KR20180053980A - Compound for organic optoelectronic device, and organic optoelectronic device and display device - Google Patents

Abstract

The present invention relates to a compound for an organic optoelectronic device represented by chemical formula 1, an organic optoelectronic device using the same, and a display device. Details of chemical formula 1 are defined in the specification. According to the present invention, a high-efficient and long-living organic optoelectronic device can be realized.

Description

Technical Field [0001] The present invention relates to a compound for organic optoelectronic devices, organic optoelectronic devices, and display devices. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

A compound for an organic optoelectronic device, an organic optoelectronic device and a display device.

An organic optoelectronic diode is an element that can switch between electric energy and light energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode. The organic layer may include a light emitting layer and an optional auxiliary layer. The auxiliary layer may include, for example, a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, And a hole blocking layer.

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

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

One embodiment provides a compound for an organic optoelectronic device capable of implementing a high-efficiency and long-lived organic optoelectronic device.

Another embodiment provides an organic optoelectronic device comprising such a compound.

Another embodiment provides a display device comprising the organic opto-electronic device.

According to one embodiment, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

R ¹ and R ² are each independently hydrogen, deuterium, cyano, nitro, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocycle Group, or a combination thereof,

ET represents a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinolinyl group Substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl groups, substituted or unsubstituted benzothieno [2,3-d] pyrimidinyl groups, substituted or unsubstituted benzofuro [3,2-d] pyrimidinyl group, or a substituted or unsubstituted benzofura [2,3-d] pyrimidinyl group,

Means that at least one hydrogen is substituted with deuterium, a C1 to C10 alkyl group, a C6 to C20 aryl group, or a C2 to C20 heteroaryl group.

According to another embodiment, there is provided an organic electroluminescent device comprising an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, wherein the organic layer comprises an organic optoelectronic device including the above- do.

According to another embodiment, there is provided a display device including the organic optoelectronic device.

High-efficiency long-lived organic optoelectronic devices can be realized.

1 and 2 are cross-sectional views illustrating an organic light emitting device according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one hydrogen in the substituent or compound is replaced with a substituent selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, A C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 aryl group, A C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof.

In one embodiment of the invention, " substituted " means that at least one of the substituents or the hydrogen in the compound is deuterium, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, A heterocycloalkyl group, a C6 to C30 aryl group, or a C2 to C30 heteroaryl group. In a specific example of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, C1 to C30 alkyl group, C6 to C18 aryl group, or C2 to C20 heteroaryl group. In the most specific embodiment of the present invention, " substituted " means that at least one hydrogen in the substituent or compound is substituted with deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C18 heteroaryl group.

Means one to three heteroatoms selected from the group consisting of N, O, S, P and Si in one functional group, and the remainder being carbon unless otherwise defined .

As used herein, the term "alkyl group" means an aliphatic hydrocarbon group, unless otherwise defined. 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 of C1 to C30. More specifically, the alkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

As used herein, the term " aryl group " refers to a grouping of groups having one or more hydrocarbon aromatic moieties,

A structure in which all the elements of the hydrocarbon aromatic moiety have a p-orbital and these p-orbital forms a conjugation, such as a phenyl group and a naphthyl group,

A structure in which two or more hydrocarbon aromatic moieties are connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quarter-phenyl group,

Two or more hydrocarbon aromatic moieties may also include non-aromatic fused rings fused directly or indirectly. For example, a fluorenyl group and the like.

The aryl groups include monocyclic, polycyclic or fused ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

As used herein, the term " heterocyclic group " is a superordinate concept including a heteroaryl group, and includes N, O, and S substituents in the ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, Means at least one heteroatom selected from the group consisting of S, P and Si. When the heterocyclic group is a fused ring, the heterocyclic group or the ring may include one or more heteroatoms.

As used herein, the term " heteroaryl group " means containing at least one heteroatom selected from the group consisting of N, O, S, P and Si in the aryl group. Two or more heteroaryl groups may be directly connected through a sigma bond, or when the heteroaryl group includes two or more rings, two or more rings may be fused together. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

The heterocyclic group may include, for example, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group and the like.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heterocyclic group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra 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 naphthacenyl group, A substituted or unsubstituted thienyl group, a substituted 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 fluorenyl 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 furanyl group, a substituted or unsubstituted thiophenyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiadiazolyl 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 Substituted or unsubstituted indolyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted isoquinazolyl groups, A substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted naphthyridinyl group, Substituted or unsubstituted phenanthryl groups, substituted or unsubstituted phenothiazyl groups, substituted or unsubstituted phenanthryl groups, substituted or unsubstituted dibenzofuranyl groups, or substituted or unsubstituted di Substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl groups, substituted or unsubstituted benzothieno [2,3-d] pyrimidinyl groups, substituted or unsubstituted benzopure A [3,2-d] pyrimidinyl group, or a substituted or unsubstituted benzofura [2,3-d] pyrimidinyl group, or a combination thereof.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level to inject electrons formed in the cathode into the light emitting layer, move electrons formed in the light emitting layer to the cathode, It is a characteristic that facilitates movement.

The compounds for organic optoelectronic devices according to one embodiment will be described below.

The compound for organic optoelectronic devices according to one embodiment is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

R ¹ and R ² are each independently hydrogen, deuterium, cyano, nitro, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocycle Group, or a combination thereof,

ET represents a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinolinyl group Substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl groups, substituted or unsubstituted benzothieno [2,3-d] pyrimidinyl groups, substituted or unsubstituted benzofuro [3,2-d] pyrimidinyl group, or a substituted or unsubstituted benzofura [2,3-d] pyrimidinyl group,

Means that at least one hydrogen is substituted with deuterium, a C1 to C10 alkyl group, a C6 to C20 aryl group, or a C2 to C20 heteroaryl group. In the present invention, the "substitution" means that at least one hydrogen is substituted with a substituent selected from the group consisting of a C1 to C4 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a pyridinyl group, a pyrimidinyl group, A benzothieno [3,2-d] pyrimidinyl group, a benzothieno [2,3-d] pyrimidinyl group, an isoquinolinyl group, a quinazolyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, ] Pyrimidinyl group, a benzofura [3,2-d] pyrimidinyl group, or a benzofura [2,3-d] pyrimidinyl group.

In one embodiment of the present invention, the "substitution" means that at least one hydrogen is substituted with a C1 to C4 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, It means that it has been replaced by a diary.

In the present invention, the "substitution" means that at least one hydrogen is substituted with a C1 to C4 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a dibenzofuranyl group or a dibenzothiophenyl group .

The compound for organic optoelectronic devices according to the present invention contains three substituents in the A ring of triphenylene, and thus has a spherical structure, has a low deposition temperature, and has a three-dimensional structure.

In addition, it has a low deposition temperature and a high transition temperature relative to the molecular weight, so that decomposition upon deposition can be suppressed and the heat stability can be improved due to the rigid structure of the molecules.

In one embodiment of the present invention, the formula 1 is represented by any one of the following formulas 1-I, 1-II, 1-III, 1-IV and 1-V according to the specific structure of the ET group .

[Chemical Formula 1-I] [Chemical Formula 1-II] [Chemical Formula 1-III]

[Chemical Formula 1-IV] [Chemical Formula 1-V]

L, R ¹ and R ² have the same meanings as described above, and R ¹ and R ² are the same as defined in the above formula (1-I), (1 -III)

Z ¹ to Z ³ are each independently N or CR ^a ,

At least one of Z ¹ to Z ³ is N,

R ^a and R ³ to R ¹⁰ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, Or a combination thereof,

X is O or S;

In one embodiment of the present invention, L is a single bond, or a substituted or unsubstituted C6 to C20 arylene group, specifically a single bond, or a substituted or unsubstituted C6 to C18 arylene group, , A substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

In one embodiment of the present invention, R ^a and R ³ to R ¹⁰ are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C4 alkyl groups, substituted or unsubstituted C6 to C20 aryl groups, A substituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

In one embodiment of the present invention, each of R ^a and R ³ to R ¹⁰ is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group , A substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenylene group.

In one embodiment of the present invention, R ¹ and R ² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, C20 heterocyclic group. In one embodiment of the present invention, R ¹ and R ² may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, , A substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted terphenyl group.

Depending on the specific substitution positions of R ¹ and R ² , the formula 1 may be represented by one of the following formulas (1A), (1B), (1C), (1D) and (1E).

[Chemical Formula 1B] [Chemical Formula 1C] [Chemical Formula 1D] [Chemical Formula 1E]

In the above Formulas 1A, 1B, 1C, 1D and 1E, L, ET, R ¹ and R ² are as described above.

In a specific embodiment of the present invention, L is a single bond, or a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and ET is a substituted or unsubstituted pyridinyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl group, a substituted or unsubstituted benzothiene A substituted or unsubstituted benzofura [3,2-d] pyrimidinyl group, or a substituted or unsubstituted benzofura [2,3-d] pyrimidinyl .

In a more specific embodiment of the present invention, L is a single bond, or a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and ET is a substituted or unsubstituted pyrimidinyl group, Substituted or unsubstituted thiazinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl groups, substituted or unsubstituted benzofura [3,2-d] and a pyrimidinyl group, wherein R ¹ and R ² are both hydrogen, wherein R ^a, and R ³ to R ¹⁰ may be each independently hydrogen, substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group unsubstituted .

The ET can be selected, for example, from substituents listed in the following Group I.

[Group I]

In Group I above, * is a binding site with neighboring atoms.

In a specific embodiment of the present invention, the formula 1 may be represented by any one of the formulas 1-I, 1-II and 1-V, V, respectively.

In one more specific embodiment of the present invention, the compound for organic optoelectronic devices represented by Formula 1 may be selected from compounds listed in the following Group 1, but is not limited thereto.

[Group 1]

A-01A-02A-03A-04A-05

A-06A-07A-08A-09A-10

A-11 A-12 A-13 A-14 A-15

A-16 A-17 A-18 A-19 A-20

A-21 A-22 A-23 A-24 A-25

A-26 A-27 A-28 A-29 A-30

A-31 A-32 A-33 A-34 A-35

A-36 A-37 A-38 A-39 A-40

A-41A-42A-43A-44A-45

A-46 A-47 A-48 A-49 A-50

A-51 A-52 A-53 A-54 A-55

A-56A-57A-58A-59A-60

The above-mentioned compounds for organic optoelectronic devices can be applied to organic optoelectronic devices alone or in combination with other compounds for organic optoelectronic devices. When the above-mentioned compound for an organic optoelectronic device is used together with another compound for an organic optoelectronic device, it can be applied in the form of a composition.

The compound for an organic optoelectronic device may further include a dopant. The dopant may be a red, green or blue dopant, for example a green dopant.

The dopant may be a material that emits light by mixing a small amount of light, and may be a material such as a metal complex that emits light by multiple excitation that excites it to a triplet state. The dopant may be, for example, an inorganic, organic, or organic compound, and may include one or more species.

Examples of the phosphorescent dopant include Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof And the like. The phosphorescent dopant may be, for example, a compound represented by the following formula (Z), but is not limited thereto.

(Z)

L ₂ MX

In the above formula (Z), M is a metal, L and X are the same or different from each other and are ligands that complex with M.

M may be Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof, Lt; / RTI >

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

Another organic optoelectronic device according to another embodiment includes an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer may include the compound for the organic optoelectronic device described above have.

For example, the organic layer includes a light emitting layer, and the compound for the organic optoelectronic device may be included as a host of the light emitting layer, for example, a green host.

The organic layer may include at least one auxiliary layer selected from a light emitting layer and a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, an electron injecting layer and a hole blocking layer, . ≪ / RTI >

The auxiliary layer may further include an electron transporting auxiliary layer adjacent to the light emitting layer, and the electron transporting auxiliary layer may include the compound for the organic optoelectronic device.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy. Examples of the organic optoelectronic device include organic light emitting devices, organic solar cells, and organic photoconductor drums.

Here, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 and 2 are cross-sectional views illustrating an organic light emitting device according to an embodiment.

1, an organic optoelectronic device 100 according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 located between the anode 120 and the cathode 110 .

The anode 120 may be made of a conductor having a high work function to facilitate, for example, hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 110 may be made of a conductor having a low work function, for example, to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 105 includes the light emitting layer 130 including the compound for the organic optoelectronic device described above.

2 is a cross-sectional view illustrating an organic light emitting device according to another embodiment.

Referring to FIG. 2, the organic light emitting diode 200 further includes a hole-assist layer 140 in addition to the light-emitting layer 130. The hole auxiliary layer 140 can further enhance hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons. The hole-assist layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer.

1 or 2 may further include an electron injection layer, an electron transport layer, an electron transporting auxiliary layer, a hole transporting layer, a hole transporting auxiliary layer, a hole injecting layer, or a combination layer thereof have. The compound for organic optoelectronic devices of the present invention can be included in these organic layers. The organic light emitting devices 100 and 200 may be formed by forming an anode or a cathode on a substrate and then performing a dry deposition method such as evaporation, sputtering, plasma plating, and ion plating; Or a wet film formation method such as spin coating, dipping or flow coating, and then forming a cathode or anode on the organic layer.

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

Hereinafter, the starting materials and reaction materials used in Examples and Synthesis Examples were purchased from Sigma-Aldrich or TCI unless otherwise stated, or synthesized by known methods.

(Preparation of compound for organic optoelectronic device)

The compounds shown as more specific examples of the compounds of the present invention were synthesized by the following steps.

<Full Reaction Scheme>

Step 1: Synthesis of intermediate L-1

<Reaction Scheme 1>

56.8 g (200.80 mmol) of 1-bromo-3-iodobenzene was dissolved in 800 ml of tetrahydrofuran solvent. Slowly drop 21.69 ml (220.87 mmol) of ethynyltrimethylsilane in a nitrogen stream using a dropping funnel. Ethynyltrimethylsilane was added thereto, followed by stirring at room temperature for 3 hours, and the reaction was terminated. Tetrahydrofuran was condensed through a distillation column and column purification (dichloromethane 1: hexane 9) gave Intermediate L-1 (yield of 51 g 80%).

calcd. C11 H13 Br: C, 52.18; H, 5.17; Br, 31.56; Si, 11.09; Found: C, 52.38; H, 5.10; Br, 31.57; Si, 11.11;

Step 2: Preparation of intermediate L- 2 of  synthesis

<Reaction Scheme 2>

In a 1000 mL flask, 43.873 g (173.27 mmol) of Intermediate L-1 is stirred in 500 mL of methanol solvent. 24 g (173.27 mmol) of potassium carbonate was added thereto, and the mixture was stirred at room temperature for 10 minutes. The reaction product is filtered to remove potassium carbonate, 500 ml of water and ethyl acetate are added, and then water is separated by extraction. The separated organic solvent was distilled off through a distiller to obtain intermediate L-2 (yield of 30.12 g 96%).

calcd. C8H5Br: C, 53.08; H, 2.78; Br, 44.14; Found: C, 53.16; H, 2.71; Br, 44.11;

Step 3: Preparation of intermediate L- 3 of  synthesis

<Reaction Scheme 3>

In a 2000 mL flask, 47.65 g (208.21 mmol) of phenanthrenequinone and 48.12 g (210.27 mmol) of the intermediate 1,3-diphenylpropane-2-one are placed and 800 ml of methanol is added and stirred while heating. 1.28 g (56.11 mmol) of KOH was slowly added thereto, and the reaction was terminated after 30 minutes. After completion of the reaction, a solid is obtained through a filter. The solid is stirred with water and then filtered again. Methanol, and then filtered to obtain Intermediate L-3 (55 g, 63% yield).

calcd. C29H18O: C, 91.07; H, 4.74; 4.18; Found: C, 91.17; H, 4.78; 4.24;

Step 4: Intermediate L- 4 of  synthesis

<Reaction Scheme 4>

Add 50 g (130.74 mol) of L-3 and 26.043 g (143.81 mmol) of the intermediate L-2 to a 250 mL flask and add 150 mL of solvent xylene. And the mixture is heated and stirred at a temperature of 180 DEG C under a nitrogen stream. The reaction is terminated after 2 hours. After completion of the reaction, the reaction product is gradually dropped into 1000 mL of methanol to form a solid. Stirring was continued for 2 hours and filtration gave Intermediate L-4 (64 g, 91% yield).

calcd. C36H23Br: C, 80.75; H, 4.33; Br, 14.92; Found: C, 80.71; H, 4.35; Br, 14.90;

Step 5: Synthesis of intermediate L-5

<Reaction Scheme 5>

Intermediate L-4 in 1000ml flask, 41.37g (77.27mmol), Bis (pinacolato ) diboron 29.43.g the (115.90mmol), potassium acetate 22.75g (231.80mmol), Pd (dppf ) Cl 2 3.15g (3.86mmol) toluene , And the mixture was heated under reflux in a nitrogen stream for 10 hours. The resulting mixture was added to 1500 mL of methanol, and the crystallized solid was filtered. The filtrate was washed with dichloromethane and silica gel / celite. The organic solvent was removed in an appropriate amount and then recrystallized with a nucleic acid to obtain Compound L-5 (31.5 g, 70 % Yield).

calcd. C ₄₂ H ₃₅ BO ₂ : C, 86.60; H, 6.06; B, 1.86; O, 7.41; found: C, 86.57; H, 6.02; B, 1.81; O, 7.45;

The following intermediates L-6 and L-7 were also synthesized as described above.

Synthetic example  1: Synthesis of Compound A-04

<Reaction Scheme 6>

(29.62 mmol) of Intermediate L-7, 8.8 g (29.62 mmol) of 2-chloro-4-phenylbenzo [4,5] thieno [3,2-d] pyrimidine, 10.23 g (74.05 mmol) of potassium carbonate, And 1.71 g (1.48 mmol) of Pd (PPh ₃ ) ₄ (Tetrakis (triphenylphosphine) palladium (0)) were placed in 100 mL of tetrahydrofuran and 30 mL of water. The mixture was heated under reflux in a nitrogen stream for 12 hours. Compound A-04 (14.06 g, 74%) was recrystallized from methanol to remove an organic solvent, and the residue was purified by silica gel column chromatography Yield). The result of the elemental analysis of the resulting compound is as follows.

calcd. C ₄₆ H ₂₈ N ₂ S: C, 86.22; H, 4.40; N, 4.37; S, 5.00 Found: C, 86.27; H, 4.41; N, 4.35; S, 5.07

Synthetic example  2: Compound A- 24  synthesis

<Reaction Scheme 7>

Intermediate L-5 in 250mL flask 15.0g (25.72mmol), 2-chloro -4-phenylquinazoline 6.2g (25.72mmol), potassium carbonate 8.9g (64.37mmol), Pd (PPh 3) 4 (Tetrakis (triphenylphosphine) palladium ( 0) (1.49 g, 1.29 mmol) were dissolved in 100 mL of tetrahydrofuran and 30 mL of water, and the mixture was heated under reflux in a nitrogen stream for 12 hours. Compound A-24 (13.47 g, 79%) was recrystallized from methanol by removing an appropriate amount of an organic solvent, and then recrystallizing from methanol. Yield). The result of the elemental analysis of the resulting compound is as follows.

calcd. C ₅₀ H ₃₂ N ₂ : C, 90.88; H, 4.88; N, 4.24; Found: C, 90.90; H, 4.84; N, 4.27;

Synthetic example  3: Synthesis of Compound A-25

<Reaction Scheme 8>

To a 250 mL flask was added 15.0 g (25.75 mmol) of Intermediate L-5, 2 - ([1,1'-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5- 29.61mmol), potassium carbonate 8.9g (64.37mmol), Pd (PPh 3) 4 (Tetrakis (triphenylphosphine) palladium (0)) 1.49g ( tetrahydrofuran to 1.29mmol) 100mL, and then put in a given 30mL of water, a stream of nitrogen &Lt; / RTI &gt; for 12 hours. Compound A-25 (13.8 g, 70%) was recrystallized from methanol to remove an organic solvent, and the resulting residue was purified by column chromatography on silica gel Yield). The result of the elemental analysis of the resulting compound is as follows.

calcd. C ₅₇ H ₃₇ N ₃ : C, 89.62; H, 4.88; N, 5.50; Found: C, 89.60; H, 4.83; N, 5.51;

Synthetic example  4 to 7: Synthesis of compounds A-03, A-06, A-16 and A-20

A-03, A-06, A-16 and A-20 were synthesized in the same manner as in Synthesis Example 3.

Comparative Synthetic Example  1 and 2

Reference is made to the synthesis method described in KR2014-0135524. The following compounds B-07 and B-08 were synthesized.

(Comparison of simulation characteristics of the prepared compound for organic optoelectronic devices)

Using the super computer GAIA (IBM power 6), the energy levels were calculated for the following six materials together with the respective materials according to the present invention by the Gaussian 09 method, and the results are shown in Table 1 below.

Yes compound HOMO (eV) LUMO (eV) T1 (eV) S1 (eV) Invention of the present invention A-03 -5.601 -1.82 2.708 3.401 A-04 -5.546 -1.76 2.677 3.322 A-06 -5.581 -1.835 2.701 3.428 A-16 -5.619 -1.828 2.678 3.402 A-20 -5.672 -1.832 2.68 3.404 A-25 -5.595 -1.78 2.703 3.415 Comparative Example 1 B-01 -4.903 -1.245 2.581 3.217 Comparative Example 2 B-02 -5.292 -1.257 2.701 3.604 Comparative Example 3 B-03 -4.856 -1.234 2.572 3.196 Comparative Example 4 B-04 -4.921 -1.25 2.55 3.227 Comparative Example 5 B-05 -5.294 -1.408 2.591 3.444 Comparative Example 6 B-06 -4.855 -1.129 2.657 3.29

The T1 value of the compound suitable for use in the green host and the electron transport layer (A-ETL) is from 2.65 eV to 2.79 eV, the LUMO energy level is from -1.75 eV to -2.10 eV, A-04, A-06, A-16, A-20, A, and A, which are the compounds of the present invention, can be expected to be advantageous when used for the above- -25 and the comparative examples, it can be seen that T1 of the comparative example has a low T1 of 2.5 eV to 2.65 eV, and such T1 value has low efficiency in the green host. In the comparative example, the LUMO energy level becomes shallow, driving is pushed, the LUMO value is higher than the HOMO level, and the balance of holes and electrons is not expected to be balanced. As a result of such a simulation, it can be seen that the present compound has a T1 value close to 2.7 eV and a deep LUMO value close to -1.8 eV, which is a simulation value showing good electron transport characteristics, .

(Preparation of organic light emitting device 1- The light- )

Example  One

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 10 minutes, and then the substrate was transferred to a vacuum evaporator. Compound A was vacuum deposited on the ITO substrate using the prepared ITO transparent electrode as an anode to form a hole injection layer having a thickness of 700 A and Compound B was deposited on the injection layer to a thickness of 50 ANGSTROM, To form a hole transporting layer. The compound A-03 of Synthesis Example 4 was used as a host on the hole transport layer, doped with 10 wt% of dopant trops tris (2-phenylpyridine) iridium (III) [Ir (ppy) ₃ ] . Subsequently, Compound D and Liq were simultaneously vacuum-deposited on the light emitting layer at a ratio of 1: 1 to form an electron transport layer having a thickness of 300 Å. Liq 15 Å and Al 1200 Å were sequentially vacuum deposited on the electron transport layer to form a cathode, Respectively.

The organic light emitting device has a structure having five organic thin film layers. Specifically, the organic light emitting device has the following structure.

Compound A-03: Ir (ppy) ₃ = 90 wt%: 10 wt%] (400 Å) / Compound D: Liq (300 Å) ) / Liq (15 Å) / Al (1200 Å).

Compound A: N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-

Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN),

Compound C: N- (biphenyl-4-yl) -9,9-dimethyl- N- (4- (9-phenyl-9H-carbazol-

Compound D: 8- (4- (4,6-di (naphthalen-2-yl) -1,3,5-triazin- 2- yl) phenyl) quinoline

Example  2 to Example  5

The devices of Examples 2 to 5 were fabricated in the same manner as in Example 1 except that the compounds A-06, A-16, A-20 and A-25 were used instead of the compound A-03.

Comparative Example  1 to 3

The same procedure as in Example 1 was carried out except that Compound B-07 of Comparative Synthesis Example 1, B-08 and CBP of Comparative Synthesis Example 2 were used in place of Compound A-03, Respectively.

Evaluation 1: Driving voltage and luminous efficiency

The driving voltage and luminous efficiency of the organic light emitting devices according to Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated. The specific measurement method is as follows, and the results are shown in Table 2.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm ² ) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Measurement of driving voltage

The driving voltage of each device was measured at 15 mA / cm ² using a current-voltage meter (Keithley 2400).

No. The light- color
(EL color) The driving voltage (V) efficiency
(cd / A) Example 1 A-03 Green 4.09 58.7 Example 2 A-06 Green 3.87 56.6 Example 3 A-16 Green 3.98 57.9 Example 4 A-20 Green 4.12 57.2 Example 5 A-25 Green 4.03 59.4 Comparative Example 1 B-07 Green 4.21 51.3 Comparative Example 2 B-08 Green 4.32 54.2 Comparative Example 3 CBP Green 6.70 34.8

Referring to Table 2, it can be seen that the driving efficiency is increased by about 20 cd / A on the average and the drive is 40% lower than the conventional host CBP. Also, it can be seen that the driving voltage is lower by 0.2 V than the B-07 and B-08 shown in the comparative example, and the efficiency is also higher by 5 cd / A as a whole. Through the two substitutions of the phenyl, the drive can be made lower and the host more efficient.

(Production of organic light emitting device 2- Electron transporting auxiliary layer )

Example 6

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500Å was washed with distilled water ultrasonic wave. After the distilled water was cleaned, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a plasma cleaner, the substrate was cleaned using oxygen plasma for 10 minutes, and then the substrate was transferred to a vacuum deposition machine. HT13 was vacuum deposited on the ITO substrate using the prepared ITO transparent electrode as an anode to form a hole injection and transport layer having a thickness of 1400A. Then, a blue fluorescent light emitting host and dopant 9,10-di (2-naphthyl) anthracene (ADN) and BD01 were doped with 5 wt% and vacuum deposition was performed to form a 200 Å thick light emitting layer. The structures of ADN and BD01 are shown below. Thereafter, A-03 of Synthesis Example 4 was vacuum-deposited on the light-emitting layer to form an electron transporting auxiliary layer having a thickness of 50 Å. Tris (8-hydroxyquinoline) aluminum (Alq3) was vacuum deposited on the electron transporting auxiliary layer to form an electron transporting layer having a thickness of 310 Å. Liq 15 Å and Al 1200 Å were sequentially vacuum deposited on the electron transporting layer to form a cathode Thereby preparing an organic light emitting device.

The organic light emitting device has a structure having five organic thin film layers. Specifically,

The structure of ITO / HT13 (1400 Å) / EML [ADN: BD01 = 95: 5 wt%] (200 Å) / Compound A-03 (50 Å) / Alq3 (310 Å) / Liq Respectively.

Example  7 to 10

The devices of Examples 7 to 10 were fabricated in the same manner as in Example 6 except that the compounds A-06, A-16, A-20 and A-25 were used instead of the compound A-03, respectively.

Comparative Example  4 to 6

Except that the electron transporting auxiliary layer was not used (Comparative Example 4), and Compound B-07 (Comparative Example 5) and B-08 (Comparative Example 6) were used in place of Compound A-03, The devices of Comparative Examples 4 to 6 were fabricated.

Evaluation 2: Measurement of luminous efficiency and life span

The organic light-emitting devices manufactured in Examples 6 to 10 and Comparative Examples 4 to 6 were measured for current density change, luminance change and luminous efficiency according to voltage.

The specific measurement method of the luminous efficiency is the same as in (Evaluation 1), and the life measurement method is as follows. The results are shown in Table 3 below.

Life measurement

The devices of Examples 6 to 10 and Comparative Examples 4 to 6 were irradiated with an initial luminance (cd / m ² ) of 750 cd / m ² using a Polarronix lifetime measuring system for the organic light emitting device manufactured, The decrease in luminance was measured, and the point at which the luminance was reduced to 97% of the initial luminance was measured with the T97 lifetime.

device Electronic transportation
Auxiliary layer Driving
Voltage (V) Luminous efficiency
(cd / A) The color coordinates (x, y) T97 Life (h)
@ 750nit Example 6 Compound A-03 4.29 8.5 (0.133, 0.149) 180 Example 7 Compound A-06 4.18 8.1 (0.133, 0.149) 175 Example 8 Compound A-16 4.25 8.8 (0.133, 0.149) 170 Example 9 Compound A-20 4.30 9.1 (0.133, 0.149) 200 Example 10 Compound A-25 4.21 9.0 (0.133, 0.149) 180 Comparative Example 4 not used 5.01 6.8 (0.133, 0.146) 120 Comparative Example 5 Compound B-07 4.88 7.0 (0.133, 0.149) 130 Comparative Example 6 Compound B-08 4.94 7.3 (0.133, 0.149) 125

As shown in Table 3, in the case of Comparative Examples 5 and 6, although the use of the electron transporting auxiliary layer was not significantly different from the case where the electron transporting auxiliary layer was not used, in the case of the embodiment, In comparison with the case where the transporting auxiliary layer is not used, it can be confirmed that the driving voltage is pulled about 0.5V on the average when the electron transporting auxiliary layer is used, and the efficiency is increased by about 30% The data can be increased.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100, 200: Organic light emitting device
105: organic layer
110: cathode
120: anode
130: light emitting layer
140: hole assist layer

Claims (9)

A compound for an organic optoelectronic device represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
L is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹ and R ² are each independently hydrogen, deuterium, cyano, nitro, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocycle Group, or a combination thereof,
ET represents a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinolinyl group Substituted or unsubstituted benzothieno [3,2-d] pyrimidinyl groups, substituted or unsubstituted benzothieno [2,3-d] pyrimidinyl groups, substituted or unsubstituted benzofuro [3,2-d] pyrimidinyl group, or a substituted or unsubstituted benzofura [2,3-d] pyrimidinyl group,
Means that at least one hydrogen is substituted with deuterium, a C1 to C10 alkyl group, a C6 to C20 aryl group, or a C2 to C20 heteroaryl group. The method according to claim 1,
A compound for an organic optoelectronic device represented by any one of the following formulas (I-1), (I-2), (I-III)
[Chemical Formula 1-I] [Chemical Formula 1-II] [Chemical Formula 1-III]

[Chemical Formula 1-IV] [Chemical Formula 1-V]

In the above general formulas 1-I, 1-II, 1-III, 1-IV and 1-V,
L is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
Z ¹ to Z ³ are each independently N or CR ^a ,
At least one of Z ¹ to Z ³ is N,
R ¹ and R ² are each independently hydrogen, deuterium, cyano, nitro, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocycle Group, or a combination thereof,
R ³ to R ¹⁰ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, ego,
X is O or S; The method according to claim 1,
Wherein L is a single bond or a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group,
Wherein ET represents a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted benzothieno [3, Substituted or unsubstituted benzothio [2,3-d] pyrimidinyl groups, substituted or unsubstituted benzofura [3,2-d] pyrimidinyl groups, or substituted or unsubstituted benzothieno [ Lt; / RTI &gt; is a substituted benzofura [2,3-d] pyrimidinyl group. The method of claim 3,
Wherein said ET is selected from the substituents listed in the following Group &lt; RTI ID = 0.0 &gt; I: &lt; / RTI &
[Group I]

In Group I above, * is a binding site with neighboring atoms. The method according to claim 1,
A compound for an organic optoelectronic device selected from the compounds listed in the following Group 1:
[Group 1]
A-01A-02A-03A-04A-05

A-06A-07A-08A-09A-10

A-11 A-12 A-13 A-14 A-15

A-16 A-17 A-18 A-19 A-20

A-21 A-22 A-23 A-24 A-25

A-26 A-27 A-28 A-29 A-30

A-31 A-32 A-33 A-34 A-35

A-36 A-37 A-38 A-39 A-40

A-41A-42A-43A-44A-45

A-46 A-47 A-48 A-49 A-50

A-51 A-52 A-53 A-54 A-55

A-56A-57A-58A-59A-60

. Positive and negative facing each other, and
And at least one organic layer positioned between the anode and the cathode,
Wherein the organic layer comprises the compound for an organic optoelectronic device according to any one of claims 1 to 5. The method according to claim 6,
Wherein the organic layer includes a light emitting layer,
Wherein the compound for an organic optoelectronic device is included as a host of the light emitting layer. 8. The method of claim 7,
Wherein the organic layer further comprises an electron transporting auxiliary layer adjacent to the light emitting layer,
Wherein the electron transport assisting layer comprises the compound for the organic optoelectronic device. A display device comprising the organic opto-electronic device according to claim 6.

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