavelength of the organic alloy is different from light emitting
wavelengths of the first organic compound, the second organic
compound, and a simple mixture of the first organic compound and
the second organic compound.
2. The organic alloy of claim 1, wherein the difference between
evaporation temperatures of the first organic compound and the
second organic compound is 0.degree. C. to 10.degree. C. at less
than or equal to 10.sup.-3 torr.
3. The organic alloy of claim 1, wherein a maximum light emitting
wavelength of the organic alloy is shifted greater than or equal to
20 nm compared with a maximum light emitting wavelength of a simple
mixture of the first organic compound and the second organic
compound.
4. The organic alloy of claim 1, wherein the organic alloy has a
color with a longer wavelength region than those of the first
organic compound, the second organic compound, and the simple
mixture of the first organic compound and the second organic
compound.
5. The organic alloy of claim 1, wherein the organic alloy has a
different melting point (Tm) than those of the first organic
compound, the second organic compound, and the simple mixture of
the first organic compound and the second organic compound.
6. The organic alloy of claim 1, wherein the organic alloy has a
constant melting point (Tm).
7. The organic alloy of claim 1, wherein the first organic compound
and the second organic compound become liquid or vapor at an
evaporation temperature.
8. The organic alloy of claim 1, wherein the organic alloy is
obtained by liquidating or gasifying the first organic compound and
the second organic compound through heat-treatment at greater than
or equal to evaporation temperatures thereof and solidifying them
through cooling.
9. The organic alloy of claim 1, wherein the organic alloy is
present as a solid or powder at room temperature.
10. The organic alloy of claim 1, wherein the first organic
compound and the second organic compound are used in a mole ratio
of 1:10 to 10:1.
11. The organic alloy of claim 1, wherein the first organic
compound and the second organic compound are used in a mole ratio
of 1:1.
12. The organic alloy of claim 1, wherein the first organic
compound has electron characteristics, and the second organic
compound has hole characteristics.
13. The organic alloy of claim 1, wherein the first organic
compound comprises at least one compound represented by the
following Chemical Formula 1, and the second organic compound
comprises at least one compound represented by the following
Chemical Formula 2: ##STR00099## wherein, in the above Chemical
Formula 1, Z is independently N or CR.sup.a, at least one of Z is
N, R.sup.1 to R.sup.10 and R.sup.a are independently hydrogen,
deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a
substituted or unsubstituted C6 to C12 aryl group, or a combination
thereof, the total number of 6-membered rings substituting the
triphenylene group in the Chemical Formula 1 is less than or equal
to 6, L is a substituted or unsubstituted phenylene group, a
substituted or unsubstituted biphenylene group or a substituted or
unsubstituted terphenylene group, n1 to n3 are independently 0 or
1, and n1+n2+n3.ltoreq.1, ##STR00100## wherein, in the above
Chemical Formula 2, Y.sup.1 and Y.sup.2 are independently a single
bond, a substituted or unsubstituted C6 to C30 arylene group, a
substituted or unsubstituted C2 to C30 heterocyclic group, or a
combination thereof, Ar.sup.1 and Ar.sup.2 are independently
substituted or unsubstituted C6 to C30 aryl group, a substituted or
unsubstituted C2 to C30 heterocyclic group, or a combination
thereof, and R.sup.11 to R.sup.13 and R.sup.43 to R.sup.44 are
independently hydrogen, deuterium, a substituted or unsubstituted
C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50
aryl group, a substituted or unsubstituted C2 to C50 heterocyclic
group, or a combination thereof.
14. The organic alloy of claim 13, wherein the first organic
compound is represented by the following Chemical Formula 1-I or
Chemical Formula 1-II: ##STR00101## wherein, in the above Chemical
Formula 1-I or 1-II, Z is independently N or CR.sup.a, at least one
of Z is N, R.sup.1 to R.sup.10 and R.sup.a are independently
hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl
group, a substituted or unsubstituted C6 to C12 aryl group, or a
combination thereof, the total number of 6-membered rings
substituting the triphenylene group is less than or equal to 6 in
the above Chemical Formula 1-I and Chemical Formula 1-II, L is a
substituted or unsubstituted phenylene group, a substituted or
unsubstituted biphenylene group or a substituted or unsubstituted
terphenylene group, n1 to n3 are independently 0 or 1, and
n1+n2+n3.gtoreq.1.
15. The organic alloy of claim 13, wherein the L of the above
Chemical Formula 1 is a single bond, a substituted or unsubstituted
phenylene group having a kink structure, a substituted or
unsubstituted biphenylene group having a kink structure, or a
substituted or unsubstituted terphenylene group having a kink
structure.
16. The organic alloy of claim 13, wherein the L of the above
Chemical Formula 1 is a single bond or one selected from
substituted or unsubstituted groups listed in the following Group
1: ##STR00102## ##STR00103## wherein, in the Group 1, R.sup.15 to
R.sup.42 are independently hydrogen, deuterium, a substituted or
unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted
C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to
C30 heterocycloalkyl group, a substituted or unsubstituted C6 to
C30 aryl group, a substituted or unsubstituted C2 to C30
heterocyclic group, a substituted or unsubstituted amine group, a
substituted or unsubstituted C6 to C30 arylamine group, a
substituted or unsubstituted C6 to C30 heterocyclic amine group, a
substituted or unsubstituted C1 to C30 alkoxy group, a halogen, a
halogen-containing group, a cyano group, a hydroxyl group, an amino
group, a nitro group, a carboxyl group, a ferrocenyl group, or a
combination thereof.
17. The organic alloy of claim 13, wherein the Ar.sup.1 and
Ar.sup.2 of the above Chemical Formula 2 are independently
substituted or unsubstituted phenyl group, a substituted or
unsubstituted biphenyl group, a substituted or unsubstituted
terphenyl group, a substituted or unsubstituted naphthyl group, a
substituted or unsubstituted anthracenyl group, a substituted or
unsubstituted carbazolyl group, a substituted or unsubstituted
benzofuranyl group, a substituted or unsubstituted benzothiophenyl
group, a substituted or unsubstituted fluorenyl group, a
substituted or unsubstituted pyridyl group, a substituted or
unsubstituted pyrimidinyl group, a substituted or unsubstituted
pyrazinyl group, a substituted or unsubstituted triazinyl group, a
substituted or unsubstituted triphenylene group, a substituted or
unsubstituted dibenzofuranyl group, a substituted or unsubstituted
dibenzothiophenyl group, or a combination thereof.
18. The organic alloy of claim 13, wherein the first organic
compound is at least one of compounds listed in the following Group
A, and the second organic compound is at least one of compounds
listed in the following Group B: ##STR00104## ##STR00105##
##STR00106## ##STR00107##
19. An organic optoelectric device, comprising an anode and a
cathode facing each other, at least one organic layer interposed
between the anode and the cathode, wherein the organic layer
comprises the organic alloy of claim 1.
20. A display device comprising the organic optoelectric device of
claim 19.
Description
TECHNICAL FIELD
[0001] An organic alloy for an organic optoelectric device, an
organic optoelectric device, and a display device are
disclosed.
BACKGROUND ART
[0002] An organic optoelectric device is a device that converts
electrical energy into photoenergy, and vice versa.
[0003] An organic optoelectric device may be classified as follows
in accordance with its driving principles. One is a photoelectric
device where excitons generated by photoenergy are separated into
electrons and holes and the electrons and holes are transferred to
different electrodes respectively and electrical energy is
generated, and the other is a light emitting device to generate
photoenergy from electrical energy by supplying a voltage or a
current to electrodes.
[0004] Examples of the organic optoelectric device include an
organic photoelectric device, an organic light emitting diode, an
organic solar cell, and an organic photo-conductor drum, and the
like.
[0005] Among them, the organic light emitting diode (OLED) has
recently drawn attention due to an increase in demand for flat
panel displays. The organic light emitting diode converts
electrical energy into light by applying current to an organic
light emitting material, and has a structure in which an organic
layer is interposed between an anode and a cathode. Herein, the
organic layer may include an emission layer and optionally an
auxiliary layer, and the auxiliary layer may include at least one
layer selected from, for example a hole injection layer, a hole
transport layer, an electron blocking layer, an electron transport
layer, an electron injection layer, and a hole blocking layer in
order to improve efficiency and stability of an organic light
emitting diode.
[0006] Performance of an organic light emitting diode may be
affected by characteristics of the organic layer, and among them,
may be mainly affected by an organic material of the organic
layer.
[0007] Particularly, development for an organic material being
capable of increasing hole and electron mobility and simultaneously
increasing electrochemical stability is needed so that the organic
light emitting diode may be applied to a large-size flat panel
display.
DISCLOSURE
Technical Problem
[0008] One embodiment provides an organic alloy applicable for an
organic optoelectric device.
[0009] Another embodiment provides organic optoelectric device
including the organic alloy.
[0010] Yet another embodiment provides a display device including
the organic optoelectric device.
Technical Solution
[0011] According to one embodiment, provided is an organic alloy
for an organic optoelectric device that is an organic alloy of at
least two kinds of organic compounds, the at least two kinds of
organic compounds includes a first organic compound and a second
organic compound, a difference between evaporation temperatures of
the first organic compound and the second organic compound is less
than or equal to about 20.degree. C. at less than or equal to about
10.sup.-3 tom and a light emitting wavelength of the organic alloy
is different from light emitting wavelengths of the first organic
compound, the second organic compound, and a simple mixture of the
first organic compound and the second organic compound.
[0012] According to another embodiment, provided is an organic
optoelectric device including an anode and a cathode facing each
other, at least one organic layer interposed between the anode and
the cathode, wherein the organic layer includes the organic
alloy.
[0013] According to yet another embodiment, a display device
including the organic optoelectric device is provided.
Advantageous Effects
[0014] The present invention may provide an organic alloy having
different characteristics from those of a conventional single
organic compound and a simple mixture thereof and realize an
organic optoelectric device having high efficiency and long
life-span by applying the organic alloy to the organic optoelectric
device.
DESCRIPTION OF DRAWINGS
[0015] FIGS. 1 and 2 are cross-sectional views showing organic
light emitting diodes according to each embodiment the present
invention,
[0016] FIG. 3 is a graph showing light emitting characteristics of
an organic alloy according to Example 1 and organic materials
according to Comparative Examples 1 to 3 depending on a wavelength,
and
[0017] FIG. 4 is a graph showing light emitting characteristics of
an organic alloy according to Example 2 and organic materials
according to Comparative Examples 1, 4 and 5 depending on a
wavelength.
BEST MODE
[0018] Hereinafter, embodiments of the present invention are
described in detail. However, these embodiments are exemplary, and
this disclosure is not limited thereto.
[0019] As used herein, when a definition is not otherwise provided,
the term "substituted" refers to one substituted with deuterium, a
halogen, a hydroxy group, an amino group, a substituted or
unsubstituted C1 to C30 amine group, a nitro group, a substituted
or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a
C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C2 to
C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30
heterocyclic group, a C1 to C20 alkoxy group, a fluoro group, a C1
to C10 trifluoroalkyl group such as a trifluoromethyl group and the
like, or a cyano group, instead of at least one hydrogen of a
substituent or a compound.
[0020] In addition, two adjacent substituents of the substituted
halogen, hydroxy group, amino group, substituted or unsubstituted
C1 to C20 amine group, nitro group, substituted or unsubstituted C3
to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl
group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl
group, C6 to C30 aryl group, C2 to C30 heterocyclic group, C1 to
C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group such
as trifluoromethyl group and the like, or cyano group may be fused
to each other to form a ring. For example, the substituted C6 to
C30 aryl group may be fused with another adjacent substituted C6 to
C30 aryl group to form a substituted or unsubstituted fluorene
ring.
[0021] In the present specification, when specific definition is
not otherwise provided, the term "hetero" refers to one including 1
to 3 hetero atoms selected from N, O, S, P and Si, and remaining
carbons in one compound or substituent.
[0022] In the present specification, when a definition is not
otherwise provided, the term "alkyl group" may refer to an
aliphatic hydrocarbon group. The alkyl group may refer to "a
saturated alkyl" without any double bond or triple bond.
[0023] The alkyl group may be a C1 to C30 alkyl group. More
specifically, the alkyl group may be a C1 to C20 alkyl group or a
C1 to C10 alkyl group. For example, a C1 to C4 alkyl group includes
1 to 4 carbons in alkyl chain, and may be selected from methyl,
ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and
t-butyl.
[0024] Specific examples of the alkyl group may be a methyl group,
an ethyl group, a propyl group, an isopropyl group, a butyl group,
an isobutyl group, a t-butyl group, a pentyl group, a hexyl group,
a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a
cyclohexyl group, and the like.
[0025] In the present specification, the term "aryl group" refers
to a substituent including all element of the cycle having
p-orbitals which form conjugation, and may be monocyclic or fused
ring polycyclic (i.e., rings sharing adjacent pairs of carbon
atoms) functional group.
[0026] As used herein, the term "heterocyclic group" may refer to
cyclic group including 1 to 3 hetero atoms selected from N, O, S, P
and Si, and remaining carbons in a cyclic group. The heterocyclic
group may be a fused ring where each ring may include the 1 to 3
heteroatoms.
[0027] More specifically, the substituted or unsubstituted C6 to
C30 aryl group and/or the substituted or unsubstituted C2 to C30
heterocyclic group may be a substituted or unsubstituted phenyl
group, a substituted or unsubstituted naphthyl group, a substituted
or unsubstituted anthracenyl group, a substituted or unsubstituted
phenanthryl group, a substituted or unsubstituted naphthacenyl
group, a substituted or unsubstituted pyrenyl group, a substituted
or unsubstituted biphenyl group, a substituted or unsubstituted
p-terphenyl group, a substituted or unsubstituted m-terphenyl
group, a substituted or unsubstituted chrysenyl group, a
substituted or unsubstituted triphenylenyl group, a substituted or
unsubstituted perylenyl group, a substituted or unsubstituted
indenyl group, a substituted or unsubstituted furanyl group, a
substituted or unsubstituted thiophenyl group, a substituted or
unsubstituted pyrrolyl group, a substituted or unsubstituted
pyrazolyl group, a substituted or unsubstituted imidazolyl group, a
substituted or unsubstituted triazolyl group, a substituted or
unsubstituted oxazolyl group, a substituted or unsubstituted
thiazolyl group, a substituted or unsubstituted oxadiazolyl group,
a substituted or unsubstituted thiadiazolyl group, a substituted or
unsubstituted pyridyl group, a substituted or unsubstituted
pyrimidinyl group, a substituted or unsubstituted pyrazinyl group,
a substituted or unsubstituted triazinyl group, a substituted or
unsubstituted benzofuranyl group, a substituted or unsubstituted
benzothiophenyl group, a substituted or unsubstituted
benzimidazolyl group, a substituted or unsubstituted indolyl group,
a substituted or unsubstituted quinolinyl group, a substituted or
unsubstituted isoquinolinyl group, a substituted or unsubstituted
quinazolinyl group, a substituted or unsubstituted quinoxalinyl
group, a substituted or unsubstituted naphthyridinyl group, a
substituted or unsubstituted benzoxazinyl group, a substituted or
unsubstituted benzthiazinyl group, a substituted or unsubstituted
acridinyl group, a substituted or unsubstituted phenazinyl group, a
substituted or unsubstituted phenothiazinyl group, a substituted or
unsubstituted phenoxazinyl group, a substituted or unsubstituted
fluorenyl group, a substituted or unsubstituted dibenzofuranyl
group, a substituted or unsubstituted dibenzothiophenyl group, a
substituted or unsubstituted carbazole group, a combination
thereof, or a fused group of the combination, but are limited
thereto.
[0028] In the specification, hole characteristics refer to
characteristics capable of donating an electron to form a hole when
electric field is applied, and characteristics that hole formed in
the anode is easily injected into the emission layer and
transported in the emission layer due to conductive characteristics
according to HOMO level.
[0029] In addition, electron characteristics refer to
characteristics capable of accepting an electron when electric
field is applied, and characteristics that electron formed in the
cathode is easily injected into the emission layer and transported
in the emission layer due to conductive characteristics according
to LUMO level.
[0030] Hereinafter, an organic alloy for an organic optoelectric
device according to one embodiment is described.
[0031] The organic alloy is a material obtained by pre-treating
more than two single organic compounds and a chemical interaction
among the single organic compounds may be provided due to the
pre-treatment. The pre-treating may be a heat treatment such as
heating and sublimation followed by cooling, but is not limited
thereto.
[0032] When the more than two single organic compounds include
first and second organic compounds, the first and second organic
compounds may have an evaporation temperature within the same or a
predetermined range. Herein, the evaporation temperature indicates
a temperature at which the first and second organic compounds may
be deposited on a substrate at a predetermined rate under high
vacuum of less than or equal to about 10.sup.-3 Torr, for example,
an average temperature when the first and second organic compounds
are thermally evaporated to be about 300 nm to about 800 nm thick
at a rate of about 0.5 to about 2 .ANG./sec under high vacuum of
less than or equal to about 10.sup.-3 Torr.
[0033] For example, the difference between evaporation temperatures
of the first organic compound and the second organic compound may
be less than or equal to about 20.degree. C. at less than or equal
to about 10.sup.-3 torr. Within the range, a difference between
evaporation temperatures of the first organic compound and the
second organic compound may be about 0.degree. C. to 10.degree. C.
and specifically about 0.degree. C. to about 5.degree. C.
[0034] The organic alloy has a chemical interaction among more than
two single organic compounds as described above and thus, different
intrinsic characteristics from the single organic compounds and
their simple mixture having no chemical interaction among single
organic compounds. Herein, the simple mixture is obtained by
physically mixing single organic compounds without any
pre-treatment. In other words, when the more than two single
organic compounds include the first and second organic compounds,
the organic alloy of the first and second organic compounds may
have different intrinsic characteristics from those of the first
organic compound, the second organic compound, and a simple mixture
thereof, while the single mixture of the first and second organic
compounds show characteristics of the first organic compound, the
second organic compound, or a combination thereof.
[0035] For example, the light emitting wavelength of the organic
alloy may be different from light emitting wavelengths of the first
organic compound, the second organic compound, and a simple mixture
thereof.
[0036] The organic alloy may release new energy and emit light by a
new energy bandgap between a high HOMO energy level and a low LUMO
energy level of the first and second organic compounds due to
intermolecular electron transfer system of the two organic
compounds. For example, the energy bandgap of the organic alloy may
be an energy difference between LUMO energy level of the first
organic compound and HOMO energy level of the second organic
compound or between LUMO energy level of the second organic
compound and HOMO energy level of the first organic compound. On
the other hand, the simple mixture of the first and second organic
compounds may have either an energy bandgap between LUMO energy and
HOMO energy of the first organic compound or a bandgap between LUMO
energy and HOMO energy of the second organic compound. Herein, the
organic alloy may have a smaller or larger bandgap than that of the
first organic compound, the second organic compound, and the simple
mixture thereof. Accordingly, the light emitting wavelength of the
organic alloy may be different from light emitting wavelengths of
the first organic compound, the second organic compound, and a
simple mixture thereof.
[0037] A maximum light emitting wavelength (.lamda..sub.max) of the
organic alloy may be shifted greater than or equal to about 20 nm
compared with a maximum light emitting wavelength of the simple
mixture of the first and second organic compounds, for example,
shifted greater than or equal to about 20 nm toward a long
wavelength region.
[0038] In addition, the organic alloy may have a different color
from those of the first organic compound, the second organic
compound, and the simple mixture thereof. For example, the organic
alloy may have a color with a longer wavelength region than those
of the first organic compound, the second organic compound, and the
simple mixture thereof.
[0039] Furthermore, the organic alloy may have a different glass
transition temperature (Tg) from that of the first organic
compound, the second organic compound, and the simple mixture
thereof. In addition, the organic alloy may have a different
crystallization temperature (Tc) from that of the first organic
compound, the second organic compound, and the simple mixture
thereof. In addition, the organic alloy may have a different
melting point (Tm) from that of the first organic compound, the
second organic compound, and the simple mixture thereof. Since the
glass transition temperature (Tg), the crystallization temperature
(Tc), and the melting point (Tm) show inherent thermodynamic
characteristics of a molecule, the compounds having the different
glass transition temperature (Tg), the different crystallization
temperature (Tc) and the different melting point (Tm) may be
different compounds.
[0040] The organic alloy may have inherent thermodynamic
characteristics such as the glass transition temperature (Tg), the
crystallization temperature (Tc), and the melting point (Tm), which
may be substantially constant within an error range. The error
range may vary depending on a measurement condition, for example,
may be within about .+-.5.degree. C. and specifically, within about
.+-.2.degree. C. These thermodynamic characteristics may be
different from those of the simple mixture of the first and second
organic compounds having no inherent thermodynamic
characteristics.
[0041] The organic alloy may be pre-treated in various methods, for
example, in a method of heat-treating the first and second organic
compounds at greater than or equal to an evaporation temperature
and liquidating or gasifying the first and second organic compounds
and then, cooling and solidifying the heat-treated compounds. The
first and second organic compounds may be melted liquid or gasified
vapor at the evaporation temperature, and the pre-treated organic
alloy may be a solid like a mass or powder. In addition, the
organic alloy obtained as a solid mass may be additionally
physically ground with a blender and the like.
[0042] The organic alloy is a resulting material obtained through
the aforementioned pre-treatment and may be supplied by using one
source to form a thin film. Accordingly, the deposition process may
become simple without a control process required when more than two
organic compounds are respectively supplied by using separate
sources.
[0043] In addition, the organic alloy is a resulting material
obtained through the aforementioned pre-treatment and thus, may
secure uniformity and consistency for deposition compared with the
more than two single organic compounds supplied by using more than
two separate sources or their simple mixture of supplied by using
one single source. Accordingly, when a plurality of thin films are
formed through a continuous process, the organic alloy may be used
to continuously produce the thin films including components in a
substantially equivalent ratio and thus, increase reproducibility
and reliability of the thin films.
[0044] The first and second organic compounds may include any
material having an evaporation temperature for pre-treatment at a
predetermined temperature without a particular limit, for example,
a compound having electron characteristics and a compound having
hole characteristics to improve mobility of electrons and holes.
For example, the first organic compound may be a compound having
relatively strong electron characteristics, and the second organic
compound may be a compound having relatively strong hole
characteristics, and thus, the organic alloy of the first organic
compound having relatively strong electron characteristics and the
second organic compound having relatively strong hole
characteristics may have bipolar characteristics.
[0045] The first organic compound is a compound having relatively
strong electron characteristics, for example a compound represented
by the following Chemical Formula 1.
##STR00001##
[0046] In the above Chemical Formula 1,
[0047] Z is independently N or CR.sup.a,
[0048] at least one of Z is N,
[0049] R.sup.1 to R.sup.10 and R.sup.a are independently hydrogen,
deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a
substituted or unsubstituted C6 to C12 aryl group, or a combination
thereof,
[0050] In the above Chemical Formula 1, the total number of
6-membered rings substituting the triphenylene group is less than
or equal to 6,
[0051] L is a substituted or unsubstituted phenylene group, a
substituted or unsubstituted biphenylene group or a substituted or
unsubstituted terphenylene group,
[0052] n1 to n3 are independently 0 or 1, and
n1+n2+n3.gtoreq.1.
[0053] Herein, the 6-membered rings substituting the triphenylene
group indicate all the 6-membered rings directly or indirectly
linked to the triphenylene group and include 6-membered rings
including a carbon atom, a nitrogen atom, or a combination
thereof.
[0054] The first organic compound may be represented by for example
the following Chemical Formula 1-I or 1-II, depending on the
bonding position of the triphenylene group.
##STR00002##
[0055] In the above Chemical Formula 1-I or 1-II, Z, R.sup.1 to
R.sup.10, L and n1 to n3 are the same as described above.
[0056] The first organic compound includes the triphenylene group
and at least one nitrogen-containing heterocyclic group.
[0057] The first organic compound includes at least one
nitrogen-containing ring and thereby, may have a structure of
easily accepting electrons when an electric field is applied
thereto and thus, decrease a driving voltage of an organic
optoelectric device including the first organic compound.
[0058] In addition, the first organic compound has a bipolar
structure by including both a triphenylene structure of easily
accepting holes and a nitrogen-containing ring moiety of easily
accepting electrons and may appropriately balance a flow of the
holes and the electrons, and accordingly, improve efficiency of an
organic optoelectric device when applied thereto.
[0059] The first organic compound represented by the above Chemical
Formula 1 has at least one kink structure as a center of an arylene
group and/or a heterocyclic group.
[0060] The kink structure is a structure that a linking moiety of
the arylene group and/or the heterocyclic group is not a linear
structure. For example, as for phenylene, ortho phenylene
(o-phenylene) and meta phenylene (m-phenylene) have the kink
structure where a linking moiety does not form a linear structure,
while para phenylene (p-phenylene) has no kink structure because
where a linking moiety forms a linear structure.
[0061] In the above Chemical Formula 1, the kink structure may be
formed as a center of a linking group (L) and/or an arylene group/a
heterocyclic group.
[0062] For example, when n1 in the above Chemical Formula 1 is 0,
that is, there is no linking group (L), a kink structure may be
formed as a center of an arylene group/a heterocyclic group, and
for example, the compound may be represented by the following
Chemical Formula 1a or 1 b.
##STR00003##
[0063] In the above Chemical Formula 1a or 1b, Z, R.sup.1 to
R.sup.10 and L are the same as described above.
[0064] For example, when n1 in the above Chemical Formula 1 is 1, a
kink structure is formed as a center of a linking group (L), and
for example, the L is may be a substituted or unsubstituted
phenylene having the kink structure, a substituted or unsubstituted
biphenylene group having the kink structure, or a substituted or
unsubstituted terphenylene group having the kink structure. The L
may be selected from, for example substituted or unsubstituted
groups listed in the following Group 1.
##STR00004## ##STR00005##
[0065] In the Group 1,
[0066] R.sup.15 to R.sup.42 are independently hydrogen, deuterium,
a substituted or unsubstituted C1 to C10 alkyl group, a substituted
or unsubstituted C3 to C30 cycloalkyl group, a substituted or
unsubstituted C2 to C30 heterocycloalkyl group, a substituted or
unsubstituted C6 to C30 aryl group, a substituted or unsubstituted
C2 to C30 heterocyclic group, a substituted or unsubstituted amine
group, a substituted or unsubstituted C6 to C30 arylamine group, a
substituted or unsubstituted C6 to C30 heteroarylamine group, a
substituted or unsubstituted C1 to C30 alkoxy group, a halogen, a
halogen-containing group, a cyano group, a hydroxyl group, an amino
group, a nitro group, a carboxyl group, a ferrocenyl group, or a
combination thereof.
[0067] The first organic compound may have at least two kink
structures and for example, two to four kink structures.
[0068] The first organic compound may appropriately localize
charges and control a conjugation-system flow due to the above kink
structure, and thus improve a life-span of an organic optoelectric
device to which the composition is applied.
[0069] In addition, in Chemical Formula 1, the number of R.sup.1 to
R.sup.6, that is the total number of 6-membered rings substituting
the triphenylene group is limited to be less than or equal to 6,
and thereby thermal decomposition of the compound by a high
temperature during a deposition process may be decreased.
[0070] In addition, the first organic compound may be effectively
prevented from stacking depending on the structure and decrease
process stability and simultaneously, a deposition temperature.
This stacking prevention effect may be further increased when the
compound includes the linking group (L) of the above Chemical
Formula 1.
[0071] The first organic compound may be, for example represented
by one of the following Chemical Formulae 1c to it.
##STR00006## ##STR00007## ##STR00008## ##STR00009##
##STR00010##
[0072] In the above Chemical Formulae 1c to it,
[0073] Z and R.sup.1 to R.sup.10 are independently the same as
described above, and
[0074] R.sup.60 to R.sup.77 are independently hydrogen, deuterium,
a substituted or unsubstituted C1 to C10 alkyl group, a substituted
or unsubstituted C3 to C30 cycloalkyl group, a substituted or
unsubstituted C2 to C30 heterocycloalkyl group, a substituted or
unsubstituted C6 to C30 aryl group, a substituted or unsubstituted
C2 to C30 heterocyclic group, a substituted or unsubstituted amine
group, a substituted or unsubstituted C6 to C30 arylamine group, a
substituted or unsubstituted C6 to C30 heteroarylamine group, a
substituted or unsubstituted C1 to C30 alkoxy group, a halogen, a
halogen-containing group, a cyano group, a hydroxyl group, an amino
group, a nitro group, a carboxyl group, a ferrocenyl group, or a
combination thereof.
[0075] The first organic compound may be, for example, a compound
listed in the following Group 2 but is not limited thereto.
##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015##
##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##
##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##
##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##
##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041## ##STR00042## ##STR00043## ##STR00044##
##STR00045##
[0076] At least one or more kinds of the first organic compound may
be used.
[0077] The second organic compound may be a compound having
relatively strong hole characteristics, for example, a compound
represented by the following Chemical Formula 2.
##STR00046##
[0078] In the above Chemical Formula 2,
[0079] Y.sup.1 and Y.sup.2 are independently a single bond, a
substituted or unsubstituted C1 to C20 alkylene group, a
substituted or unsubstituted C2 to C20 alkenylene group, a
substituted or unsubstituted C6 to C30 arylene group, a substituted
or unsubstituted C2 to C30 heterocyclic group, or a combination
thereof,
[0080] Ar.sup.1 and Ar.sup.2 are a substituted or unsubstituted C6
to C30 aryl group, a substituted or unsubstituted C2 to C30
heterocyclic group, or a combination thereof, and
[0081] R.sup.11 to R.sup.13, R.sup.43 and R.sup.44 are
independently hydrogen, deuterium, a substituted or unsubstituted
C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50
aryl group, a substituted or unsubstituted C2 to C50 heterocyclic
group, or a combination thereof.
[0082] The second organic compound is a compound having bipolar
characteristics in which hole characteristics are relatively
stronger than electron characteristics and thus, increases charge
mobility and stability by forming an organic alloy with the first
organic compound and resultantly, may improve luminous efficiency
and life-span characteristics.
[0083] Ar.sup.1 and Ar.sup.2 of the above Chemical Formula 2 are
substitutents having hole or electron characteristics, and may be
independently for example a substituted or unsubstituted phenyl
group, a substituted or unsubstituted biphenyl group, a substituted
or unsubstituted terphenyl group, a substituted or unsubstituted
naphthyl group, a substituted or unsubstituted anthracenyl group,
substituted or unsubstituted triphenylenyl group, a substituted or
unsubstituted carbazolyl group, a substituted or unsubstituted
benzofuranyl group, a substituted or unsubstituted benzothiophenyl
group, a substituted or unsubstituted fluorenyl group, a
substituted or unsubstituted pyridyl group, a substituted or
unsubstituted pyrimidinyl group, a substituted or unsubstituted
pyrazinyl group, a substituted or unsubstituted triazinyl group, a
substituted or unsubstituted dibenzofuranyl group, a substituted or
unsubstituted dibenzothiophenyl group, or a combination
thereof.
[0084] At least one of Ar.sup.1 and Ar.sup.2 of the above Chemical
Formula 2 may be for example substituents having electron
characteristics, and may be for example substituents represented by
the following Chemical Formula A.
##STR00047##
[0085] In the above Chemical Formula A,
[0086] Z is independently N or CR.sup.b,
[0087] A1 and A2 are independently a substituted or unsubstituted
C6 to C30 aryl group, a substituted or unsubstituted C2 to C30
heterocyclic group, or a combination thereof,
[0088] at least one of the Z, A1 and A2 includes N, and
[0089] a and b are independently 0 or 1.
[0090] The substituent represented by the above Chemical Formula A
may be for example one of functional groups listed in the following
Group 3.
##STR00048## ##STR00049## ##STR00050## ##STR00051##
[0091] In addition, at least one of Ar.sup.1 and Ar.sup.2 of the
above Chemical Formula 2 may be, for example a substituent having
hole characteristics, and may be, for example substituents listed
in the following Group 4.
##STR00052## ##STR00053##
[0092] The compound represented by the above Chemical Formula 2 may
be, for example selected from compounds listed in the following
Group 5, but is not limited thereto.
##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##
##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068##
##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073##
##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078##
##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083##
##STR00084## ##STR00085## ##STR00086##
[0093] At least one or more kinds of the second organic compound
may be used.
[0094] The above first and second organic compounds may be
variously combined to prepare various organic alloys. For example
the first organic compound may be at least one of compounds listed
in the following Group A, and the second organic compound may be at
least one of compounds listed in the following Group B, but they
are not limited thereto.
##STR00087## ##STR00088## ##STR00089## ##STR00090##
[0095] As described above, the first organic compound is a compound
having relatively strong electron characteristics, the second
organic compound is a compound having relatively strong hole
characteristics, and they are pre-treated to form an organic alloy
to increase mobility of electrons and holes and thus, to remarkably
improve luminous efficiency compared with when the first compound
or the second compound is used at alone.
[0096] When the single material having biased toward electron
characteristics or biased toward hole characteristics is used to
form an emission layer, excitons may be relatively more formed at
an interface of an emission layer and the electron transport layer
(ETL) or hole transport layer (HTL). As a result, the excitons in
the emission layer may interact with charges at the interface of
the electron transport layer (ETL) or the hole transport layer
(HTL) and thus, cause a roll-off of sharply deteriorating
efficiency and also, sharply deteriorate light emitting life-span
characteristics. In order to solve this problem, the organic alloy
of the first organic compound and the second organic compound is
introduced into the emission layer to manufacture a device
balancing carriers in the emission layer, so that a light emitting
area may not be biased toward either the electron transport layer
(ETL) or hole transport layer (HTL) and thus, remarkably improving
roll-off and simultaneously life-span characteristics.
[0097] The organic alloy may be obtained by using the first organic
compound and the second organic compound in a mole ratio, for
example about 1:10 to about 10:1. As another examples, the organic
alloy may be obtained by using the first organic compound and the
second organic compound in a mole ratio of about 1:4 to about 4:1,
or in a mole ratio of about 1:1.
[0098] Within the range, bipolar characteristics may be realized
more efficiently and efficiency and life-span may be improved.
[0099] The organic alloy may be obtained by pre-treating the above
first organic compound and second organic compound, or may be
obtained by pre-treating at least one kind of an organic compound
besides the above first organic compound and second organic
compound.
[0100] The organic alloy may be used as an organic material for an
organic optoelectric device, and may be used as, for example a
light emitting material, a light absorbing material, a charge
transport material, a charge injection material, a charge blocking
material, or a combination thereof.
[0101] For example, the organic alloy may be used as a light
emitting material for an organic optoelectric device. Herein, the
organic alloy may be used as a host, and may further include at
least one kind of a dopant. The dopant may be a red, green, or blue
dopant, for example a phosphorescent dopant.
[0102] The dopant is mixed with the organic alloy in a small amount
to cause light emission, and may be generally a material such as a
metal complex that emits light by multiple excitation into a
triplet or more. The dopant may be, for example an inorganic,
organic, or organic/inorganic compound, and one or more kinds
thereof may be used.
[0103] Examples of the phosphorescent dopant may be an organic
metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe,
Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent
dopant may be, for example a compound represented by the following
Chemical Formula Z, but is not limited thereto.
L.sub.2MX [Chemical Formula Z]
[0104] In the above Chemical Formula Z, M is a metal, and L and X
are the same or different, and are a ligand to form a complex
compound with M.
[0105] The M may be, for example Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb,
Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and the L and
X may be, for example a bidendate ligand.
[0106] The organic material may form a film using a dry
film-forming method such as chemical vapor deposition or a solution
process.
[0107] Hereinafter, an organic optoelectric device to which the
organic material is applied is described.
[0108] The organic optoelectric device may be any device to convert
electrical energy into photoenergy and vice versa without
particular limitation, and may be, for example an organic
photoelectric device, an organic light emitting diode, an organic
solar cell, and an organic photo-conductor drum.
[0109] The organic optoelectric device includes an anode and a
cathode facing each other, and at least one organic layer
interposed between the anode and the cathode, wherein the organic
layer includes the above organic material.
[0110] Herein, an organic light emitting diode as one example of an
organic optoelectric device is described referring to drawings.
[0111] FIGS. 1 and 2 are cross-sectional views of each organic
light emitting diode according to one embodiment.
[0112] Referring to FIG. 1, an organic light emitting diode 100
according to one embodiment includes an anode 120 and a cathode 110
facing each other and an organic layer 105 interposed between the
anode 120 and cathode 110.
[0113] The anode 120 may be made of a conductor having a large work
function to help hole injection, and may be for example metal,
metal oxide and/or a conductive polymer. The anode 120 may be a
metal such as nickel, platinum, vanadium, chromium, copper, zinc,
gold, and the like or an alloy thereof; metal oxide such as zinc
oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide
(IZO), and the like; a combination of metal and oxide such as ZnO
and Al or SnO.sub.2 and Sb; a conductive polymer such as
poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene)
(PEDOT), polypyrrole, and polyaniline, but is not limited
thereto.
[0114] The cathode 110 may be made of a conductor having a small
work function to help electron injection, and may be for example
metal, metal oxide and/or a conductive polymer. The cathode 110 may
be for example a metal or an alloy thereof such as magnesium,
calcium, sodium, potassium, titanium, indium, yttrium, lithium,
gadolinium, aluminum silver, tin, lead, cesium, barium, and the
like; a multi-layer structure material such as LiF/Al,
LiO.sub.2/Al, LiF/Ca, LiF/Al and BaF.sub.2/Ca, but is not limited
thereto.
[0115] The organic layer 105 may include an emission layer 130
including the above organic material.
[0116] The emission layer 130 may include, for example the above
organic material.
[0117] Referring to FIG. 2, an organic light emitting diode 200
further includes a hole auxiliary layer 140 as well as an emission
layer 130. The hole auxiliary layer 140 may further increase hole
injection and/or hole mobility between the anode 120 and emission
layer 130 and block electrons. The hole auxiliary layer 140 may be,
for example a hole transport layer (HTL), a hole injection layer
(HIL), and/or an electron blocking layer (EBL), and may include at
least one layer.
[0118] In one embodiment of the present invention, an organic light
emitting diode may further include an electron transport layer
(ETL), an electron injection layer (EIL), a hole injection layer
(HIL), and the like, in an organic layer 105 in FIG. 1 or FIG.
2.
[0119] The organic light emitting diodes 100 and 200 may be
manufactured by forming an anode or a cathode on a substrate,
forming an organic layer in accordance with a dry coating method
such as evaporation, sputtering, plasma plating, and ion plating;
and forming a cathode or an anode thereon.
[0120] The organic light emitting diode may be applied to an
organic light emitting diode (OLED) display.
MODE FOR INVENTION
[0121] Hereinafter, the embodiments are illustrated in more detail
with reference to examples. These examples, however, are not in any
sense to be interpreted as limiting the scope of the invention.
Preparation of Single Organic Compound
Synthesis of First Organic Compound
Compound A-33
Synthesis Example 1
Synthesis of Intermediate I-2
##STR00091##
[0123] 32.7 g (107 mmol) of 2-bromotriphenylene was dissolved in
0.3 L of tetrahydrofuran (THF) under a nitrogen atmosphere, 20 g
(128 mmol) of 3-chlorophenylboronic acid and 1.23 g (1.07 mmol) of
tetrakis(triphenylphosphine)palladium were added thereto, and the
mixture was agitated. Subsequently, 36.8 g (267 mmol) of potassium
carbonate saturated in water was added thereto, and the mixture was
heated and refluxed at 80.degree. C. for 24 hours. When the
reaction was complete, water was added to the reaction solution,
and the mixture was treated with dichloromethane (DCM) for
extraction and with anhydrous MgSO.sub.4 to remove moisture and
then, filtered and concentrated under a reduced pressure. The
obtained residue was separated and purified through flash column
chromatography, obtaining 22.6 g (63%) of the compound I-2.
[0124] HRMS (70 eV, EI+): m/z calcd for C24H15Cl: 338.0862. found:
338.
[0125] Elemental Analysis: C, 85%; H, 5%
Synthesis Example 2
Synthesis of Intermediate I-3
##STR00092##
[0127] 22.6 g (66.7 mmol) of the compound I-2 was dissolved in 0.3
L of dimethylformamide (DMF) under a nitrogen atmosphere, 25.4 g
(100 mmol) of bis(pinacolato)diboron, 0.54 g (0.67 mmol) of
(1,1'-bis(diphenylphosphine)ferrocene)dichloropalladium (II), and
16.4 g (167 mmol) of potassium acetate were added thereto, and the
mixture was heated and refluxed at 150.degree. C. for 48 hours.
When the reaction was complete, water was added to the reaction
solution, and the mixture was filtered and dried in a vacuum oven.
The obtained residue was separated and purified through flash
column chromatography, obtaining 18.6 g (65%) of a compound
I-3.
[0128] HRMS (70 eV, EI+): m/z calcd for C30H27BO2: 430.2104. found:
430.
[0129] Elemental Analysis: C, 84%; H, 6%
Synthesis Example 3
Synthesis of Intermediate I-6
##STR00093##
[0131] 50 g (116 mmol) of the compound I-3 was dissolved in 0.5 L
of tetrahydrofuran (THF) under a nitrogen atmosphere, 39.4 g (139
mmol) of 1-bromo-3-iodobenzene and 1.34 g (1.16 mmol) of
tetrakis(triphenylphosphine)palladium were added thereto, and the
mixture was agitated. Subsequently, 40.1 g (290 mmol) of potassium
carbonate saturated in water was added thereto, and the mixture was
heated and refluxed at 80.degree. C. for 12 hours. When the
reaction was complete, water was added to the reaction solution,
and the mixture was treated dichloromethane (DCM) for extraction
and treated with anhydrous MgSO.sub.4 to remove moisture and then,
filtered and concentrated under a reduced pressure. The obtained
residue was separated and purified through flash column
chromatography, obtaining 42.6 g (80%) of the compound I-6.
[0132] HRMS (70 eV, EI+): m/z calcd for C30H19Br: 458.0670. found:
458.
[0133] Elemental Analysis: C, 78%; H, 4%
Synthesis Example 4
Synthesis of Intermediate I-7
##STR00094##
[0135] 40 g (87.1 mmol) of the compound I-6 was dissolved in 0.3 L
of dimethylformamide (DMF) under a nitrogen atmosphere, 26.5 g (104
mmol) of bis(pinacolato)diboron, 0.71 g (0.87 mmol) of
(1,1'-bis(diphenylphosphine)ferrocene)dichloropalladium (II) and
21.4 g (218 mmol) of potassium acetate were added thereto, and the
mixture was heated and refluxed at 150.degree. C. for 26 hours.
When the reaction was complete, water was added to the reaction
solution, and the mixture was filtered and dried in a vacuum oven.
The obtained residue was separated and purified through flash
column chromatography, obtaining 34 g (77%) of the compound
I-7.
[0136] HRMS (70 eV, EI+): m/z calcd for C36H31BO2: 506.2417. found:
506.
[0137] Elemental Analysis: C, 85%; H, 6%
Synthesis Example 5
Synthesis of Compound A-33
##STR00095##
[0139] 20 g (39.5 mmol) of the compound I-7 was dissolved in 0.2 L
of tetrahydrofuran (THF) under a nitrogen atmosphere, 10.6 g (39.5
mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 0.46 g (0.4 mmol)
of tetrakis(triphenylphosphine)palladium were added thereto, and
the mixture was agitated. Subsequently, 13.6 g (98.8 mmol) of
potassium carbonate saturated in water was added thereto, and the
mixture was heated and refluxed at 80.degree. C. for 23 hours. When
the reaction was complete, water was added to the reaction
solution, and the mixture was treated with dichloromethane (DCM)
for extraction and with anhydrous MgSO4 to remove moisture and
then, filtered and concentrated under a reduced pressure. The
obtained residue was separated and purified through flash column
chromatography, obtaining 17.9 g (74%) of the compound A-33.
[0140] HRMS (70 eV, EI+): m/z calcd for C45H29N3: 611.2361. found:
611.
[0141] Elemental Analysis: C, 88%; H, 5%
[0142] The compound A-33 had an evaporation temperature of about
226.+-.10.degree. C. under less than or equal to 10.sup.-3
Torr.
Synthesis Example 1 of Second Organic Compound
Compound B-10
##STR00096## ##STR00097##
[0143] First Step: Synthesis of Compound J
[0144] 26.96 g (81.4 mmol) of N-phenyl carbazole-3-boronic acid
pinacolate, 23.96 g (97.36 mmol) of 3-bromo carbazole, and 230 mL
of tetrahydrofuran were mixed with 100 ml of a 2 M-potassium
carbonate aqueous solution, and the mixture was heated and refluxed
under a nitrogen current for 12 hours. When the reaction was
complete, a solid produced by pouring methanol to the reactant was
filtered and dissolved in chlorobenzene again, activated carbon and
anhydrous magnesium sulfate were added thereto, and the mixture was
agitated. The solution was filtered and recrystallized by using
chlorobenzene and methanol, obtaining 22.6 g of a compound J (a
yield: 68%).
[0145] HRMS (70 eV, EI+): m/z calcd for C30H20N2: 408.16. found:
408.
[0146] Elemental Analysis: C, 88%; H, 5%
Second Step: Synthesis of Compound B-10
[0147] 22.42 g (54.88 mmol) of the compound J, 20.43 g (65.85 mmol)
of 2-bromo-4,6-diphenylpyridine, and 7.92 g (82.32 mmol) of
tertiarybutoxysodium were dissolved in 400 ml of toluene, and 1.65
g (1.65 mmol) of palladium dibenzylideneamine and 1.78 g (4.39
mmol) of tri-tertiarybutylphosphine (P(t-Bu).sub.3) were added in a
dropwise fashion. The reaction solution was heated 110.degree. C.
and agitated under a nitrogen current for 12 hours. When the
reaction was complete, a solid produced by pouring methanol to the
reactant was filtered and dissolved in chlorobenzene again,
activated carbon and anhydrous magnesium sulfate were added
thereto, and the mixture was agitated. The solution was filtered
and recrystallized by using chlorobenzene and methanol, obtaining
28.10 g of a compound B-10 (a yield: 80%).
[0148] HRMS (70 eV, EI+): m/z calcd for C47H31N3: 637.25. found:
637.
[0149] Elemental Analysis: C, 89%; H, 5%
[0150] The compound B-10 had an evaporation temperature of about
225.+-.10.degree. C. under less than or equal to 10.sup.-3
Torr.
Synthesis Example 2 of Second Organic Compound
Compound B-43
##STR00098##
[0152] 12.33 g (30.95 mmol) of biphenylcarbazolyl bromide, 12.37 g
(34.05 mmol) of biphenylcarbazolylboronic acid, and 12.83 g (92.86
mmol) of potassium carbonate, and 1.07 g (0.93 mmmol) of
tetrakis-(triphenylphosphine)palladium (0) were suspended in 120 ml
of toluene and 50 ml of distilled water, and the suspended solution
was refluxed and agitated for 12 hours. Subsequently, the reactant
was extracted with dichloromethane and distilled water, and an
organic layer obtained therefrom was filtered with silica gel.
Subsequently, an organic solution therein was removed, and a solid
product therefrom was recrystallized with dichloromethane and
n-hexane, obtaining a compound B-43 18.7 g (a yield: 92%).
[0153] HRMS (70 eV, EI+): m/z calcd for C48H32N2: 636.26. found:
636.
[0154] Elemental Analysis: C, 91%; H, 5%
[0155] The compound B-43 had an evaporation temperature of about
232.+-.10.degree. C. under less than or equal to 10.sup.-3
Torr.
Example
Preparation of Organic Alloy
Example 1
Organic Alloy of Compound A-33 and Compound B-10
[0156] A powder-type organic alloy was obtained by putting the
compound A-33 and the compound B-10 in a mole ratio of 1:1 in a
vacuum chamber of less than or equal to 10.sup.-3 Torr, melting the
compound A-33 and the compound B-10 by increasing temperature of
the vacuum chamber, solidifying them by cooling down to room
temperature of 25.degree. C., and grinding the solid with a
blender.
Example 2
Organic Alloy of Compound A-33 and Compound B-43
[0157] A powder-type organic alloy was obtained by putting the
compound A-33 and the compound B-43 in a mole ratio of 1:1 in a
vacuum chamber of less than or equal to 10.sup.-3 Torr, melting the
compound A-33 and the compound B-43 by increasing temperature of
the vacuum chamber, solidifying them by cooling down to room
temperature of 25.degree. C., and grinding the solid with a
blender.
Comparative Example
Preparation of Simile Compound and Simple Mixture
Comparative Example 1
Single Compound A-33
[0158] A powder-type compound A-33 was prepared by grinding the
compound A-33 according to Synthesis Example 5 with a blender at
room temperature (25.degree. C.).
Comparative Example 2
Single Compound B-10
[0159] The powder-type compound B-10 was prepared by grinding the
compound B-10 according to Synthesis Example 1 of a second organic
compound at temperature (25.degree. C.) with a blender.
Comparative Example 3
Simple Mixture of Compound A-33 and Compound B-10
[0160] The compound A-33 according to Synthesis Example 5 and the
compound B-10 according to Synthesis Example 1 of a second organic
compound were physically ground in a mole ratio of 1:1 with a
blender, obtaining a simple mixture.
Comparative Example 4
Single Compound B-43
[0161] A powder-type compound B-43 was obtained by grinding the
compound B-43 according to Synthesis Example 2 of a second organic
compound at room temperature (25.degree. C.) with a blender.
Comparative Example 5
Simple Mixture of Compound A-33 and Compound B-43
[0162] The compound A-33 according to Synthesis Example 5 and the
compound B-43 according to Synthesis Example 1 of a second organic
compound were physically ground in a mole ratio of 1:1 at room
temperature (25.degree. C.) with a blender, preparing a simple
mixture.
Evaluation
Evaluation 1
[0163] Optical properties of the organic alloys according to
Examples 1 and 2 and the organic materials according to Comparative
Examples 1 to 5 were evaluated. The optical properties were
evaluated by measuring photoluminescence (PL) spectrum of powders
of the organic alloys according to Examples 1 and 2 and the organic
materials according to Comparative Examples 1 to 5 with a
Fluorescence spectrophotometer (F-4500, Hitachi). The powders were
used as a sample, and herein, a solid sample holder of 650-0161
(Hitachi) was used as a PL holder.
[0164] The results are illustrated referring to FIGS. 3 and 4 and
the following Tables 1 and 2.
[0165] FIG. 3 is a graph showing light emitting characteristics of
the organic alloy according to Example 1 and the organic materials
according to Comparative Examples 1 to 3 depending on a wavelength,
and FIG. 4 is a graph showing light emitting characteristics of the
organic alloy according to Example 2 and the organic materials
according to Comparative Examples 1, 4, and 5 depending on a
wavelength.
TABLE-US-00001 TABLE 1 Maximum light emitting wavelength .lamda.max
(nm) eV Example 1 483 2.57 Comparative Example 1 411 3.02
Comparative Example 2 449 2.76 Comparative Example 3 463 2.78
TABLE-US-00002 TABLE 2 Maximum light emitting wavelength .lamda.max
(nm) eV Example 2 488 2.55 Comparative Example 1 411 3.02
Comparative Example 4 420 2.95 Comparative Example 5 421 2.95
[0166] Referring to FIGS. 3 and 4 and the Tables 1 and 2, the
organic alloy of Example 1 showed different optical properties from
the organic materials according to Comparative Examples 1 to 3, and
the organic alloy of Example 2 showed different optical properties
from the organic materials according to Comparative Examples 1, 4,
and 5.
[0167] In particular, the organic alloy of Example 1 showed
inherent optical properties differing from those of the first
organic compound A-33 and the second organic compound B-10, for
example, a maximum light emitting wavelength greater than or equal
to about 20 nm moving toward a long wavelength, while the organic
material of Comparative Example 3, that is, a simple mixture of the
first organic compound A-33 and the second organic compound B-10,
showed optical properties of the first organic compound A-33, the
second organic compound B-10, or a combination thereof.
[0168] Likewise, the organic alloy of Example 2 showed inherent
optical properties differing from those of the first organic
compound A-33 and the second organic compound B-43, for example, a
maximum light emitting wavelength greater than or equal to about 20
nm toward a long wavelength, while the organic material of
Comparative Example 5, that is, a simple mixture of the first
organic compound A-33 and the second organic compound B-43 showed
optical properties of the first organic compound A-33, the second
organic compound B-43, or a combination thereof.
[0169] In addition, the organic alloy according to Example 1 showed
inherent energy level differing from those of the first organic
compound A-33 and the second organic compound B-10, while the
organic material of Comparative Example 3, that is, a mixture of
the first organic compound A-33 and the second organic compound
B-10, showed substantially similar energy level to that of the
first organic compound A-33 or the second organic compound
B-10.
[0170] Likewise, the organic alloy of Example 2 showed inherent
energy level differing from those of first organic compound A-33
and the second organic compound B-43, while the organic material of
Comparative Example 5, that is, a simple mixture of the first
organic compound A-33 and the second organic compound B-43 showed
substantially similar energy level to that of the first organic
compound A-33 or the second organic compound B-43.
Evaluation 2
[0171] Thermodynamic characteristics of the organic alloys of
Examples 1 and 2 and the organic materials of Comparative Examples
1 to 5 were evaluated. The thermodynamic characteristics of the
organic alloys of Examples 1 and 2 and the organic materials of
Comparative Examples 1 to 5 were measured through differential
scanning calorimetry by using DSC1 (Mettler-Toledo Inc.).
[0172] The results are provided in Tables 3 and 4.
TABLE-US-00003 TABLE 3 Thermodynamic characteristics glass
transition crystallization temperature temperature melting point
(Tg, .degree. C.) (Tc, .degree. C.) (Tm, .degree. C.) Example 1 122
215 261 Comparative Example 1 -- -- 287 Comparative Example 2 133
-- -- Comparative Example 3 133 -- 255
TABLE-US-00004 TABLE 4 Thermodynamic characteristics glass
transition crystallization temperature temperature melting point
(Tg, .degree. C.) (Tc, .degree. C.) (Tm, .degree. C.) Example 2 116
184 260 Comparative Example 1 -- -- 287 Comparative Example 4 122
-- -- Comparative Example 5 124 -- 252
[0173] Referring to Tables 3 and 4, the organic alloy of Example 1
showed different thermodynamic characteristics from those of the
organic materials of Comparative Examples 1 to 3, and the organic
alloy of Example 2 showed different thermodynamic characteristics
from the organic materials according to Comparative Examples 1, 4,
and 5.
[0174] In particular, the organic alloy of Example 1 showed
inherent thermodynamic characteristics differing from those of the
first organic compound A-33, the second organic compound B-10, and
a simple mixture thereof, while the organic material of Comparative
Example 3, that is, a simple mixture of the first organic compound
A-33 and the second organic compound B-10 showed substantially
similar thermodynamic characteristics to those of the organic
material of Comparative Example 2.
[0175] Likewise, the organic alloy of Example 2 showed different
thermodynamic characteristics from those of the first organic
compound A-33, the second organic compound B-43, and a simple
mixture of the first organic compound A-33 and the second organic
compound B-43, while the organic material of Comparative Example 5,
a simple mixture of the first organic compound A-33 and the second
organic compound B-43 showed substantially similar thermodynamic
characteristics to those of the organic material of Comparative
Example 4, that is, the second organic compound B-43.
Evaluation 3
[0176] Consistency of the thermodynamic characteristics of the
organic alloy of Examples 1 and 2 and organic materials of
Comparative Examples 3 and 5 was evaluated. The consistency of
thermodynamic characteristics was evaluated by more than once
measuring the thermodynamic characteristics of Evaluation 2 and
seeing if the measurements were constant.
[0177] The results are illustrated referring to Tables 5 and 6.
TABLE-US-00005 TABLE 5 Comparative Example 3 Example 1 #1 #2 #3 #1
#2 #3 #4 #5 Melting point 259.9 255.2 280.1 260.7 261.4 260.1 261.3
261.3 (Tm, .degree. C.)
TABLE-US-00006 TABLE 6 Comparative Example 5 Example 2 #1 #2 #3 #1
#2 #3 #4 #5 Melting point 259.9 280.3 276.3 260.3 261.5 260.2 262.1
261.9 (Tm, .degree. C.)
[0178] Referring to Tables 5 and 6, the organic alloys of Examples
1 and 2 showed constant melting points within an error range of
.+-.5.degree. C., especially, within an error range of
.+-.2.degree. C. over more than one measurement, while the organic
materials of Comparative Examples 3 and 5 showed largely different
melting points over the measurements, for example, within an error
range of about 20.degree. C. Accordingly, the organic alloys of
Examples 1 and 2 showed more constant organic thermodynamic
characteristics than a single organic compound or a simple mixture
thereof.
Evaluation 4
[0179] Variation of the organic alloys according to Examples 1 and
2 with time during continuous process was evaluated.
[0180] The variation with time during continuous process was
evaluated by continuously depositing the organic alloys of Examples
1 and 2 and the organic materials of Comparative Examples 3 and 5
on a glass substrate to form a plurality of films and examining if
single organic compounds constantly maintained a ratio in each film
through a high performance liquid chromatography (HPLC) analysis
method. The variation with time during continuous process may be
evaluated by seeing how much constantly a ratio among the
components forming a film in a continuous process was managed.
[0181] The results are provided in Tables 7 and 8.
[0182] In the following Table 7, three samples of the organic alloy
according to Example 1 were prepared and used to form each thin
film by repeating three times a continuous process, and the thin
films were respectively marked as Examples 1-1, 1-2, and 1-3, and
in the following Table 8, two samples of the organic alloy
according to Example 2 were prepared and used to form each thin
film by three times or five times repeating a continuous process
and the films were respectively marked as Examples 2-1 and 2-2.
TABLE-US-00007 TABLE 7 Variation with time during continuous
process A-33 B-10 Variation ratio (mol %) (mol %) A-33/B-10 with
time (%) Example 1-1 1 52.2 47.8 1.09 2.67 2 52.6 47.4 1.11 3 52.8
47.2 1.12 Example 1-2 1 53.3 46.7 1.14 1.90 2 53.5 46.5 1.15 3 53.8
46.2 1.16 Example 1-3 1 53.1 46.9 1.13 2.90 2 53.7 46.3 1.16 3 53.8
46.2 1.16 Comparative 1 50.7 49.3 1.03 11.02 Example 3 2 53.4 46.6
1.14 3 53.6 46.4 1.16
TABLE-US-00008 TABLE 8 Variation with time during continuous
process sample A-33 B-43 A-33/B- Variation ratio No. (mol %) (mol
%) 43 with time (%) Example 2-1 1 53.6 46.4 1.16 1.36 2 53.7 46.3
1.16 3 54.0 46.0 1.17 Example 2-2 1 54.3 46.7 1.19 0.79 2 54.5 45.5
1.20 3 54.5 45.5 1.20 4 54.5 45.5 1.20 5 54.5 45.5 1.20 Comparative
1 49.6 50.4 0.98 22.01 Example 5 2 53.5 46.5 1.15 3 55.7 44.3
1.26
[0183] Referring to Tables 7 and 8, the films formed of the organic
alloys according to Examples 1 and 2 showed almost constant ratio
among single organic compounds, that is, A-33/B-10 or A-33/B-43
compared with the thin films formed of the organic materials
according to Comparative Examples 3 and 5. Accordingly, a thin film
formed of an organic alloy may be reproduced through a continuous
process compared with a thin film formed of a simple mixture.
Manufacture of Organic Light Emitting Diode
Example 3
[0184] A glass substrate coated with a 1500 .ANG.-thick ITO (Indium
tin oxide) was cleaned with distilled water and an ultrasonic wave.
When the glass substrate is cleaned with distilled water, glass
substrate was ultrasonic wave-cleaned with a solvent such as
isopropyl alcohol, acetone, methanol and the like and dried, and
then, moved to a plasma cleaner, cleaned by using oxygen plasma for
10 minutes and to a vacuum depositor. This ITO transparent
electrode was used as an anode, a 700 .ANG.-thick hole injection
layer (HIL) was formed on the ITO substrate by vacuum-depositing
N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4'-diamin-
e (the compound A), and a hole transport layer (HTL) was formed by
depositing 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile
(HAT-CN) (the compound B) to be 50 .ANG. thick and then,
N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-
-fluoren-2-amine (the compound C) to be 1020 .ANG. thick on the
injection layer. On the hole transport layer (HTL), a 400
.ANG.-thick emission layer was formed by vacuum-depositing the
organic alloy of Example 1 as a host doped with 10 wt % of
tris(4-methyl-2,5-diphenylpyridine)iridium (Ill) (the compound D)
as a dopant.
[0185] Subsequently, a 300 .ANG.-thick electron transport layer
(ETL) was formed on the emission layer by vacuum-depositing
8-(4-(4-(naphthalen-2-yl)-6-(naphthalen-3-yl)-1,3,5-triazin-2-yl)phenyl)q-
uinoline (the compound E) and simultaneously hydroxyquinoline
lithium (Liq) in a ratio of 1:1, and a cathode was formed on the
electron transport layer (ETL) by sequentially vacuum-depositing
Liq to be 15 .ANG. thick and Al to be 1200 .ANG. thick,
manufacturing an organic light emitting diode.
[0186] The organic light emitting diode had a structure of
five-story organic thin films and specifically,
[0187] a structure of ITO/A 700 .ANG./B 50 .ANG./C 1020
.ANG./EML[organic alloy:D=X:10%] 400 .ANG./E:Liq 300 .ANG./Liq 15
.ANG./Al 1200 .ANG..
[0188] (X=weight ratio)
Example 4
[0189] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic alloy
of Example 2 instead of the organic alloy of Example 1.
Comparative Example 6
[0190] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic
material of Comparative Example 1, that is, the compound A-33 as a
single host instead of the organic alloy of Example 1.
Comparative Example 7
[0191] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic
material of Comparative Example 2, that is, the compound B-10 as a
single host instead of the organic alloy of Example 1.
Comparative Example 8
[0192] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic
material of Comparative Example 3, that is, a simple mixture of the
compound A-33 and the compound B-10 instead of the organic alloy of
Example 1.
Comparative Example 9
[0193] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic
material of Comparative Example 4, that is, the compound B-43 as a
single host instead of the organic alloy of Example 1.
Comparative Example 10
[0194] An organic light emitting diode was manufactured according
to the same method as Example 3 except for using the organic
material of Comparative Example 5, that is, a simple mixture of the
compound A-33 and the compound B-43 instead of the organic alloy of
Example 1.
Evaluation 4
[0195] Luminous efficiency and life-span characteristics of the
organic light emitting diodes according to Examples 3 and 4 and
Comparative Examples 6 to 10 were evaluated.
[0196] The measurements were specifically performed in the
following method, and the results were provided in the following
Table 9 and Table 10.
[0197] (1) Measurement of Current Density Change Depending on
Voltage Change
[0198] Current values flowing in the unit device of the
manufactured organic light emitting diodes were measured for, while
increasing the voltage from 0 V to 10 V using a current-voltage
meter (Keithley 2400), and the measured current values were divided
by an area to provide the results.
[0199] (2) Measurement of Luminance Change Depending on Voltage
Change
[0200] Luminance of the manufactured organic light emitting diodes
was measured for luminance, while increasing the voltage from 0 V
to 10 V using a luminance meter (Minolta Cs-1000A).
[0201] (3) Measurement of Luminous Efficiency
[0202] Current efficiency (cd/A) at the same current density (10
mA/cm2) were calculated by using the luminance, current density,
and voltages obtained from items (1) and (2).
[0203] (4) Measurement of Life-Span
[0204] Luminance (cd/m.sup.2) was maintained at 6000 cd/m.sup.2 and
a time at current efficiency (cd/A) decreases to 97% was
measured.
TABLE-US-00009 TABLE 9 Luminous Life- efficiency spanT97 Host
(cd/A) (h) Example 3 A-33 + B-10 organic 47.7 450 alloy Comparative
Example 6 A-33 31.1 150 Comparative Example 7 B-10 34.8 10
Comparative Example 8 A-33 + B-10 simple 45.1 350 mixture
TABLE-US-00010 TABLE 10 Luminous Life- efficiency spanT97 Host
(cd/A) (h) Example 4 A-33 + B-43 organic 47.8 900 alloy Comparative
Example 6 A-33 31.1 150 Comparative Example 9 B-43 2.6 10
Comparative Example 10 A-33 + B-43 simple 44.0 720 mixture
[0205] Referring to Tables 9 and 10, the organic light emitting
diode of Example showed equivalent or improved luminous efficiency
and life-span characteristics compared with the organic light
emitting diodes of Comparative Examples 6 to 8, and the organic
light emitting diode of Example 4 showed equivalent or improved
luminous efficiency and life-span characteristics compared with the
organic light emitting diodes of Comparative Examples 6, 9, and 10.
Accordingly, an organic light emitting diode using the organic
alloy turned out to have equivalent or improved performance
compared with an organic light emitting diode using a single
organic compound or a simple mixture thereof.
[0206] While this invention has been described in connection with
what is presently considered to be practical exemplary embodiments,
it is to be understood that the invention is not limited to the
disclosed embodiments, but, on the contrary, is intended to cover
various modifications and equivalent arrangements included within
the spirit and scope of the appended claims. Therefore, the
aforementioned embodiments should be understood to be exemplary but
not limiting the present invention in any way.
DESCRIPTION OF SYMBOLS
[0207] 100, 200: organic light emitting diode [0208] 105: organic
layer [0209] 110: cathode [0210] 120: anode [0211] 130: emission
layer [0212] 140: hole auxiliary layer
* * * * *