WO2015199303A1

WO2015199303A1 - Compound, and organic photoelectronic device and display device comprising same

Info

Publication number: WO2015199303A1
Application number: PCT/KR2015/000049
Authority: WO
Inventors: 이상신; 유은선; 이준엽; 조용주; 최윤호
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-06-24
Filing date: 2015-01-05
Publication date: 2015-12-30
Also published as: KR101783650B1; KR20160000331A

Abstract

Provided are a compound represented by chemical formula I; an organic photoelectronic device comprising the same; and a display device comprising the organic photoelectronic device.

Description

【Specification】

[Name of invention]

Compound, organic optoelectronic device and display device comprising same

Technical Field

A compound, an organic optoelectronic device, and a display device are provided.

Background Art

Organic optoelectric diodes are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be divided into two types according to the principle of operation. One is an optoelectronic device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electric energy. It is a light emitting device that generates light energy from energy.

Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting device, an organic solar cell and an organic photo conductor drum.

The organic light emitting diode (OLED) has attracted much attention recently as the demand for flat panel display devices increases. The organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material, and has a structure in which an organic layer is inserted between an anode and a cathode.

consist of. The organic layer may include a light emitting layer and an auxiliary layer, and the auxiliary layer may include, for example, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer to increase efficiency and stability of the organic light emitting device. And at least one layer selected from a hole blocking layer.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and in particular, is affected by the organic material included in the organic layer.

In particular, in order for the organic light emitting diode to be applied to a large flat panel display, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing electrochemical stability.

[Detailed Description of the Invention]

[Technical problem] It is to provide a compound that can provide an organic optoelectronic device having characteristics such as high efficiency, long life, thermal stability.

An organic optoelectronic device and a display device including the compound are provided. Technical Solution

In one embodiment of the present invention, a compound represented by the following formula (I) is provided.

I]

In Formula I,

D ¹ and D ² are each independently represented by the following chemical formulas d-1 or d-2:

[Formula d-1] [Formula d-2]

In Chemical Formulas d-1 and d-2,

X ¹ to X ⁸ are each independently N or CR ^a ,

L ¹ is N, B, CR ^b or SiR ^c ,

M ¹ is a single bond, 0 or S,

L ² is C or Si,

M ² is N,

* Is the junction point,

R ^a is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group ego,

R and R ^c are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkyl group, substituted or unsubstituted Amine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or Unsubstituted CI to C30 carbonylamino group, substituted or unsubstituted C1 to C30

Sulfamoylamino groups, substituted or unsubstituted C2 to C30 alkenyl groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted silyloxy groups substituted or unsubstituted C1 to C30 Acyl, Substituted or Unsubstituted C1 to C20

Acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthio group, substituted or unsubstituted C1 to C30 heterocyclothiol group , A substituted or unsubstituted C1 to C30 ureide group, halogen group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group or a combination thereof,

W ¹ and W ² are each independently a C1 to C10 alkyl group unsubstituted or substituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group, or phosphoryl group; C6 to C20 aryl group unsubstituted or substituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group, or phosphoryl group; Cyano group; Nitro group; Halogen group; Amide group; Sulfonyl group; Phosphine groups; Phosphoryl group; Or a combination thereof,

a, b, c and d are each independently an integer of 1 or more,

3 <a + b <7, 3 <c + d <7.

In another embodiment of the present invention, a compound for an organic optoelectronic device is provided. In another embodiment of the present invention, it comprises an anode and a cathode facing each other, and a layer of an organic layer located between the anode and the cathode, the organic layer is a compound according to an embodiment of the present invention described above It provides an organic optoelectronic device comprising. In another embodiment of the present invention, the above-described embodiment of the present invention

Provided is a display device including an organic optoelectronic device.

Advantageous Effects

The organic optoelectronic device including the compound ol has excellent electrochemical and thermal stability, excellent life characteristics, and high luminous efficiency even at a low driving voltage.

[Brief Description of Drawings]

1 and 2 are cross-sectional views showing various embodiments of an organic light emitting device that can be manufactured using a compound according to an embodiment of the present invention.

3 is a graph showing light emission spectra according to a comparative example. 4 is a graph showing the absorption spectrum of Compound 1, the emission spectrum in solution, and the emission spectrum at a concentration of 1% of polystyrene (PS). 5 is a current density-voltage graph according to a comparative example.

6 is a graph showing current density-voltage-luminance according to an embodiment of the present invention.

7 is a graph showing current density-external quantum efficiency according to a comparative example.

8 is a graph showing the external quantum efficiency according to an embodiment of the present invention at a specific current density and emission wavelength.

100: organic light emitting device, 200: organic light emitting device

105: organic layer

1 10: cathode

120: anode

130: light emitting layer, 230: light emitting layer

140: hole auxiliary layer

[The best form to carry out invention]

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, unless otherwise defined, "substituent" means that at least one hydrogen in a substituent or compound is a deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted Ring C3 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, polouro group, trifluorouromethyl group, etc. C1 to CH) means a trifluoroalkyl group or a cyano group.

In addition, the substituted halogen group, 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, C1 to C10 such as C3 to C30 cycloalkyl group, C6 to C30 aryl group, C 1 to C20 alkoxy group, fluoro group, trifluoromethyl group, etc.

Two adjacent substituents of the trifluoroalkyl group or the cyano group are fused to form a ring. It may be formed.

As used herein, "hetero" means one to three heteroatoms selected from the group consisting of Ν, Ο, S and Ρ, and the remainder is carbon unless otherwise defined.

As used herein, unless otherwise defined, an "alkyl group" is aliphatic

It means a hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an alkyl group that is C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, with methyl, ethyl, propyl, iso-propyl, η-butyl, iso-butyl, _sec -butyl and t-butyl Selected from the group consisting of:

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nuclear group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means a practical skill.

"Aryl group" 'means a substituent in which all elements of the cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic or fused ring polycyclic ( That is, a ring) group that shares adjacent pairs of carbon atoms.

As used herein, a “heterocyclic group” refers to a hetero atom selected from the group consisting of N, 0, S, P, and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. Containing at least one, and the rest being carbon. When the heterocyclic group is a fused ring, the heterocyclic group may include one or more heteroatoms for each or each ring. Thus, the heterocyclic group is a higher concept encompassing the heteroaryl group.

More specifically, a substituted or unsubstituted aryl group and / or a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, Substituted or unsubstituted phenan ^ reylene group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m- Terphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted peryleneyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted Substituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted Or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazoleyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted Pyrazinyl groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or Unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted

Quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted

Benzoxazineyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted

Acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenothiazineyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted carbazolyl group, A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

In the present specification, a single bond refers to a bond directly connected without passing through carbon or a hetero atom other than carbon, and specifically, M means a single bond means that both atoms connected to M are directly connected. That is, when M, one of the six atoms constituting the hexagonal ring in the present specification, is a single bond, it forms a pentagonal ring.

In the present specification, the halogen group means a fluoro group, a chloro group, a bromo group or an iodine group, and in one example, may be a fluoro group.

In the present specification, thermal delayed fluorescence refers to a phenomenon in which fluorescence is emitted by using thermally activated delayed fluorescence (TADF) from a tritium excited state to a singlet excited state. Delayed fluorescence is called in the sense that long-lived light emission occurs because of the triplet excited state. Because it uses fluorescent singlet excited state and triplet excited state High efficiency fluorescence can be expressed.

In one embodiment of the present invention provides a compound represented by the following formula (I). [Formula I]

In formula (I)

[Formula d-1] [Formula d-2]

χ ² Υ Υ ⁽⁷ x ² x X ^{7 in the} above formulas d-1 and d-2,

X ¹ to X ⁸ are each independently N or CR ^a ,.

L ¹ is N, B, CR ^b or SiR ^c ,

M ¹ is a single bond, 0 or S,

L ² is C or Si,

M ² is N,

* Is the junction point,

R ^b and！ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkyl group, substituted or unsubstituted Substituted amine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C1 to C30 carbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted Or an unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted silyloxy group Substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20

Acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthi group, substituted or unsubstituted C1 to C30 heterocycloty group Substituted or unsubstituted C1 to C30 ureide group, halogen group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group or a combination thereof,

W ¹ and W ² are each independently a C1 to C10 alkyl group unsubstituted or substituted with a cyano group, a nitro group, a halogen group, an amide group, a sulfonyl group, a phosphine group, or a phosphoryl group; C6 to C20 aryl group unsubstituted or substituted with a cyano group, a nitro group, a halogen group, an amide group, a sulfonyl group, a phosphine group, or a phosphoryl group; Cyano group; Nitro group; Halogen group; Amide group; Sulfonyl group; Phosphine groups; Phosphoryl group; Or a combination thereof,

a, b, c and d are each independently an integer of 1 or more,

3 <a + b <7, 3 <c + d <7.

The compound represented by the formula (I) of the present specification has a rotational degree of freedom due to the steric hindrance between the biphenyl core and the substituent by dividing the region of the electron donating group and the electron withdrawing group into the biphenyl core. It is lowered to have a rigid molecular structure.

This rigid molecular structure facilitates the separation of HOMO-LUMO, thereby reducing the energy gap between triplet excitation energy and singlet excitation energy. This small energy gap facilitates the transition between the triplet to the singlet excited state of the triplet, so that the luminescence efficiency can be improved by designing a molecule that utilizes the fluorescence of the singlet as well as the fluorescence transferred from the triplet to the reverse system.

Generally, axtone is 25% in singlet excited state, in triplet excited state

There is a 75% probability that light emission from the singlet excited state is fluorescence and light emission from the triplet excited state is phosphorescence. That is, phosphorescent light emitting materials have been indispensable for driving devices with high efficiency.

However, the phosphorescent material has a limitation in terms of freedom of molecular design because a complex compound containing a metal or heavy metal such as Ir, Pt, C _U , Be, etc. must be used.

The compound represented by the formula (I) according to the present invention can be used to It is a pure organic compound that does not contain and can increase the degree of freedom of molecular design, and can be used for high-efficiency light emitting materials due to delayed fluorescence.

D ¹ and D ² refer to a substituent as an electron donor, and may be represented by the following Chemical Formula d-1 or d-2.

[Formula d-1] [Formula d-2]

丫 L ₇

In Formulas d-1 and d-2, X ¹ to X ⁸ are as defined above, L ¹ is N, B, CR ^b or SiR ^c , Μ ¹ is a single bond, 0 or S, and L ² Is C or Si, Μ ² is

Ν and * is the junction point.

R ^b and！ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkyl group, substituted or unsubstituted A substituted amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 carbonyl group, a substituted or unsubstituted C1 to C30 carbonylamino group, a substituted or unsubstituted C1 to C30

Sulfamoylamino groups, substituted or unsubstituted C2 to C30 alkenyl groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted silyloxy groups, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20

Acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted

C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthio group, substituted or unsubstituted C1 to C30 heterocyclothiyl group, substituted or unsubstituted C1 to C30 ureide group, halogen group, cyano group, hydroxide It is a siloxane group, an amino group, a nitro group, a carboxyl group, or a combination thereof.

More specifically, it may be represented by any one of the following formula d-3 to d-7. [Formula d-3] [Formula d-4] [Formula d-5]

[Formula d-6] [Formula d-7]

In Chemical Formulas d-3 to d-7,

X ¹ to X ⁸ are each independently N or CR ^a

R ^a , ^al and R ³² are each independently hydrogen, deuterium, substituted or unsubstituted C10 alkyl group in C1, substituted or unsubstituted C1 to C10 alkenyl group, substituted or unsubstituted C1 to C10 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ^b is as defined above.

For example, D ¹ and D ² are each independently a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenoxazine group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted Fluorenyl group, or a substituted or unsubstituted amine group. ^'

Wherein “substituted” means a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted C6 to Mean substituted by C20 aryl group.

In the compound represented by the formula (I) according to an embodiment of the present invention, specific examples of the substituent include methyl group, ethyl group, propyl group, isobutyl group, meso groups,

Group, propoxy group, isopropoxy group, phenyl group, naphthyl group, or biphenyl group. The W ¹ and W ² means a substituent as an electron acceptor, each independently, a cyano group, a nitro group, a halogen group, A C1 to C10 alkyl group unsubstituted or substituted with an amide group, sulfonyl group, phosphine group, or phosphoryl group; Cyano group, nitro group, halogen group, amide group C6 to C20 aryl group unsubstituted or substituted with a sulfonyl group, a phosphine group, or a phosphoryl group; Cyano group; Nitro group; Halogen group; Amide group; Sulfonyl group; Phosphine groups; Phosphoryl group; Or combinations thereof.

Wherein the amide group, sulfonyl group, phosphine group, and phosphoryl group are each a functional group represented by -CONR, -SO ₃ R, -PRR ', -PORR',

R and R 'are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C10 alkenyl group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof. Formula I may be represented by the following Formula 1-1 or 1-2 depending on the zoning of the substituents.

[Formula 1 -1] [Formula 1 -2]

In Formulas I-1 and I-2,

D ', D ^2, defined in the W ¹ and W ² are as described above, a 3≤a + b≤6, 3≤c + d≤6. Since a substituent functioning as an electron donor or an electron acceptor is simultaneously present at a position adjacent to the biphenyl core, it is possible to more effectively prevent rotational freedom due to steric hindrance between substituents, and thus formation of a rigid molecular structure can be expected. Since the molecular structure further increases the probability of intercalation transition due to thermal activation, theoretically 100% of internal quantum efficiency can be achieved, and the light emission efficiency can be further improved by suppressing triplet-triple extinction. . Specific examples of compounds according to one embodiment of the invention are listed below

It may be a compound, but is not limited thereto.

31 32

33 34 35

36 37 38

39 40

The compound may be for an organic optoelectronic device.

Hereinafter, an organic optoelectronic device to which the above-described compound is applied will be described.

In another embodiment of the present invention, it includes an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, the organic layer provides an organic optoelectronic device comprising the compound. The organic layer may include a light emitting layer, and the light emitting layer may include the compound.

Specifically, the compound may be included as a thermal delayed fluorescent material of the light emitting layer.

In addition, the light emitting layer may further include a host material in addition to the thermal delayed fluorescent material. The compound may be used in the organic layer to improve the life characteristics, efficiency characteristics, electrochemical stability and thermal stability of the organic optoelectronic device, and lower the driving voltage.

More specifically, the organic optoelectronic device may be an organic light emitting device.

1 and 2 include a compound according to an embodiment of the present invention

A cross-sectional view of an organic light emitting device.

1 and 2, the organic light emitting diodes 100 and 200 according to the exemplary embodiment of the present invention may include an anode 120, a cathode 110, and at least one layer positioned between the anode and the cathode.

It has a structure including the organic thin film layer 105.

The anode 120 comprises an anode material, which is typically

A material having a large work function is preferable to facilitate hole injection into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof, and include zinc oxide, indium oxide, indium tin oxide (ΠΌ), and indium zinc oxide (IZO). And metal oxides such as ZnO and A1 or combinations of metals and oxides such as Sn0 ₂ and Sb, and poly (3-methylthiophene), poly (3,4- (ethylene-1, Conductive materials such as 2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole, and polyaniline, and the like, but are not limited thereto. Preferably, a transparent electrode including indium tin oxide (ITO) may be used as the anode.

The negative electrode 1 10 includes a negative electrode material, which is usually used as a negative electrode material.

It is preferable that the material has a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, sesame, barium, or alloys thereof, and LiF / Al. , Multilayer structures such as Li0 ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, and the like, but are not limited thereto. Preferably, a metal electrode such as aluminum may be used as the cathode.

Referring first to FIG. 1, FIG. 1 illustrates that only the light emitting layer 130 exists as the organic layer 105. As the organic light emitting device 100 is illustrated, the organic layer 105 may exist only as the light emitting layer 130.

Referring to FIG. 2, FIG. 2 includes an electron transport layer as the organic layer 105.

As shown in FIG. 2, the organic layer 105 includes the light emitting layer 230 and the hole transport layer 140, in which the light emitting layer 230 and the hole transport layer 140 exist. It may be two-layered. In this case, the light emitting layer 230 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve bonding and hole transporting properties with a transparent electrode such as πΌ. Although not shown in FIG. 1 and FIG. 2, the organic layer 105 may further include an electron injection layer, an auxiliary electron transport layer, an electron transport layer, a major transport layer, an auxiliary major transport layer, a major injection layer, and the like.

1 and 2, the light emitting layers 130 and 230 and the hole transport layer 140 forming the organic layer 105, an electron injection layer, an auxiliary electron transport layer, an electron transport layer, an electron transport layer, and an auxiliary hole, which may not be added, may be added. Any one selected from the group consisting of a hole transport layer, a hole injection layer, and a combination thereof includes the compound for an organic optoelectronic device.

In particular, the compound for an organic optoelectronic device may be used in the light emitting layers 130 and 230, and may be used as a green fluorescent material in the light emitting layer.

In the organic light emitting device described above, after forming an anode on a substrate,

Dry film formation methods such as evaporation, sputtering, plasma plating and ion plating; Alternatively, the organic thin film layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode thereon. ᅳ 、

Another embodiment of the present invention provides a display device including the organic optoelectronic device.

[Mode for Carrying Out the Invention] The following provides specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Example 1 Synthesis of Compound 1

The above presented as a specific example of the compound for an organic photoelectric device of the present invention Compound of formula (i) was synthesized through a three step route, such as Banung 1 below.

[Banungsik 1]

(Intermediate 1) (Intermediate 2)

(Compound 1)

Synthesis Example 1 Synthesis of Intermediate 1

[Medium Banungsik 1

(Intermediate 1)

1,5-Dibromo-2,4-difluorobenzene (30 g, 110.3 mmol) and cyano cooper (22.7 g, 253.7 mmol) were dissolved in DMF (120 ml) and brought to nitrogen atmosphere. The mixture was stirred at reflux for 17 hours. After extracting the semi-aqueous solution with MC, column chromatography was performed on the ethyl acetate / nucleic acid mixed solvent as a developing solvent to obtain 6.0 g of intermediate 1. Intermediate 1: Mass Spectrometry (FAB) m / z 164 [(M + H) < + >]. 1 H MR (200 MHz, CDC13): δ 8.04 (t, 1H), 7.24 (t, 1H). Synthesis Example 2 Synthesis of Intermediate 2

[Medium Banungsik 2]

(Intermediate 2)

Wash the sodium hydride (0.9 g, 24.3 mmol) containing 60% in paraffin oil with normal nucleic acid, and then dissolve the solution in which carbazole (3.1 g, 18.2 mmol) was dissolved in THF (tetrahydroforan) at 1 M concentration. Put it on the ride. After stirring for 30 minutes

When the sodium hydride is completely dissolved, intermediate 1 (1.0 g, 6.1 mmol) is slowly added to THF as a 1 M solution. After stirring for 2 hours at room temperature, the reaction was terminated by pouring methanol or distilled water. The reaction product was extracted with MC and subjected to column chromatography using a mixed developing solvent of chloroform / nucleic acid to obtain 2.3 g of intermediate 2.

Intermediate 2: Mass Spectrometry (FAB) m / z 459 [(Μ + Η) +] · 1Η NMR (200 MHz, CDC13): δ 8.46 (s, 1H), 8.14 (d, J = 7.2 HZ, 3H), 7.94 (s, 1 H), 7.50-7.46 (m, 3 H), 7.40-7.35 (m, 10 H). Synthesis Example 3 Synthesis of Compound 1

[

(Compound 1)

The intermediate 2 (1.0 g, 2.2 mmol) obtained in Synthesis Example 2 was added with a mixed THF / DMPU solvent, and the temperature was lowered to -90 ^° C. or lower under a nitrogen atmosphere, followed by stirring for 30 minutes. 2 M concentration of LDA (0.3 g, 2.4 mmol) was added slowly to the reaction. After stirring for an hour, iodine (0.3 g, 1.1 mmol) was dissolved in THF and slowly added to the reaction. After raising the temperature of the reaction product to room temperature, the reaction was terminated by adding hydrochloric acid having a concentration of ΙΜ. The reaction product was extracted with MC and washed three times with distilled water. The extract was dried over anhydrous magnesium sulfate and the solvent was removed. The reaction product was purified by column chromatography using a mixed developing solvent of chloroform / nucleic acid, and finally sublimed purification gave 0.5 g of a pure yellow solid.

Compound 1: yield 50%, mass spectrometry (FAB) m / z 914 [(M + H) +]. Elemental analysis

Theoretical C64H34N8: C, 84.01%; H, 3.75%; N, 12.25%. Found: C, 84.00%; H, 3.55%; N, 12.46%. 1 H NMR (200 MHz, CDC13): 6 7.99 (d, 4H), 7.67 (d, 4H), 7.41 (d, 4H), 7.32 (s, 2H), 7.12-6.56 (m, 20H). (Measurement of emission spectrum)

The emission spectrum of Compound 1 according to Example 1 was measured and the results are shown in FIG. ⁴ .

4 is an absorption spectrum of Compound 1, a light emission spectrum in solution, and

It is a graph showing the emission spectrum at 1% concentration of polystyrene (PS, polystyrene). Absorption fractions were measured at 10 μM concentration using THF. The scan rate was used at l nm / s and was measured from 800 nm to 250 nm.

In order to confirm the emission spectrum of the material, it was measured using Hitachi's F-7000. The solution was measured with the sample used for absorbance analysis. In order to minimize the interaction between the material and the solvent to determine the intrinsic spectrum of the material, polystyrene was dissolved in THF using 1 \ ^% of polystyrene and coated on a quartz substrate at a speed of 1000 rpm using a spin coater. In order to check the HOMO and LUMO levels of the materials, ferrocene was used as the standard material, and the reference electrode and the counter electrode were used as Ag / AgCl and platinum wire, respectively. The electrolyte solvent was removed by oxygen bubbling ol. ^'

Referring to Figure 4, the absorption spectrum of compound 1 (red), in solution

The emission spectrum (blue) and the emission spectrum (light green) at PS 1% concentration can be confirmed.

In addition, it can be seen that the luminescence spectrum suitable for the green luminescent material is shown through the fluorescence spectrum (purple) at low temperature. On the other hand, the difference between the calculated singlet energy (SO 2.60 eV and triplet energy (TO 2.47 eV) is 0.13 eV, which is relatively small.

Example 2: Synthesis of Compound 39

Synthesis Example 4 Synthesis of Intermediate 3

[Medium Banungsik 4]

(Intermediate 3)

A compound of Intermediate 3 was obtained in 82% yield in a similar manner to the preparation of Intermediate 2, except using 9H-carbazole as 3,6-dimethyl-9H-carbazole.

Intermediate 3: Mass Spectrometry (FAB) m / z 514 [(M + H) +]. 1 H NMR (200 MHz, CDC13): δ 8.57 (s, 2H), 8.24 (s, 2H), 7.82-7.12 (m, 10H), 2.32 (s, 12H).

Synthesis Example 5 Synthesis of Compound 39

[Medium Banungsik 5]

(Compound 39)

Preparation of compound 1, except that intermediate 3 is used instead of intermediate 2 In a similar manner, compound 39 was obtained in a yield of 60%.

Compound 3 ⁹ : yield 60% mass spectrometry (FAB) m / z l026 [(M + H) < + >]. Elemental Analysis Theoretical C72H50N8: C (84.19%) H (4.91%) N (10.91%) Measured Value: C, 84.67%; H, 4.51%; N, 10.83%, 1 H NMR (200 MHz, CDC13): δ 7.87 (s, 4H), 7.28 (s, 4H), 7.14-6.54 (m, 14H), 6.23 (d, 4H), 2.21 (s _; 24H ). Comparative example

The compound represented by the following formula d was synthesized with reference to the synthesis method described in WO2013-154064.

(Manufacture of organic light emitting device)

An organic electroluminescent device having a compound synthesized according to the present embodiment and a light emitting layer comprising a comparative compound represented by the above formula d as a light emitting material

It produced and evaluated the characteristic. Device comparison example

On a glass substrate on which an anode made of indium tin oxide (ITO) having a thickness of 100 nm was formed, each thin film was laminated with a vacuum degree of 5.0 × 10 −4 Pa by vacuum deposition. First, α-NPD was formed at a thickness of 35 nm on πΌ, and then mCP was formed at a thickness of 10 nm. Furthermore, the comparative compound represented by the formula d and mCP were co-deposited from another evaporation source to form a 15 nm thick layer to form a light emitting layer. At this time, the concentration of the comparative compound represented by the formula (d) was 3.0 weight ⁰ /. Next, ΡΡΤ is formed at a thickness of 10 nm, TPBi is formed thereon at a thickness of 40 nm, and lithium fluoride (LiF) is vacuum deposited at 0.8 nm, followed by deposition of aluminum (A1) at a thickness of 100 nm. Was formed, and it was set as the organic electroluminescent element. The organic electroluminescent element manufactured by the semiconductor parameter. analyzer (Ajirent ^■ technology company make: E5273A), optical power meter measurement device (new pot) Company: 1930 C) and an optical spectrometer (manufactured by Ocean Optics: USB2000). Device Examples 1-A, 1-B, and 1-C

In place of the comparative example compound represented by the dopant d, using the compound 1 prepared in Example 1 it was doped with 5 weight ^_0/0, mCP, and 100 to each TmPyPB: _0: 90: 10, 75: 25 Doped hosts were mixed at the ratio of. Except for this, organic light emitting diodes were manufactured in the same manner as in the device comparison example, respectively, in Example 1-A, Example 1-B, and Example 1-C. 6 is shown. Device Examples 2-A, 2-B, and 2-C

In place of the comparative compound represented by d as the dopant, the compound 1 prepared in Example 1 was used to be doped at 1 weight ⁰ /., 3 weight%, and 5 weight%, and mCP and TmPyPB were 50:50. Doped hosts were weighted by weight. Except for this, an organic light emitting diode was manufactured in the same manner as in Comparative Example, and the device example 2-A, the device example 2-B, and the device example 2-C were manufactured, and the quantum efficiency results are shown in FIG. 8. .

(Performance Measurement of Organic Light Emitting Diode)

For each organic light emitting device manufactured in Examples 1-A, 1-B, 1-C, 2-A, 2-B, 2-C, and Device Comparative Examples, current density change according to voltage, and external Quantum efficiency was measured and the results are shown in FIGS. 5 to 8. The specific measuring method is as follows.

(1) Measurement of change in current density according to voltage change

Prepared according to the device examples ί-Α, Ι-B, 1-C, and the device comparative example

With respect to the organic light emitting device, while measuring the current value flowing through the unit device using a current-voltmeter (Keithley 2400) while increasing the voltage from 0 V to 10 V, the measured current value is divided by the area and the result is shown in FIGS. 6 is shown.

5 is a current density-voltage graph according to a comparative example.

In particular, referring to Figure 6 according to an embodiment of the present application, in the graph of measuring the current density-voltage-luminance for each mixing ratio of the host, the current density characteristics according to the voltage as the ratio of the host, and the luminance according to the voltage It can be seen that the difference in characteristics is not large. (2) External quantum efficiency measurement method

For the organic light emitting diodes manufactured in Examples 2A, 2-B, 2-C and Comparative Examples, all devices were evaluated by encapsulating with a moisture absorbent, and using keithley 2635 source measurement unit and CS IOOO spectroradiometer. IVL curve was measured. The quantum efficiency of all devices was calculated assuming a lambertian distribution. The results are shown in FIGS. 7 and 8.

7 is a current density-external quantum efficiency graph according to a comparative example.

8 is a graph showing the external quantum efficiency of the organic light emitting device manufactured according to an embodiment of the present invention at a specific current density and emission wavelength.

Referring to FIGS. 7 and 8, in the case of the device to which the compound according to the exemplary embodiment of the present invention is applied, the maximum external quantum efficiency is excellent at the same emission wavelength and similar current density as compared to the device to which the compound of the comparative example is applied. have. That is, when the compound of the comparative example is applied in FIG. 7, the external quantum efficiency is 11% or less, whereas when the compound of the example is applied in FIG. 8, the external quantum efficiency of 18.7% is achieved.

On the other hand, when the doping concentration of the dopant according to the present embodiment, the first weight _{^0/0, and} can identify represents the best efficiency. The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

[Claims] [Claim 11] Compound represented by the following formula (I): [Formula (I)] In the formula (I), D1 and D2 are each independently represented by the following formula (d-1 or d-2):

[Formula d-1] [Formula d- ² ]

In the above formulas d-1 and d-2,

X ¹ to X ⁸ are each independently N or CR ^a ,

L ¹ is N, B, CR ^b or SiR ^c ,

M ¹ is a single bond, 0 or S,

L ² is C or Si,

M ² is N,

* is the connection point,

R ^a is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group. ego,

R ^b and R ^c are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, substituted or unsubstituted. Substituted amine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C1 to C30 carbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted silyl group, substituted or unsubstituted silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C1 to C30 heterocyclothiol group, substituted or unsubstituted C1 to C30 C30 ureide group, halogen group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, or a combination thereof,

W ¹ and W ² are each independently a C1 to C10 alkyl group unsubstituted or substituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group, or phosphoryl group; C6 to C20 aryl group substituted or unsubstituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group _, or phosphoryl group; Cyano group; nitro group; halogen group; amide group; Sulfonyl group; phosphine group; phosphoryl group; Or a combination thereof,

a, b, c and d are each independently an integer of 1 or more,

3 < a + b < 7, 3 < c + d < 7.

【Claim 2】

According to clause 1,

D ¹ and D ² are each independently a compound represented by any one of the following formulas d-3 to d-7:

[Formula d-3] [Formula d-4] [Formula d-5]

[Formula d-6] [Formula d-7]

In the above formulas d-3 to d-7,

X ¹ to X ⁸ are each independently N or CR ^a and R ^a , R ^al and R ³² are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or A substituted or unsubstituted C6 to C20 aryl group,

R ^b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30

Heterocycloalkyl group, substituted or unsubstituted amine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C1 to C30 carbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted silyl group, substituted or unsubstituted silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkyl A thiol group, a substituted or unsubstituted C1 to C30 heterocyclothiol group, a substituted or unsubstituted C1 to C30 ureide group, a halogen group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, or a combination thereof,

* is the connection point.

【Claim 3】

In clause U,

D ¹ and D ² are each independently a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenoxazine group, or a substituted or unsubstituted group.

Phenothiazine group, substituted or unsubstituted fluorenyl group, or substituted or unsubstituted

It is an amine group,

Here, "substitution" means that at least one hydrogen is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted ^' C6 to a compound substituted with a C20 aryl group.

【Claim 4】

In clause U,

The formula I is a compound represented by the following formula 1-1 or 1-2: [Formula ι _η [Formula 1-2]

In the above formulas 1-1 and I-2,

D ¹ and D ² are each independently represented by the following formula d-1 or d-2:

[Formula d-1] [Formula d- ² ]

In the above formulas d-1 and d-2,

X ¹ to X ⁸ are each independently N or CR ^a ,

L ¹ is N, B, C ^b or SiR ^c ,

M ¹ is a single bond, 0 or S,

L ² is C or Si,

M ² is N,

* is the connection point,

R ^b and ! are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkyl group, substituted or unsubstituted amine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C1 to C30 carbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted silyl group, substituted or unsubstituted silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 Acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C1 to C30 heterocyclothiol group. , Substituted or unsubstituted C1 to C30 ureide group, halogen group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, or a combination thereof,

W ¹ and W ² are each independently a C1 to C10 alkyl group unsubstituted or substituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group, or phosphoryl group; C6 to C20 aryl group unsubstituted or substituted with a cyano group, nitro group, halogen group, amide group, sulfonyl group, phosphine group, or phosphoryl group; Cyano group; nitro group; halogen group; amide group; Sulfonyl group; phosphine group; phosphoryl group; Or a combination thereof,

a, b, c and d are each independently an integer of 1 or more,

3 < a + b < 6, 3 < c + d < 6.

【Claim 5】

According to clause 1,

The compound represented by Formula 1 is one selected from the compounds listed in Group I below:

[Group I]

WO 2015/199303 PCT/KR2015/000049

39 40 41 42

[Claim 6]

The compound according to any one of items 1 to 5 is a compound for organic optoelectronic devices. ^:

【Claim 7】

An anode and a cathode facing each other, and

An organic optoelectronic device comprising at least one organic layer located between the anode and the cathode, wherein the organic layer includes the compound according to any one of claims 1 to 5.

【Claim 8】

In paragraph 7,

The organic layer includes a light-emitting layer,

The commercial light-emitting layer is an organic optoelectronic device containing the above compound.

【Claim 9】

According to clause 8,

The compound is an organic optoelectronic device included as a heat-delayed fluorescent material of the light emitting layer. 【Claim 10】

In clause 8,

The light emitting layer is an organic optoelectronic device further comprising a host material.

【Claim 1 1】

A display device including the organic optoelectronic device according to claim 7.