KR20190134142A - New organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic light emitting compound and an organic light emitting device comprising the same. When employing a compound according to the present invention as a phosphorescent host material in a light emitting layer, it is possible to realize the organic light emitting device having excellent light emission characteristics such as driving voltage, brightness, and long lifespan. The compound according to the present invention has excellent interfacial properties with an electrode due to improved solubility and heat resistance in various organic solvents.

Description

New organic electroluminescent compound and organic electroluminescent device comprising the same

The present invention relates to an organic light emitting compound which is a novel phosphorescent host compound and an organic light emitting device including the same.

An organic light emitting device is a device that emits light by dissipating electrons and holes after pairing when an electric charge is injected into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode). The device can be formed on a flexible transparent substrate such as plastic, and can be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic EL display, and also consumes power. It is relatively small and has the advantage of excellent color.

A general organic light emitting device includes a substrate, an anode, a hole injection layer that receives holes from an anode, a hole transport layer that transports holes, a light emitting layer that combines holes and electrons to emit light, an electron transport layer that receives electrons from a cathode and delivers them to the light emitting layer, And a cathode. In some cases, a light emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into an electron transporting layer or a hole transporting layer without a separate light emitting layer, and in the case of using a polymer, it generally serves as a hole transporting layer, a light emitting layer, and an electron transporting layer. The polymer can be carried out simultaneously. The organic thin film layers between the two electrodes are formed by vacuum deposition or spin coating, inkjet printing, roll coating, or the like, and a separate electron injection layer may be inserted to efficiently inject electrons from the cathode.

The most important factor for determining the luminous efficiency in the organic light emitting device is the light emitting material. Fluorescent materials are widely used as light emitting materials, but development of phosphorescent materials is one of the best ways to improve luminous efficiency theoretically up to 4 times. To date, iridium (III) complexes are widely known as phosphorescent materials, and for each RGB, materials such as (acac) Ir (btp) ₂ , Ir (ppy) _3, and Firpic are known. CBP is the most widely known phosphorescent light emitting host material to date, and highly efficient OLEDs using a hole blocking layer such as BCP and BAlq are known. In Japan, Pioneer has developed a high-performance OLED using BAlq derivatives as a host. There is a bar.

However, the organic electroluminescent device using the conventional phosphorescent material has a significantly higher current efficiency (cd / A) than the device using the fluorescent material, but when using a material such as BAlq, CBP as a host of the phosphorescent material, the fluorescent material The driving voltage is higher than the device using the device, and there is no big advantage in terms of power efficiency (lm / w), and the device is not satisfactory in terms of the lifetime of the device. Therefore, development of a more stable and high-performance host material is required. .

Accordingly, the present inventors have repeatedly studied the light emitting host material in consideration of the problems of the prior art, and as a result, an organic light emitting compound which is a novel phosphorescent host compound which can greatly improve luminous efficiency, stability and device life, and organic light emitting light using the same The present invention has been completed to provide a device.

KR 10-2016-0017055 A

An object of the present invention is to provide an organic light emitting compound which is a novel phosphorescent host compound.

In addition, the present invention provides an organic light emitting device that uses the organic light emitting compound as a phosphorescent host material and not only has excellent light emission characteristics but also enhances a driving voltage, thereby inducing an increase in power efficiency and quantum efficiency, thereby improving power consumption. There is another purpose.

The present invention relates to a novel organic light emitting compound and an organic light emitting device comprising the same, and more particularly, 2,3,3-trisubstituted with a fused carbazole skeleton and 1-substituted in the benzene ring of the carbazole moiety. The present invention relates to an organic light emitting compound having a novel structure (hereinafter referred to as a compound) in which an indolinyl moiety is bonded through a cyclic linking group, and an organic light emitting device including the same.

The present invention provides a compound represented by the following formula (1).

[Formula 1]

[In Formula 1,

R, R 'and R' 'are each independently hydrogen, deuterium, (C1-C30) alkyl or (C3-C30) cycloalkyl;

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

Ring L and Ar ₁ are each independently (C6-C30) arylene or (C3-C30) heteroarylene;

Q is NR ₃ , O, S, Se, CR ₄ R ₅ or CR ₆ R ₇ CR ₈ R ₉ , each of R ₃ to R ₉ is independently hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

Alkyl, cycloalkyl, aryl or heteroaryl of R ₁ to R ₉ and arylene or heteroarylene of ring L are each independently (C 1 -C 30) alkyl, halo (C 1 -C 30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Aryl, (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6 -C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;

Wherein said heterocycloalkyl and heteroaryl include one or more selected from B, N, O, S, P (= 0), Si and P.]

In addition, the present invention provides an organic light emitting device comprising the compound.

Compounds according to the invention have a fused carbazole backbone and a deposition or solution process in which a 1-substituted-2,3,3-trisubstituted indolinyl moiety is bonded to a benzene ring of the carbazole moiety via a cyclic linker. This possible new structured compound, which is included in the light emitting layer of the organic light emitting device as a phosphorescent host material, has better luminous efficiency, global efficiency, quantum efficiency and device life than conventional materials, and exhibits appropriate color coordinates.

In addition, the compound according to the present invention is excellent in the interfacial properties with the electrode due to the improved solubility and heat resistance to various organic solvents, it is possible to the solution process when manufacturing the organic light emitting device.

In addition, the compound according to the present invention has a high electron transfer efficiency to prevent crystallization during device fabrication, and also to form a good layer to improve the current characteristics of the device to enhance the driving voltage, leading to an increase in power efficiency, power consumption This improved organic light emitting device has an advantage that can be manufactured.

1 is a graph showing efficiency (E; cd / A) vs. luminance (cd / m 2) of organic light emitting diodes manufactured in Examples 3 to 4 and Comparative Example 1. FIG.
2 is a graph showing power efficiency (PE; lm / W) vs. brightness (cd / m 2) of the organic light emitting diodes manufactured in Examples 3 to 4 and Comparative Example 1. FIG.
3 is a graph showing quantum efficiency (QE;%) vs. luminance (cd / m 2) of the organic light emitting diodes manufactured in Examples 3 to 4 and Comparative Example 1. FIG.

A novel phosphorescent host compound and an organic light emitting device using the same according to the present invention will be described in detail below. However, unless otherwise defined in the technical and scientific terms used herein, a person having ordinary knowledge in the technical field to which the present invention belongs will typically In the following description, descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.

The term "alkyl", "alkoxy" and other substituents comprising the "alkyl" moiety herein includes both straight and pulverized forms. In addition, the substituent including the alkyl, alkoxy and other alkyl moieties according to the present invention is a substituent having a short chain of 1 to 7 carbon atoms, but a substituent of 8 or more long chain is also an aspect of the present invention.

In addition, the term “aryl” as used herein refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, each ring having a single or suitably 4 to 7, preferably 5 or 6 ring atoms, or It includes a fused ring system, and includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like. However, it is not limited to this.

In addition, the term “arylene” herein means a divalent organic radical derived by one hydrogen removal from the aryl, and follows the definition of aryl.

In addition, the term “heteroaryl” as used herein includes 1 to 4 heteroatoms selected from B, N, O, S. P (═O), Si, and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeletons. Means an aryl group in which the atom is carbon, and includes 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like. Monocyclic heteroaryl; Benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolinyl, indolyl, indazolyl, quinolyl, iso Polycyclic heteroaryl such as quinolyl; And the like, but are not limited thereto.

The term “heteroarylene” herein also refers to a divalent organic radical derived by one hydrogen removal from the heteroaryl and follows the definition of the heteroaryl.

In addition, the term "cycloalkyl" as used herein means a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, including when the aromatic ring is fused.

In addition, the term “heterocycloalkyl” used herein includes 1 to 4 heteroatoms selected from B, N, O, S. P (═O), Si, and P as the alicyclic ring skeleton atom, and the remaining alicyclic rings. It means the cycloalkyl group whose group ring skeleton atom is carbon, and also includes monocyclic or polycyclic cases.

In addition, the term "halogen" as used herein means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atoms.

In addition, in the present specification, the carbon number according to the substituent definition described in Formula 1 does not include the carbon number of the substituent which may be further substituted.

Compound according to an embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

[In Formula 1,

R, R 'and R' 'are each independently hydrogen, deuterium, (C1-C30) alkyl or (C3-C30) cycloalkyl;

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

) 및 Ar₁은 각각 독립적으로 (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고;Ring L (

And Ar ₁ are each independently (C6-C30) arylene or (C3-C30) heteroarylene;

Q is NR ₃ , O, S, Se, CR ₄ R ₅ or CR ₆ R ₇ CR ₈ R ₉ , each of R ₃ to R ₉ is independently hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

Alkyl, cycloalkyl, aryl or heteroaryl of R ₁ to R ₉ and arylene or heteroarylene of ring L are each independently (C 1 -C 30) alkyl, halo (C 1 -C 30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Aryl, (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6 -C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;

Wherein said heterocycloalkyl and heteroaryl include one or more selected from B, N, O, S, P (= 0), Si and P.]

The compound may have a fused carbazole skeleton and a structure in which a 1-substituted-2,3,3-trisubstituted indolinyl moiety is bonded to a benzene ring of a carbazole moiety through a cyclic linking group.

Specifically, the compound is 1,3-dihydroindeno [2,1-b] carbazole, 6,8-dihydro-5H-naphtho [2,1-b] carbazole, indolo [2, 3-b] carbazole, 7H-benzofuro [2,3-b] carbazole or 1-substituted to the benzene ring of the carbazole moiety of the 7H-benzothieno [2,3-b] carbazole skeleton The 2,3,3-trisubstituted indolinyl moiety may be one having a structure bonded through a cyclic linker.

Thus, the compound is chemically stable and has a high electron density and high luminous efficiency. In addition, since the compound can be easily dissolved in organic solvents such as halogenated solvents and environmentally friendly halogen-free solvents, the compound can not only maintain a large light emitting area but also have excellent heat resistance and excellent interfacial properties with electrodes.

The compound according to an embodiment of the present invention may be represented by the following Chemical Formula 2 or 3 in terms of achieving excellent light emission efficiency and improved driving life.

[Formula 2]

[Formula 3]

[In Formula 2 and 3,

R, R 'and R' 'are each independently (C1-C30) alkyl or (C3-C30) cycloalkyl;

R ₁ is hydrogen, deuterium, halogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

R ₂ is (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

Ring L and Ar ₁ are each independently (C6-C30) arylene or (C3-C30) heteroarylene;

R ₃ to R ₅ are each independently hydrogen, deuterium, (C 1 -C 30) alkyl or (C 3 -C 30) cycloalkyl;

Alkyl, cycloalkyl, aryl or heteroaryl of R ₁ and R ₂ , alkyl or cycloalkyl of R ₃ to R ₅ and arylene or heteroarylene of ring L are each independently (C 1 -C 30) alkyl, Halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, nitro and hydroxy It may be further substituted with one or more selected from the group consisting of

The compound according to an embodiment of the present invention is a compound of Formula 2, wherein R, R 'and R''are each independently (C1-C30) alkyl; R ₁ is hydrogen, deuterium, halogen, (C6-C30) aryl or (C3-C30) heteroaryl; R ₂ is (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl; The aryl or heteroaryl of R ₁ and the alkyl, aryl or heteroaryl of R ₂ are each independently selected from the group consisting of (C1-C30) alkyl, (C6-C30) aryl and (C3-C30) heteroaryl May be further substituted with one or more; The ring L is (C6-C30) arylene with or without (C1-C30) alkyl or (C3-C30) heteroarylene with or without (C1-C30) alkyl; Ar ₁ is (C6-C30) arylene or (C3-C30) heteroarylene; R ₃ may be hydrogen, (C 1 -C 30) alkyl or (C 6 -C 30) aryl.

The compound according to an embodiment of the present invention is a compound of Formula 3, wherein R, R 'and R''are each independently (C1-C30) alkyl; R ₁ is hydrogen, deuterium, halogen, (C6-C30) aryl or (C3-C30) heteroaryl; R ₂ is (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl; The aryl or heteroaryl of R ₁ and the alkyl, aryl or heteroaryl of R ₂ are each independently selected from the group consisting of (C1-C30) alkyl, (C6-C30) aryl and (C3-C30) heteroaryl May be further substituted with one or more; The ring L is (C6-C30) arylene with or without (C1-C30) alkyl or (C3-C30) heteroarylene with or without (C1-C30) alkyl; Ar ₁ is (C6-C30) arylene or (C3-C30) heteroarylene; R ₄ and R ₅ may each independently be (C1-C30) alkyl or (C6-C30) aryl.

The compound is specifically 1,3-dihydroindeno [2,1-b] of Formula 3 in terms of achieving excellent chemical and electrical stability, luminous efficiency, power efficiency, quantum efficiency and improved driving life. Carbazole compounds.

The compound according to an embodiment of the present invention is a compound of Formula 3, wherein R, R 'and R''are each independently (C1-C7) alkyl; R ₁ is hydrogen, halogen, (C6-C12) aryl or (C3-C12) heteroaryl; R ₂ is (C 1 -C 7) alkyl, (C 6 -C 12) aryl or (C 3 -C 12) heteroaryl; The ring L is (C6-C12) arylene with or without (C1-C7) alkyl or (C3-C12) heteroarylene with or without (C1-C7) alkyl; R ₄ and R ₅ may be each independently (C 1 -C 7) alkyl.

For example, (C6-C12) arylene substituted with (C1-C7) alkyl of the ring L or (C3-C12) heteroarylene substituted with (C1-C7) alkyl is one (C1-C7) alkyl. May be substituted.

For example, the (C6-C12) arylene substituted with the (C1-C7) alkyl of the ring L or the (C3-C12) heteroarylene substituted with the (C1-C7) alkyl are two (C1-C7) alkyl. May be substituted.

In one embodiment, the (C6-C12) arylene substituted with the (C1-C7) alkyl of the ring L or the (C3-C12) heteroarylene substituted with the (C1-C7) alkyl is three or four (C1-C7) Alkyl may be substituted.

The compound according to an embodiment of the present invention, the compound of Formula 3, wherein R, R 'and R''are each independently methyl, ethyl or propyl; R ₁ is aryl or furyl such as hydrogen, halogen, phenyl, naphthyl, biphenyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, tria Heteroaryl, such as true, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; R ₂ is alkyl such as butyl, pentyl, hexyl, heptyl, aryl such as phenyl, naphthyl, biphenyl, or furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isozozolyl, Heteroaryls such as sazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; The ring L is phenylene with or without (C1-C7) alkyl or pyridinylene with or without (C1-C7) alkyl; Ar ₁ is arylene such as phenylene, naphthylene, biphenylene or heteroarylene such as pyridinylene and triazinylene; R ₄ and R ₅ may be independently methyl, ethyl or propyl.

The compound according to an embodiment of the present invention, the compound of Formula 3, wherein R, R 'and R''are each independently methyl, ethyl or propyl; R ₁ is hydrogen, halogen, phenyl, naphthyl or biphenyl; R ₂ is aryl such as butyl, pentyl, hexyl, heptyl, aryl such as phenyl, naphthyl, biphenyl or pyrrolyl, imidazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl; The ring L is phenylene, unsubstituted or substituted with one or more methyl, ethyl or propyl, or pyridinylene unsubstituted or substituted with one or more methyl, ethyl or propyl; Ar ₁ is phenylene or naphthylene; R ₄ and R ₅ may be independently methyl, ethyl or propyl. When Ar ₁ is arylene, it is preferable in terms of implementing better efficiency (eg, luminous efficiency, global efficiency, quantum efficiency, etc.).

The compound according to an embodiment of the present invention, the compound of Formula 3, wherein R, R 'and R''are each independently methyl, ethyl or propyl; R ₁ is hydrogen, halogen, phenyl, naphthyl or biphenyl; R ₂ is aryl such as butyl, pentyl, hexyl, heptyl, aryl such as phenyl, naphthyl, biphenyl or pyrrolyl, imidazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl; The ring L is phenylene, unsubstituted or substituted with one or more methyl, ethyl or propyl, or pyridinylene unsubstituted or substituted with one or more methyl, ethyl or propyl; Ar ₁ is pyridinylene or triazinylene; R ₄ and R ₅ may be independently methyl, ethyl or propyl. When Ar ₁ is heteroarylene, it is possible to effectively suppress the roll-off phenomenon at a high current density, thereby realizing longer lifespan by enabling excellent durability.

The compound according to an embodiment of the present invention may be used in the organic material layer of the organic light emitting device due to its structural specificity, and more specifically, may be used as the host compound in the light emitting layer in the organic material layer. Specifically, the compound may be used as a phosphorescent host compound in the light emitting layer in the organic material layer.

The compound according to an embodiment of the present invention may be more specifically exemplified by compounds having the following structure, but is not limited thereto.

The compound according to the present invention may be prepared as shown in Scheme 1, but is not limited thereto, and may be prepared through known organic reactions.

Scheme 1

[Scheme 1, wherein R, R ', R'', R ₁ , R ₂ , Q, Ar ₁ and ring L are the same as defined in Formula 1; Hal is halogen.]

In addition, the present invention provides an organic light emitting device comprising the compound of Formula 1.

An organic light emitting diode according to an embodiment of the present invention includes a first electrode; Second electrode; And one or more organic material layers interposed between the first electrode and the second electrode, wherein the organic material layer may be a single layer (light emitting layer) structure consisting of one layer or a two or more multilayer structure including a light emitting layer.

For example, when the organic material layer of the organic light emitting device has a multi-layer structure, the organic material layer including at least one selected from the light emitting layer and the hole injection layer, a hole blocking layer, a hole transport layer, an electron transport layer, an electron injection layer may be stacked. .

In the organic light emitting device according to an embodiment of the present invention, the organic material layer may include a light emitting layer containing the compound of Formula 1, the compound of Formula 1 may be included as a phosphorescent host material in the light emitting layer.

For example, when the compound of Formula 1 is included as a phosphorescent host compound in the emission layer, the emission layer may further include one or more dopant compounds.

In the organic light emitting diode according to an embodiment of the present invention, the first electrode may be an anode layer, and may be an electrode injecting holes into the hole injection layer. Therefore, the material for forming the anode layer is not limited as long as the property is imparted to the anode layer. Specific examples of the material for forming the anode layer include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like. Combinations of metals and oxides such as metal oxides, ZnO: Al or SnO2: Sb, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT) Conductive polymers such as polypyrrole and polyaniline, but are not limited thereto. In addition, the anode layer may be formed of only one type of the above materials, or may be formed of a mixture of a plurality of materials, and a multi-layer structure composed of a plurality of layers of the same composition or different compositions may be formed.

In the organic light emitting device according to an embodiment of the present invention, the organic material layer is a hole injection layer (HIL), a hole blocking layer (HBL), a hole transport layer (HTL), a light emitting layer, an electron transport layer (ETL), an electron injection layer (EIL ) May be omitted, and may be omitted as necessary.

The hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, cast, LB, and the like, and the material of the hole injection layer that may be used is CuPc ( copper phthalocyanine), NPD (N, N'-dinaphthyl-N, N'-phenyl- (1,1'-biphenyl) -4,4'-diamine), m-MTDATA (4,4 ', 4 "-tris (3-Methylphenylphenylamino) triphenylamine), 1-TNATA (4,4 ', 4' '-tris [1-naphthyl (phenyl) amino] triphenyl amine), 2-TNATA (4,4', 4 ''-tris [ Aromatic amines such as 2-naphthyl (phenyl) amino] triphenyl amine), p-DPA-TDAB (1,3,5-tris [N- (4-diphenylaminophenyl) phenylamino] benzene), and polythiophene derivatives as conductive polymers. poly (3,4-ethylenedioxythiophene) -poly (styrnesulfonate) (PEDOT: PSS) may be used, etc. In the embodiment of the present invention, PEDOT: PSS is used as the hole injection layer, and the hole injection layer is 10 to 60 nm. The thickness may be coated on the upper portion of the first electrode.

In addition, the hole transport layer (HTL) is deposited on top of the hole injection layer so as to stably supply the holes introduced through the hole injection layer to the light emitting layer. As a material for the hole transport layer that can be used, a material commonly used may be used. Specific examples thereof include NPB (N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidine ), NPD (N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -2,2′-dimethylbenzidine), TPD (N, N′-Bis (3-methylphenyl)- N, N′-diphenylbenzidine), TTB (N, N, N ', N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl) -4,4-diamine), TTP (N1, N4-diphenyl -N1, N4-dim-tolylbenzene-1,4-diamine, ETPD (N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1 '-(3 , 3'-dimethyl) biphenyl] -4,4'-diamine), VNPB (N4, N4′-di (naphthalen-1-yl) -N4, N4′-bis (4-vinylphenyl) biphenyl-4,4 ′ -diamine), ONPB (N4, N4′-bis (4- (6-((3-ethyloxetan-3-yl) methoxy) hexyl) phenyl) -N4, N4′-diphenylbiphenyl-4,4′-diamine), Low molecular hole transport such as OTPD (N4, N4′-bis (4- (6-((3-ethyloxetan-3-yl) methoxy) hexyl) phenyl) -N4, N4′-diphenylbiphenyl-4,4′-diamine) matter; And polymer hole transport materials such as poly-N-vinylcarbazole (PVK), polyaniline, and (phenylmenyl) polysilane; Etc. can be mentioned. More specifically, NPD, mCP or PVK may be used. In an embodiment of the present invention, PVK was used as the hole transport layer, and the hole transport layer may be coated with a thickness of 10 to 60 nm.

In addition, the light emitting layer may be a light emitting layer exhibiting phosphorescence, and by including the compound of Formula 1 according to the present invention, it is possible to implement an organic light emitting device having high brightness and long life characteristics. In the light emitting layer of the organic light emitting device of the present invention, the film thickness of the light emitting layer is not limited, but from the viewpoint of homogeneity of the film and prevention of unnecessary high voltage at the time of light emission and improvement of the stability of the light emission color with respect to the driving current, It can be coated with a thickness of nm to 5 μm, specifically, a thickness of 5 to 50 nm, more specifically a thickness of 10 to 40 nm.

In addition, the light emitting layer may use a phosphorescent dopant together to obtain a high luminance color with higher efficiency. At this time, the dopant compound to be used is not limited, and known dopant compounds may be selected and used as necessary. The phosphorescent dopant compound is a compound capable of emitting light from triplet excitons, and is not particularly limited as long as it emits light from triplet excitons. Specific examples thereof include Ir, Ru, Pd, Pt, Os, and Re. It may be a metal complex comprising one or more metals, more specifically porphyrin metal complex or ortho metallized metal complex.

For example, the porphyrin metal complex may be a porphyrin platinum complex.

For example, the ortho metallized metal complex may include 2-phenylpyridine derivative, 7,8-benzoquinoline derivative, 2- (2-thienyl) pyridine derivative, 2- (1-naphthyl) pyridine derivative, 2-phenylquinoline It may include derivatives and the like as a ligand. This derivative may have a substituent as needed. As an auxiliary ligand, it may further have ligands other than the above ligands such as acetylacetonato and picric acid. Specific examples include bisthienylpyridine acetylacetonate Iridium, bis (benzothienylpyridine) acetylacetonate Iridium {bis (benzothienylpyridine) acetylacetonate Iridium}, bis (2-phenylbenzothiazole) acetylacetonate Iridium {Bis (2-phenylbenzothiazole) acetylacetonate Iridium}, bis (1-phenylisoquinoline) iridium acetylacetonate {bis (1-phenylisoquinoline) Iridium acetylacetonate}, tris (1-phenylisoquinoline) iridium {tris (1-phenylisoquinoline ) Iridium}, tris (phenylpyridine) Iridium}, tris (2-biphenylpyridine) Iridium}, tris (3-biphenylpyridine) iridium {tris (3 -biphenylpyridine) Iridium}, tris (4-biphenylpyridine) Iridium} and the like, but is not limited thereto.

In addition, the amount of the dopant compound included in the emission layer is not limited, but may be included in the range of 2 to 20 parts by weight based on 100 parts by weight of the host compound (compound of Formula 1).

In addition, the content of the total dopant compound with respect to the total weight of the light emitting layer is preferably in the range of 0.5 to 35% by weight.

In this case, the hole blocking layer HBL may be formed to prevent the triplet excitons or holes from diffusing into the electron transport layer. In the case of forming the hole blocking layer by vacuum deposition and spin coating, the conditions vary depending on the compound used, but can generally be within the same condition range as the formation of the hole injection layer. Known hole blocking materials may also be used, and specific examples include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and the like. As a more specific example, the following BCP may be used as the hole blocking layer material.

The electron transport layer (ETL) is mainly composed of a material containing a chemical component that attracts electrons, which requires high electron mobility and stably supplies electrons to the light emitting layer through smooth electron transport. As the material of the electron transport layer that can be used according to the present invention, a material commonly used may be used. Preferably, TSPO1 (diphenyl-4-triphenylsilylphenylphosphine oxide), TPBI (1,3,5-tris (N-phenylbenzimiazole-) 2-yl) benzene); Alq ₃ (Tris (8-hydroxyquinolinato) aluminum); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2- (4-biphenyl) -5- (4-tert-butyl) -1,3,4-oxadizole), TAZ (3- (4-biphenyl) -4-phenyl-5- (4-tert- azole compounds such as butyl) -1,2,4-triazole), OXD-7 (1,3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene) ; phenylquinozaline; TmPyPB (3,3 '-[5'-[3- (3-Pyridinyl) phenyl] [1,1 ': 3', 1 ''-terphenyl] -3,3 ''-diyl] bispyridine) But it is not limited thereto. Preferably, TSPO1, TPBi or Alq3 may be used. In an embodiment of the present invention, TSPO1 and TPBi were used as the electron transport layer, and the electron transport layer may be stacked to a thickness of 5 to 150 nm.

In addition, the electron injection layer may be deposited with a thickness of 1 to 50 nm using LIF or Liq (lithium quinolate), but is not limited thereto.

In addition, the second electrode may be a cathode layer, and specific examples thereof include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof, LiF / A metal having a low work function may be used, such as a multi-layered material such as Al or LiO 2 / Al. More specifically, Al is preferable.

The organic light emitting device according to the present invention exhibits an efficient host-dopant energy transfer mechanism, and can express light emission characteristics of high efficiency based on an improvement in electron density distribution. In addition, it is possible to secure high-performance light emission characteristics having high efficiency and long life in each color by overcoming the initial efficiency deterioration characteristics and low life characteristics of the existing materials.

The above-described organic light emitting device according to the present invention may be applied to a display device, the display device may be a display device using a backlight unit, the organic light emitting device may be used as a light source and a single light source of the backlight unit, The display device may be an organic electroluminescent display (OLED) or the like, but is not limited thereto.

Hereinafter, the light emitting characteristics of the compound according to the present invention, a method for preparing the same, and an organic light emitting device according to the present invention will be described for a detailed understanding of the present invention, and the following examples are provided for purposes of illustration of the present invention. It is not intended to limit the scope of protection of the present invention.

Example 1 Preparation of Compound 1

Preparation of Compound 1-A

2-bromo-7,7-dimethyl-5-phenyl-5,7-dihydroindeno [2,1-b] carbazole (50 g, 114 mmol), bis ( Pinacolato) diboron (31.8 g, 125 mmol), 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1.86 g, 2.3 mmol) and potassium acetate (22.4 g, 228 mmol) was added to 1,4-dioxane (750 mL) and heated to reflux for 8 hours. When the reaction was completed, the reaction was cooled to room temperature (25 ℃), extracted with water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, the obtained solid was suspended in n-hexane, filtered and washed with n-hexane to give a white solid compound 1-A (32.8 g, yield: 65%).

¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 8.28 (s, 1H), 8.18 (s, 1H), 7.84 (d, 1H), 7.77 (s, 1H), 7.68 (d, 2H), 7.63 (m , 2H), 7.58-7.47 (m, 5H), 7.30 (m, 1H), 1.62 (s, 6H), 1.22 (s, 12H)

Compound 1- B of  Produce

In a 3000 mL three-necked bottom flask, 5-bromo-2,3,3-trimethyl-1-phenylindolin (45 g, 142.3 mmol) and 4-bromophenylboronic acid (25.7 g, 128.1 mmol) were added. Toluene (600 ml) and ethanol (300 ml) were added. Tetrakis (triphenylphosphine) palladium (0) (1.64 g, 1.4 mmol) was added, 1M aqueous potassium carbonate solution (450 ml) was added thereto, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, the mixture was extracted with water and ethyl acetate and dried over anhydrous magnesium sulfate. After concentration was separated by silica gel column (hexane: methylene chloride = 100: 1) to give a yellow solid compound 1-B (20.1 g, yield: 36%).

¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.65 (m, 4H), 7.45 (s, 1H), 7.34 (m, 3H), 7.20 (m, 2H), 7.04 (m, 2H), 3.92 (m , 1H), 1.39 (s, 3H), 1.34 (s, 3H), 1.23 (s, 3H)

compound 1 of  Produce

To a 1000 mL three-necked bottom flask was added Compound 1-B (20 g, 51 mmol) and Compound 1-A (27.2 g, 56.1 mmol) with tetrahydrofuran (400 mL). Tetrakis (triphenylphosphine) palladium (0) (0.59 g, 0.5 mmol) was added, 200 ml of a 1M potassium carbonate aqueous solution was added thereto, and the mixture was heated to reflux. After the reaction for about 12 hours, the reaction was cooled to room temperature. The mixture was extracted with water and ethyl acetate, dried over anhydrous magnesium sulfate, treated with activated carbon, filtered through Celite, and concentrated under reduced pressure. Concentrated and separated by silica gel column (hexane: methylene chloride = 1: 1) to give a white solid compound 1 (21.9 g, yield: 64%) was obtained.

¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 8.24 (s, 1H), 8.03 (d, 1H), 7.95 (s, 1H), 7.83 (s, 1H), 7.75-7.53 (m, 10H), 7.44 (m, 4H), 7.31 (m, 4H), 7.22 (m, 2H), 7.06 (m, 2H), 3.93 (m, 1H), 1.60 (d, 6H), 1.36 (d, 6H), 1.24 ( d, 3H)

MALDI-TOF MS: m / z 670.88, cal. 670.26

Example 2 Preparation of Compound 25

Preparation of Compound 25-A

2-bromo-5- (4,6-diphenyl-1,3,5-triazin-2-yl) -7,7-dimethyl-5,7-dihydro into a 2000 mL three-neck round flask Indeno [2,1-b] carbazole (40 g, 91.2 mmol), bis (pinacolato) diboron (25.5 g, 100 mmol), 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) Dichloride dichloromethane complex (1.49 g, 1.8 mmol) and potassium acetate (18 g, 182 mmol) were added to 1,4-dioxane (600 mL) and heated to reflux for 8 hours. When the reaction was completed, the reaction was cooled to room temperature, extracted with water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized under ethyl acetate and n-hexane conditions, and then filtered and washed with n-hexane to obtain an ivory-colored solid compound 25-A (28.8 g, yield: 65%).

¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 8.57 (m, 5H), 8.43 (d, 1H), 8.38 (s, 1H), 8.25 (s, 1H), 7.72 (m, 2H), 7.62 (d , 1H), 7.54-7.42 (m, 8H), 1.66 (s, 6H), 1.19 (s, 12H)

compound 25 of  Produce

To a 1000 mL three-necked bottom flask was added Compound 1-B (15 g, 38.2 mmol), Compound 25-A (26.9 g, 42.1 mmol) and tetrahydrofuran (300 mL). Tetrakis (triphenylphosphine) palladium (0) (0.44 g, 0.4 mmol) was added, 1M aqueous potassium carbonate solution (150 ml) was added and heated to reflux for 10 hours. After the reaction was completed, the reaction was cooled to room temperature. Extracted with water and ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. After concentration was separated by silica gel column (hexane: methylene chloride = 5: 1) to give a solid compound 25 (27.8 g, yield: 59%).

¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 9.12 (s, 1H), 8.51 (d, 5H), 8.46 (d, 1H), 8.25 (s, 1H), 7.77-7.66 (m, 3H), 7.62 -7.45 (m, 13H), 7.33 (m, 3H), 7.26 (m, 2H), 7.06 (d, 2H), 3.93 (m, 1H), 1.64 (d, 6H), 1.37 (d, 6H), 1.24 (d, 3 H)

MALDI-TOF MS: m / z 826.04, cal. 825.88

Example 3 Fabrication of Organic Light-Emitting Device Using Compound 1 According to the Present Invention

A 25 mm × 25 mm × 0.7 mm sized glass substrate, having an ITO (indium tin oxide) transparent electrode line having a thickness of 150 nm, was ultrasonically cleaned in distilled water containing detergent for 20 minutes, and isopropyl alcohol was Washed once for 10 minutes. After isopropyl alcohol cleaning, the substrate was again ultrasonically washed twice with 10 minutes using distilled water and dried. Subsequently, the oxygen / nitrogen plasma was treated for 2 minutes in the vacuum deposition equipment.

After plasma processing of the substrate, the substrate is vacuum-adsorbed to spin coater equipment to manufacture the device for solution process, and then PEDOT: PSS, a polythiophene derivative of conductive polymer, is used to cover the transparent electrode on the surface where the transparent electrode line is formed. Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)) was diluted with isopropyl alcohol, spin coated at 2000 rpm for 1 minute, dried on a hot plate at 130 ° C for 30 minutes to form a thin film with a thickness of 50 nm. Used as injection layer. Next, PVK (poly-N-vinylcarbazole) was diluted in toluene or chlorobenzene on the hole injection layer and spin-coated at 2000 rpm for 30 seconds, followed by baking for 30 minutes on a hotplate at 130 ° C., followed by a hole transport layer of 15 nm. Formed. Next, AYPD as a dopant on the hole transport layer was mixed with toluene or chlorobenzene at a concentration of 5 wt% in Compound 1 (Example 1) according to the present invention, which is a host compound, and spin-coated at 2000 rpm for 30 seconds. Thereafter, baking was performed for 30 minutes on a hot plate at 80 ° C to form a light emitting layer having a thickness of 30 nm.

Subsequently, TSPO1 (diphenyl-4-triphenylsilylphenylphosphine oxide) and TPBi (1,3,5-tris (N-phenylbenzimiazole-2-yl) benzene) were deposited on the light emitting layer with an electron transport layer having a thickness of 25 nm, and then Liq (lithium) was formed thereon. quinolate) was deposited to form an electron injection layer having a thickness of 1 nm. Metal aluminum was deposited on the Liq film to form a metal cathode, thereby producing an organic light emitting device.

The luminescence test was performed by applying a voltage of 0 to 15V to the organic light emitting device manufactured as described above. In addition, FIG. 1 illustrates the efficiency (cd / A) versus luminance (E; cd / m 2) of the organic light emitting device manufactured as described above, and FIG. 2 illustrates the power efficiency (PE; lm / W) versus luminance (cd / M 2), and FIG. 3 shows quantum efficiency (QE;%) versus brightness (cd / m 2).

Example 4 Fabrication of Organic Light-Emitting Device Using Compound 25 According to the Present Invention

In Example 3, Compound 25 (Example 2) was used as a host compound, and an organic light emitting device was manufactured under the same process as in Example 3.

The organic light emitting device manufactured as described above was subjected to the same light emission test as in Example 3, and shows the results of electroluminescence and basic properties in Table 1 and FIGS. 1 to 3.

Comparative Example 1 Fabrication of Organic Light-Emitting Device Using Compound CBP

An organic light-emitting device was manufactured in the same manner as in Example 3, except that Compound CBP having the following structure was used instead of Compound 1 (Example 1) as the host compound in Example 3.

The organic light emitting device manufactured as described above was also subjected to the same light emission test as in Example 3, and shows the results of electroluminescent properties and basic properties in Table 1 and FIGS. 1 to 3.

As shown in Table 1 above, the organic light emitting device including the compound according to the present invention in the light emitting layer as a light emitting host compound has excellent light emission characteristics in efficiency, power efficiency and quantum efficiency as compared to CBP, which is a conventional material. It was confirmed (FIGS. 1-3).

That is, when the compound having the characteristic structure according to the present invention is used in the light emitting layer as a light emitting host material, the driving voltage is further lowered, effectively trapping the excitons in the light emitting layer to dramatically increase the efficiency, power efficiency and quantum efficiency, high current By suppressing the roll-off phenomenon in the density it is possible to implement more excellent durability can have a long life characteristics.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Claims (9)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R, R 'and R''are each independently hydrogen, deuterium, (C1-C30) alkyl or (C3-C30) cycloalkyl;
R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;
Ring L and Ar ₁ are each independently (C6-C30) arylene or (C3-C30) heteroarylene;
Q is NR ₃ , O, S, Se, CR ₄ R ₅ or CR ₆ R ₇ CR ₈ R ₉ , each of R ₃ to R ₉ is independently hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, (C 3 -C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;
Alkyl, cycloalkyl, aryl or heteroaryl of R ₁ to R ₉ and arylene or heteroarylene of ring L are each independently (C 1 -C 30) alkyl, halo (C 1 -C 30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Aryl, (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6 -C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;
The heterocycloalkyl and heteroaryl include one or more selected from B, N, O, S, P (= 0), Si and P. The method of claim 1,
A compound represented by the following formula (2) or formula (3):
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
R, R 'and R''are each independently (C1-C30) alkyl or (C3-C30) cycloalkyl;
R ₁ is hydrogen, deuterium, halogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl;
R ₂ is (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
Ring L and Ar ₁ are each independently (C6-C30) arylene or (C3-C30) heteroarylene;
R ₃ to R ₅ are each independently hydrogen, deuterium, (C 1 -C 30) alkyl or (C 3 -C 30) cycloalkyl;
Alkyl, cycloalkyl, aryl or heteroaryl of R ₁ and R ₂ , alkyl or cycloalkyl of R ₃ to R ₅ and arylene or heteroarylene of ring L are each independently (C 1 -C 30) alkyl, Halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, nitro and hydroxy It may be further substituted with one or more selected from the group consisting of. The method of claim 2,
In Chemical Formula 2,
R, R 'and R''are each independently (C1-C30) alkyl;
R ₁ is hydrogen, deuterium, halogen, (C6-C30) aryl or (C3-C30) heteroaryl;
R ₂ is (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
The aryl or heteroaryl of R ₁ and the alkyl, aryl or heteroaryl of R ₂ are each independently selected from the group consisting of (C1-C30) alkyl, (C6-C30) aryl and (C3-C30) heteroaryl May be further substituted with one or more;
The ring L is (C6-C30) arylene with or without (C1-C30) alkyl or (C3-C30) heteroarylene with or without (C1-C30) alkyl;
Ar ₁ is (C6-C30) arylene or (C3-C30) heteroarylene;
R ₃ is hydrogen, (C 1 -C 30) alkyl or (C 6 -C 30) aryl. The method of claim 2,
In Chemical Formula 3,
R, R 'and R''are each independently (C1-C30) alkyl;
R ₁ is hydrogen, deuterium, halogen, (C6-C30) aryl or (C3-C30) heteroaryl;
R ₂ is (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
The aryl or heteroaryl of R ₁ and the alkyl, aryl or heteroaryl of R ₂ are each independently selected from the group consisting of (C1-C30) alkyl, (C6-C30) aryl and (C3-C30) heteroaryl May be further substituted with one or more;
The ring L is (C6-C30) arylene with or without (C1-C30) alkyl or (C3-C30) heteroarylene with or without (C1-C30) alkyl;
Ar ₁ is (C6-C30) arylene or (C3-C30) heteroarylene;
R ₄ and R ₅ are each independently (C 1 -C 30) alkyl or (C 6 -C 30) aryl. The method of claim 2,
In Chemical Formula 3,
R, R 'and R''are each independently (C1-C7) alkyl;
R ₁ is hydrogen, halogen, (C6-C12) aryl or (C3-C12) heteroaryl;
R ₂ is (C 1 -C 7) alkyl, (C 6 -C 12) aryl or (C 3 -C 12) heteroaryl;
The ring L is (C6-C12) arylene with or without (C1-C7) alkyl or (C3-C12) heteroarylene with or without (C1-C7) alkyl;
Ar ₁ is (C6-C12) arylene or (C3-C12) heteroarylene;
R ₄ and R ₅ are each independently (C 1 -C 7) alkyl. The method of claim 1,
A compound selected from the following structures.

An organic light emitting device comprising the compound according to any one of claims 1 to 6. The method of claim 7, wherein
The organic light emitting device,
A first electrode; Second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer containing the compound. The method of claim 8,
The compound is,
Will be included as a host of the light emitting layer, the organic light emitting device.

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