KR102145019B1 - Novel cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a novel cyclic compound and an organic electroluminescent device comprising the same. The cyclic compound may be used as a material for an organic material layer of an organic electroluminescent device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in an organic electroluminescent device.

Description

Novel cyclic compound and organic light emitting device using the same {NOVEL CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to a novel cyclic compound and an organic electroluminescent device comprising the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. The organic electroluminescent device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic electroluminescent device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electroluminescent device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. .

In the structure of such an organic electroluminescent device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when the exciton falls back to the ground state.

Development of new materials for organic materials used in organic electroluminescent devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826 (2000.08.16)

The present invention is to provide a novel cyclic compound as an organic electroluminescent compound.

In addition, the present invention is to provide an organic electroluminescent device comprising the cyclic compound.

According to the present invention, a compound represented by the following formula 1 is provided:

[Formula 1]

In Formula 1,

L ¹ and L ² are each independently a direct bond; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy A C _6-50 arylene group substituted or unsubstituted with a group or a C _6-30 aryl group; Or a C _2-60 heteroarylene group that includes any one or more heteroatoms selected from the group consisting of N, O and S and is substituted or unsubstituted with an aryl group of C _6-30 ,

X ¹ , X ² and X ³ are each independently N or C (R ^a ), wherein at least one of X ¹ , X ² and X ³ is N,

R ^a is hydrogen or a C _1-30 alkyl group,

Y is any one group selected from the group consisting of the following formulas 2-a to 2-c,

[Formula 2-a]

[Formula 2-b]

[Formula 2-c]

M in Formula 2-a is 1, 2 or 3,

In Formula 1 and Formula 2-c, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alke A C _6-50 aryl group substituted or unsubstituted with a _nil group, a C _2-30 alkynyl group, a C _1-30 alkoxy group, a C _6-30 aryloxy group, or a C _6-30 aryl group; Or a C _2-60 heteroaryl group that includes any one or more heteroatoms selected from the group consisting of N, O and S, and is substituted or unsubstituted with a C _6-30 aryl group.

Further, according to the present invention,

An organic electroluminescent device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode;

At least one of the organic material layers is provided with an organic electroluminescent device including the compound represented by Formula 1.

The compound represented by Formula 1 may be used as a material for an organic material layer of an organic electroluminescent device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in an organic electroluminescent device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

1 shows an example of an organic electroluminescent device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 is an example of an organic electroluminescent device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 Is shown.

Hereinafter, a compound according to exemplary embodiments of the present invention and an organic electroluminescent device including the same will be described in detail in order to aid understanding of the present invention.

Unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the invention.

Singular forms used in this specification also include plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of “comprising” specifies a specific characteristic, region, integer, step, action, element and/or component, and other specific characteristic, region, integer, step, action, element, component and/or group It does not exclude the existence or addition of

또는

표시는 해당 그룹이 다른 그룹과 연결되는 부분을 나타낸다.In this specification

or

The mark indicates the part where the group is connected to other groups.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the aforementioned substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples of the alkenyl group include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl -1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl- 2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, and styrenyl group, but are not limited thereto. .

In the present specification, an alkynyl group is a monovalent group in the form of removing 1 hydrogen atom from an alkyne having 2 to 30 carbon atoms or a derivative thereof.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms in the aryl group is 6 to 30. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

,

,

,

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

,

,

,

Etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a cyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. Except that the heteroarylene is a divalent group, the above description of the heterocyclic group may be applied.

Meanwhile, according to an embodiment of the present invention, a compound represented by the following formula (1) is provided.

[Formula 1]

As a result of continuous research by the present inventors, the compound represented by Formula 1 has 10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] as a core and one substituent on each benzene ring As an introduced type of compound, it is applied to an organic electroluminescent device as it has the above structural characteristics, so that it is possible to improve the efficiency and lifetime characteristics of the device.

Preferably, the compound of Formula 1 may be a compound represented by the following Formula 1'depending on the bonding position:

[Formula 1']

In Formula 1',

L ¹ , L ² , X ¹ , X ² , X ³ , Ar ¹ , Ar ² , and Y are as defined in Formula 1, respectively.

In Formula 1, Ar ¹ and Ar ² are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _{A 1-30} alkoxy group, a C _6-30 aryloxy group, or a C _6-50 aryl group unsubstituted or substituted with a C _6-30 aryl group; Or a C _2-60 heteroaryl group that includes any one or more heteroatoms selected from the group consisting of N, O and S, and is substituted or unsubstituted with a C _6-30 aryl group.

Specifically, Ar ¹ and Ar ² are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl , Dibenzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl.

Preferably, Ar ¹ and Ar ² may each independently be phenyl or biphenylyl.

In Formula 1, L ¹ and L ² are each independently a direct bond; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy group, or arylene group that is not substituted with a C _6-30 aryl substituted C _6-50; Or it may be a C _2-60 heteroarylene group that includes any one or more heteroatoms selected from the group consisting of N, O and S and is substituted or unsubstituted with a C _6-30 aryl group.

Preferably, L ¹ and L ² may each independently be a direct bond or any one group selected from the group consisting of:

.

.

In Formula 1, X ¹ , X ² and X ³ are each independently N or C (R ^a ), and at least one of X ¹ , X ² and X ³ is N. Here, R ^a is hydrogen or a C _1-30 alkyl group.

For example, the group including X ¹ , X ² and X ³ in Formula 1 may be any one selected from the groups represented by the following Formulas 3-a to 3-f:

[Formula 3-a]

[Formula 3-b]

[Formula 3-c]

[Formula 3-d]

[Formula 3-e]

[Formula 3-f]

In Formulas 3-a to 3-f,

L ² , Ar ¹ and Ar ² are as defined in Formula 1, respectively.

In Formula 1, Y is any one group selected from the group consisting of the following Formulas 2-a to 2-c:

[Formula 2-a]

[Formula 2-b]

[Formula 2-c]

In Formula 2-a, m is 1, 2 or 3, preferably 1 or 2.

Ar ³ and Ar ⁴ in Formula 2-c are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, A C _1-30 alkoxy group, a C _6-30 aryloxy group, or a C _6-50 aryl group unsubstituted or substituted with a C _6-30 aryl group; Or a C _2-60 heteroaryl group that includes any one or more heteroatoms selected from the group consisting of N, O and S, and is substituted or unsubstituted with a C _6-30 aryl group.

Specifically, Ar ³ and Ar ⁴ are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl , Dibenzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl.

Preferably, Ar ³ and Ar ⁴ may each independently be phenyl or biphenylyl.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of the following.

Meanwhile, the compound represented by Formula 1 may be prepared through the following Schemes 1-1 to 1-3.

[Reaction Scheme 1-1]

[Scheme 1-2]

[Scheme 1-3]

In the above Schemes 1-1 to 1-3,

Z ¹ and Z ² are each independently halogen,

L ¹ , L ² , X ¹ , X ² , X ³ , Ar ¹ , Ar ² , and Y are as defined in Formula 1, respectively.

As a non-limiting example, the intermediate used in the method for preparing the compound represented by Formula 1 may be prepared by the following method.

[Scheme I-A]

[Scheme I-B]

[Reaction Scheme I-C]

[Scheme I-D]

[Scheme I-E]

[Scheme I-F]

[Scheme I-G]

[Scheme I-H]

The method for preparing the compound may be more specific in Preparation Examples to be described later.

Meanwhile, according to another embodiment of the present invention, an organic electroluminescent device including the compound represented by Formula 1 is provided.

For example, according to the present invention, an organic electroluminescent device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, ; An organic electroluminescent device is provided in which at least one of the organic material layers includes the compound represented by Formula 1 of claim 1.

The organic material layer of the organic electroluminescent device of the present invention may have a single-layer structure, or may have a multilayer structure in which two or more organic material layers are stacked.

For example, the organic electroluminescent device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously transports electrons and injects electrons includes the compound represented by Formula 1 above.

In addition, the organic material layer may include an emission layer and an electron transport layer, and the electron transport layer may include a compound represented by Formula 1 above.

Further, the organic electroluminescent device according to the present invention may be a normal type organic electroluminescent device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In addition, the organic electroluminescent device according to the present invention may be an inverted type organic electroluminescent device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic electroluminescent device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic electroluminescent device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In the structure as shown in FIG. 1, the compound represented by Formula 1 may be included in the emission layer.

2 is an example of an organic electroluminescent device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 Is shown. In the structure as shown in FIG. 2, the compound represented by Formula 1 may include at least one of the hole injection layer, the hole transport layer, and the electron transport layer; Preferably it may be included in the hole transport layer.

Meanwhile, the organic electroluminescent device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1.

In addition, when the organic electroluminescent device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.

At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.

In addition to this method, an organic electroluminescent device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic electroluminescent device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic electroluminescent device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890).

For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer.

Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SNO2:Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.

Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection material is a layer that injects holes from the electrode, and the hole injection material has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated in the light emitting layer. A compound that prevents the excitons from moving to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.

It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene There are a series of organic substances, anthraquinone, and polyaniline and a polythiophene series of conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.A material capable of transporting holes to the emission layer by receiving holes from the anode or the hole injection layer as a hole transport material, and having high mobility for holes This is suitable.

Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

Specific examples of the light-emitting material 8-hydroxy-quinoline aluminum complex (Alq3); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds.

Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.

Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport material is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. The electron transport material is a material that can receive electrons from the cathode and transfer them to the emission layer, and has high mobility for electrons. This is suitable.

Specific examples of the electron transport material include 8-hydroxyquinoline Al complex; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and injects holes of excitons generated in the light emitting layer A compound that prevents migration to a layer and is excellent in thin film formation ability is preferable.

Specific examples of the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone And derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese , Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h ]Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato) (o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. , Is not limited thereto.

The organic electroluminescent device according to the present invention may be of a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the compound represented by Formula 1 may be applied to an organic solar cell or an organic transistor in addition to an organic electroluminescent device.

Hereinafter, preferred embodiments are presented to aid in understanding the invention. However, the following examples are for illustrative purposes only, and the invention is not limited thereto.

Manufacturing example One

Compound A (12.63 g, 15.97 mmol) and 4-bromobenzonitrile (2.50 g, 13.89 mmol) were completely dissolved in 220 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.48 g, 0.42 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 150 ml of tetrahydrofuran to obtain Compound 1 (6.47 g, yield 67%).

MS[M+H] ⁺ = 767

Manufacturing example 2

Compound B (10.11 g, 12.78 mmol) and 4-bromobenzonitrile (2.00 g, 11.11 mmol) were completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.39 g, 0.33 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of ethyl acetate to obtain Compound 2 (4.76 g, yield 62%).

MS[M+H] ⁺ = 767

Manufacturing example 3

Compound A (8.85 g, 11.19 mmol), 4'-bromo-[1,1'-biphenyl]-4-carbonitrile (2.50 g, 9.73 mmol) and 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.34 g, 0.29 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with tetrahydrofuran (180 ml) to obtain compound 3 (6.78 g, yield 83%).

MS[M+H] ⁺ = 843

Manufacturing example 4

Compound A (12.75 g, 16.11 mmol) and 4-bromopyridine (2.20 g, 14.01 mmol) were completely dissolved in 200 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.49 g, 0.42 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 180 ml of ethyl acetate to obtain compound 4 (5.64 g, yield 54%).

MS[M+H] ⁺ = 743

Manufacturing example 5

Compound A (7.06 g, 8.92 mmol), (4-bromophenyl) dimethylphosphine oxide (1.80 g, 7.76 mmol) was completely dissolved in 160 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (80 ml) was added, tetrakis-(triphenylphosphine)palladium (0.27 g, 0.23 mmol) was added, followed by heating and stirring for 1 hour. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of acetone to obtain compound 5 (4.77 g, yield 75%).

MS[M+H] ⁺ = 818

Manufacturing example 6

Compound C (13.31 g, 16.85 mmol) and 2-bromopyridine (2.30 g, 14.65 mmol) were completely dissolved in 140 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (70 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of ethyl acetate to obtain Compound 6 (4.95 g, yield 45%).

MS[M+H] ⁺ = 743

Manufacturing example 7

Compound C (14.04 g, 17.77 mmol), (4-bromophenyl) diphenylphosphine oxide (5.50 g, 15.45 mmol) was completely dissolved in 260 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (130 ml) was added, tetrakis-(triphenylphosphine)palladium (0.54 g, 0.46 mmol) was added, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 360 ml of acetone to obtain compound 7 (10.67 g, yield 73%).

MS[M+H] ⁺ = 942

Manufacturing example 8

Compound D (12.77 g, 17.86 mmol) and 3-bromopyridine (3.20 g, 15.53 mmol) were completely dissolved in 210 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (105 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.54 g, 0.47 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 150 ml of tetrahydrofuran to obtain compound 8 (8.42 g, yield 76%).

MS[M+H] ⁺ = 667

Manufacturing example 9

Compound D (12.77 g, 17.86 mmol) and 5-bromoisophthalonitrile (3.20 g, 15.53 mmol) were completely dissolved in 210 ml of tetrahydrofuran in a 500 ml round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (105 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.54 g, 0.47 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 120 ml of tetrahydrofuran to obtain the compound 9 (8.42 g, yield 76%).

MS[M+H] ⁺ = 716

Manufacturing example 10

Compound G (14.07 g, 17.79 mmol) and 4-bromobenzonitrile (2.80 g, 15.47 mmol) were completely dissolved in 200 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.54 g, 0.46 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 150 ml of tetrahydrofuran to obtain compound 10 (8.46 g, yield 71%).

MS[M+H] ⁺ = 767

Manufacturing example 11

Compound D (11.32 g, 15.83 mmol) and (4-bromophenyl) diphenylphosphine oxide (4.90 g, 13.76 mmol) were completely dissolved in 220 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 ml) was added, tetrakis-(triphenylphosphine)palladium (0.48 g, 0.41 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of acetone to obtain compound 11 (7.78 g, yield 65%).

MS[M+H] ⁺ = 866

Manufacturing example 12

Compound E (10.61 g, 14.86 mmol), (4-bromophenyl) diphenylphosphine oxide (4.60 g, 12.92 mmol) was completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 ml) was added, tetrakis-(triphenylphosphine)palladium (0.45 g, 0.39 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of acetone to obtain compound 12 (6.47 g, yield 48%).

MS[M+H] ⁺ = 865

Manufacturing example 13

Compound F (9.92 g, 13.89 mmol), (4-bromophenyl) diphenylphosphine oxide (4.30 g, 12.08 mmol) was completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 ml) was added, tetrakis-(triphenylphosphine)palladium (0.48 g, 0.41 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of acetone to obtain the compound 13 (5.95 g, yield 57%).

MS[M+H] ⁺ = 865

Manufacturing example 14

Compound F (14.64 g, 20.51 mmol) and 4-bromopyridine (2.80 g, 17.83 mmol) were completely dissolved in 220 ml of tetrahydrofuran in a 500 ml round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.62 g, 0.54 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of acetone to obtain the compound 14 (5.95 g, yield 57%).

MS[M+H] ⁺ = 689

Manufacturing example 15

Compound H (12.25 g, 17.15 mmol) and 4-bromobenzonitrile (4.60 g, 12.92 mmol) were completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 ml) was added. Then, tetrakis-(triphenylphosphine)palladium (0.52 g, 0.45 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of acetone to obtain Compound 15 (6.47 g, yield 48%).

MS[M+H] ⁺ = 689

Comparative example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer.

The following compound, HT 1 (4,4'-(9-phenyl-9H-carbazole-3,6-diyl)bis(N,N-diphenylaniline)), which is a material for transporting holes on the hole injection layer, is 1300 Å A hole transport layer was formed by vacuum vapor deposition.

Subsequently, the following compound EB 1 was vacuum-deposited on the hole transport layer with a film thickness of 150 Å to form an electron blocking layer.

Subsequently, a light emitting layer was formed by vacuum depositing the following compound BH and compound BD at a weight ratio of 25:1 on the electron blocking layer with a film thickness of 200 Å.

A hole blocking layer was formed by vacuum-depositing the following compound HB 1 on the light emitting layer with a film thickness of 50 Å on the hole transport layer.

Subsequently, the following compound ET 1 and the following compound LiQ (Lithium Quinolate) were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310 Å.

Lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å/sec, lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å/sec, and for aluminum 2 Å/sec, the vacuum degree during deposition was 2X10 ^-7. Maintaining torr to 5X10 ^-6 torr, an organic light emitting device was manufactured.

Example 1-1 to 1-10

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 1 below was used instead of the compound HB 1 in Comparative Example 1-1.

Comparative example 1-2 to 1-4

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 1 below was used instead of the compound HB 1 in Comparative Example 1-1. In Table 1, compounds HB 2, HB 3 and HB 4 are as follows.

Test example One

When current was applied to the organic light emitting devices prepared in Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-4, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. Indicated. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1300 nit) to 95%.

compound
(Hole Blocking Layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Compound 1 4.55 46.4 (0.140, 0.045) 265 Example 1-2 Compound 2 4.63 46.62 (0.141, 0.046) 275 Example 1-3 Compound 3 4.56 46.77 (0.142, 0.045) 285 Example 1-4 Compound 4 4.64 46.98 (0.142, 0.046) 280 Example 1-5 Compound 6 4.45 46.60 (0.140, 0.047) 275 Example 1-6 Compound 8 4.51 46.31 (0.139, 0.047) 265 Example 1-7 Compound 9 4.56 46.42 (0.141, 0.046) 260 Example 1-8 Compound 10 4.5 46.57 (0.142, 0.044) 255 Example 1-9 Compound 14 4.54 46.46 (0.141, 0.046) 270 Example 1-10 Compound 15 4.5 46.26 (0.140, 0.045) 265 Comparative Example 1-1 HB 1 5.09 44.10 (0.141, 0.046) 215 Comparative Example 1-2 HB 2 4.93 42.81 (0.141, 0.046) 205 Comparative Example 1-3 HB 3 4.81 43.43 (0.143, 0.0457 220 Comparative Example 1-4 HB 4 4.84 40.30 (0.143, 0.048) 180

As shown in Table 1, in the case of an organic light-emitting device manufactured using the compound of the present invention as a hole blocking layer, the organic light-emitting device exhibits excellent characteristics in terms of efficiency, driving voltage and/or stability.

Spirobifluorene, 9,10-diphenylfluorene and 9,10-dimetylfluorene shows the characteristics of lower voltage, higher efficiency and longer life than an organic light-emitting device manufactured using HB 2 to HB 4 having cores as a hole blocking layer.

The core of the present invention has a relatively higher electron content than the Spirobifluorene, 9,10-diphenylfluorene, and 9,10-dimetylfluorene cores, and when used as a hole blocking layer, it shows strengths in voltage and efficiency, and at the same time, the lifespan is significantly increased. .

As shown in the results of Table 1, it was confirmed that the other compounds in the present invention have excellent hole blocking ability and thus can be applied to an organic light-emitting device.

Example 2-1 to 2-15

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 2 below was used instead of the compound ET 1 to form the electron transport layer in Comparative Example 1-1.

Comparative example 2-1 to 2-3

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 2 below was used instead of the compound ET 1 to form the electron transport layer in Comparative Example 1-1. In Table 2 below, compounds ET 2, ET 3 and ET 4 are as follows.

Test example 2

When a current was applied to the organic light emitting devices prepared in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 2 below. Indicated. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1300 nit) to 95%.

compound
(Electron transport layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Comparative Example 1-1 ET 1 5.09 44.10 (0.141, 0.046) 215 Example 2-1 Compound 1 4.51 46.21 (0.140, 0.045) 265 Example 2-2 Compound 2 4.42 46.33 (0.141, 0.046) 275 Example 2-3 Compound 3 4.53 46.47 (0.142, 0.047) 285 Example 2-4 Compound 4 4.54 46.53 (0.142, 0.045) 280 Example 2-5 Compound 5 4.55 46.74 (0.140, 0.046) 275 Example 2-6 Compound 6 4.54 46.65 (0.142, 0.044) 265 Example 2-7 Compound 7 4.59 46.82 (0.140, 0.047) 310 Example 2-8 Compound 8 4.48 45.74 (0.141, 0.044) 275 Example 2-9 Compound 9 4.62 46.81 (0.142, 0.044) 285 Example 2-10 Compound 10 4.43 46.46 (0.142, 0.045) 265 Example 2-11 Compound 11 4.55 46.55 (0.142, 0.045) 295 Example 2-12 Compound 12 4.48 45.81 (0.140, 0.046) 320 Example 2-13 Compound 13 4.49 46.75 (0.142, 0.045) 330 Example 2-14 Compound 14 4.41 45.52 (0.141, 0.046) 270 Example 2-15 Compound 15 4.52 46.60 (0.142, 0.046) 265 Comparative Example 2-1 ET 2 4.85 44.81 (0.143, 0.047) 235 Comparative Example 2-2 ET 3 4.92 45.33 (0.143, 0.049) 215 Comparative Example 2-3 ET 4 4.75 45.25 (0.143, 0.048) 170

As shown in Table 2, in the case of an organic light-emitting device manufactured using the compound of the present invention as an electron transport layer, the organic light-emitting device exhibits excellent characteristics in terms of efficiency, driving voltage, and/or stability.

Compared to the organic light emitting device manufactured by using the compounds of Comparative Example 4 of Spirobifluorene Core, Comparative Example 6 of 9,10-diphenylfluorene Core and Comparative Example 5 of 9,10-dimetylfluorene core as an electron transport layer, characteristics of low voltage, high efficiency, and long life were obtained. see.

The core of the present invention has a relatively higher electron content than the Spirobifluorene, 9,10-diphenylfluorene and 9,10-dimetylfluorene cores, and when used as an electron transport layer, the lifespan is increased by 20% to 30%, showing strengths in voltage and efficiency. I got the result. In particular, when phosphine oxide-substituted compounds of 7, 12, and 13 were used as the electron transport layer, the lifespan increased the most.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer

Claims (7)

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

In Formula 1,
L ¹ and L ² are each independently a direct bond,

or

ego,
X ¹ , X ² and X ³ are each independently N or C (R ^a ), wherein at least one of X ¹ , X ² and X ³ is N,
R ^a is hydrogen,
Y is any one group selected from the group consisting of the following formulas 2-a to 2-c,
[Formula 2-a]

[Formula 2-b]

[Formula 2-c]

M in Formula 2-a is 1 or 2,
In Formula 1 and Formula 2-c, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently phenyl or biphenylyl.
The method of claim 1,
Formula 1 is represented by the following Formula 1',
compound:
[Formula 1']

In Formula 1',
L ¹ , L ² , X ¹ , X ² , X ³ , Ar ¹ , Ar ² , and Y are as defined in Formula 1, respectively.
delete delete delete The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of,
compound.

An organic electroluminescent device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode;
At least one layer of the organic material layer comprises a compound represented by Formula 1 of claim 1, wherein the organic electroluminescent device.

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