KR20190044973A - 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 can be used as a material for an organic layer in the organic electroluminescent device and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic electroluminescent device.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel cyclic compound and an organic light emitting device using the same. BACKGROUND ART < RTI ID = 0.0 >

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

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electroluminescent device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, and much research has been conducted.

The organic electroluminescent device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. In order to improve the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, .

When a voltage is applied between the two electrodes in the structure of such an organic electroluminescent device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, and excitons are formed when injected holes and electrons meet. When the exciton falls back to the ground state, it will emit light.

Development of new materials for the organic materials used in the organic electroluminescent devices has been continuously required.

Korean Patent Publication No. 10-2000-0051826 (August 16, 2000)

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

The present invention further provides an organic electroluminescent device comprising the cyclic compound.

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

[Chemical Formula 1]

In Formula 1,

L ¹ and L ² are each independently a direct bond; Heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl, C _2-30 alkynyl, C _1-30 a, a C _6-30 aryloxy A C _6-50 arylene group which is unsubstituted or substituted with a C _6-30 aryl group; Or a C _2-60 heteroarylene group which contains at least one hetero atom selected from the group consisting of N, O and S and which is unsubstituted or substituted with a C _6-30 aryl group,

X ¹ , X ² and X ³ are each independently N or C (R ^a ), 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)

[Chemical Formula 2-a]

[Formula 2-b]

[Chemical Formula 2-c]

In the formula (2-a), m is 1, 2 or 3,

Formula 1) and (2-c in the ^{Ar 1, Ar 2, Ar 3} , and Ar ⁴ are each independently a heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl C _6-50 aryl group which is unsubstituted or substituted with a C _1-6 alkyl 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 containing at least one hetero atom selected from the group consisting of N, O and S, and being substituted or unsubstituted with a C _6-30 aryl group.

Further, according to the present invention,

1. An organic electroluminescent device comprising a first electrode, a second electrode opposite to the first electrode, and at least one organic material layer provided between the first electrode and the second electrode;

And at least one layer of the organic material layer includes the compound represented by the general formula (1).

The compound represented by Formula 1 can be used as a material of an organic material layer of an organic electroluminescent device, and can improve the efficiency, the driving voltage and / or the lifetime of the organic electroluminescent device. In particular, the compound represented by Formula 1 can be used as a hole injecting, hole transporting, hole injecting and transporting, light emitting, electron transporting, or electron injecting material.

1 shows an example of an organic electroluminescent device comprising a substrate 1, a cathode 2, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic electroluminescent device comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 FIG.

Hereinafter, the compounds according to embodiments of the present invention and the organic electroluminescent device including the same will be described in detail to facilitate understanding of the present invention.

It is to be understood that the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention, unless explicitly stated herein.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

또는

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

or

The mark indicates the portion of the group that is associated with another group.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl- But are not limited to, 2- (naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl, .

In the present specification, the alkynyl group is a monovalent group in which one atom of hydrogen is removed 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

,

,

,

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a 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,

,

,

,

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a ring group containing at least one of O, N, Si, and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, an isoxazolyl group, A benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group,

In the present specification, the explanation on the aryl group described above can be applied except that arylene is a divalent group. The description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group.

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

[Chemical Formula 1]

As a result of further studies by the present inventors, it has been found that the compound represented by the above formula (1) has 10,10-dimethyl-10H-spiro [anthracene-9,9'-fluorene] as a core and one substituent at each benzene ring As the compound of the introduced type, having the above-described structural features, it can be applied to an organic electroluminescent device to improve the efficiency and life characteristics of the device.

Preferably, the compound of formula (1) may be a compound represented by the following formula (1 ') according to the bonding position:

[Formula 1 ']

In the above formula (1 '),

L ¹ , L ² , X ¹ , X ² , X ³ , Ar ¹ , Ar ² and Y are each as defined in the above formula (1).

Wherein Ar ¹ and Ar ² are each independently selected from the group consisting of deuterium, halogen, amino, nitrile, nitro, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _A C _6-50 aryl group which is unsubstituted or substituted with an aryl group of C _6-30 , an alkoxy group of _1-30 , a C _6-30 aryl group, or a C _6-30 aryl group; Or a C _2-60 heteroaryl group containing at least one hetero atom selected from the group consisting of N, O and S, and being substituted or unsubstituted with a C _6-30 aryl group.

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

Preferably, Ar < ^{1 >} and Ar < ² > may each independently be phenyl or biphenyl.

In Formula 1, L ¹ and L ² are each independently a direct bond; Heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl, C _2-30 alkynyl, C _1-30 a, a C _6-30 aryloxy A C _6-50 arylene group which is unsubstituted or substituted with a C _6-30 aryl group; Or a C _2-60 heteroarylene group containing at least one hetero atom selected from the group consisting of N, O and S and being substituted or unsubstituted with a C _6-30 aryl group.

Preferably, L ¹ and L ² are each independently a direct bond or any 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 &^lt; a ^> is hydrogen or a _C1-30 alkyl group.

For example, the group containing X ¹ , X ² and X ³ in the above formula (1) may be any one selected from the group consisting of the following formulas (3) to (3-f)

[Formula 3-a]

[Formula 3-b]

[Chemical Formula 3-c]

[Chemical formula 3-d]

[Formula 3-e]

[Chemical Formula 3-f]

In the above formulas (3-a) to (3-f)

L ^2, Ar ¹ and Ar ² are as respectively defined in the general formula (1).

In the above formula (1), Y is any one group selected from the group consisting of the following formulas (2-a) to (2-c)

[Chemical Formula 2-a]

[Formula 2-b]

[Chemical Formula 2-c]

In the formula (2-a), m is 1, 2 or 3, preferably 1 or 2.

Wherein Ar ³ and Ar ⁴ are each independently selected from the group consisting of 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 _6-50 aryl group which is unsubstituted or substituted with 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 containing at least one hetero atom selected from the group consisting of N, O and S, and being substituted or unsubstituted with a C _6-30 aryl group.

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

Preferably, Ar < ³ > and Ar < ⁴ > may each independently be phenyl or biphenyl.

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

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

[Reaction Scheme 1-1]

[Reaction Scheme 1-2]

[Reaction 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 each as defined in the above formula (1).

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.

[Reaction Scheme I-A]

[Scheme I-B]

[Scheme I-C]

[Reaction Scheme I-D]

[Reaction Scheme I-E]

[Reaction Scheme I-F]

[Reaction Scheme I-G]

[Reaction Scheme I-H]

The method for producing the above compound can be further specified in the production examples to be described later.

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

For example, according to the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode opposed to the first electrode, and at least one organic layer provided between the first electrode and the second electrode, ; And at least one layer of the organic material layer comprises the compound represented by the general formula (1).

The organic material layer of the organic electroluminescent device of the present invention may have a single-layer structure or a multi-layer 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 injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. 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.

The organic material layer may include a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, And a compound to be displayed.

In addition, the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by the general formula (1).

The organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by the formula (1).

Further, the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound represented by the above formula (1).

The organic material layer may include a light emitting layer and an electron transporting layer, and the electron transporting layer may include a compound represented by the general formula (1).

The organic electroluminescent device according to the present invention may be a normal type organic electroluminescent device in which an anode, at least one organic layer, 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, at least one organic material layer and an anode are sequentially laminated on a substrate.

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

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

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

Meanwhile, the organic electroluminescent device according to the present invention can 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 the formula (1).

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

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

At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer.

In addition to such a method, an organic electroluminescent device can be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.

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

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

In one 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 a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer.

Specific examples of the positive electrode 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); A combination of a metal and an oxide such as ZnO: Al or SNO2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability is preferable.

It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer.

Specific examples of the hole injecting material include organic materials such as metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene- Based organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable.

Specific examples of the hole transporting material include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

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

Specific examples of the light emitting material include 8-hydroxy-quinoline aluminum complex (Alq3); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound.

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

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.

Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable.

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

The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable.

Specific examples of the electron injecting layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidenemethane, And their derivatives, metal complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, 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) (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) , But is not limited thereto.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-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.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Manufacturing example  One

The 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-bottomed flask under nitrogen atmosphere and 2M potassium carbonate aqueous solution (110 ml) And tetrakis- (triphenylphosphine) palladium (0.48 g, 0.42 mmol) was added thereto, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, and the water layer was removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 150 ml of tetrahydrofuran to obtain Compound 1 (6.47 g, yield 67%).

MS [M + H] < ⁺ > = 767

Manufacturing example  2

The 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-bottomed flask under nitrogen atmosphere, and 2M potassium carbonate aqueous solution (90 ml) And tetrakis- (triphenylphosphine) palladium (0.39 g, 0.33 mmol) was added thereto, 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 from 210 ml of ethyl acetate to obtain Compound 2 (4.76 g, yield 62%).

MS [M + H] < ⁺ > = 767

Manufacturing example  3

(8.85 g, 11.19 mmol) and 4'-bromo- [1,1'-biphenyl] -4-carbonitrile (2.50 g, 9.73 mmol) were dissolved in 240 mL of tetrahydrofuran , And then 2M potassium carbonate aqueous solution (120 ml) was added thereto. Tetrakis- (triphenylphosphine) palladium (0.34 g, 0.29 mmol) was added thereto, 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 from 180 ml of tetrahydrofuran to obtain Compound 3 (6.78 g, yield 83%).

MS [M + H] < ⁺ > = 843

Manufacturing example  4

The 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-bottomed flask under nitrogen atmosphere, and 2M aqueous potassium carbonate solution (100 ml) And tetrakis- (triphenylphosphine) palladium (0.49 g, 0.42 mmol) was added thereto, 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 from ethyl acetate (180 ml) to obtain Compound 4 (5.64 g, yield 54%).

MS [M + H] < ⁺ > = 743

Manufacturing example  5

The compound A (7.06 g, 8.92 mmol) and (4-bromophenyl) dimethylphosphine oxide (1.80 g, 7.76 mmol) were dissolved in 160 ml of tetrahydrofuran in a 500 ml round-bottomed flask under nitrogen atmosphere, ml) was added, tetrakis- (triphenylphosphine) palladium (0.27 g, 0.23 mmol) was added, and the mixture was heated with 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 from 250 ml of acetone to obtain Compound 5 (4.77 g, yield 75%).

MS [M + H] < ⁺ > = 818

Manufacturing example  6

The 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-bottomed flask under nitrogen atmosphere, and 2M potassium carbonate aqueous solution And tetrakis- (triphenylphosphine) palladium (0.51 g, 0.44 mmol) was added thereto, 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, and concentrated under reduced pressure. The residue was recrystallized from ethyl acetate (250 ml) to obtain the above compound 6 (4.95 g, yield 45%).

MS [M + H] < ⁺ > = 743

Manufacturing example  7

The compound C (14.04 g, 17.77 mmol) and (4-bromophenyl) diphenylphosphine oxide (5.50 g, 15.45 mmol) were dissolved in 260 ml of tetrahydrofuran in a 500 ml round bottom flask under nitrogen atmosphere, ml), tetrakis- (triphenylphosphine) palladium (0.54 g, 0.46 mmol) was added thereto, and the mixture was heated with 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 from 360 ml of acetone to obtain Compound 7 (10.67 g, yield 73%).

MS [M + H] < ⁺ > = 942

Manufacturing example  8

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

MS [M + H] < ⁺ > = 667

Manufacturing example  9

The 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-bottomed flask under nitrogen atmosphere, and 2M potassium carbonate aqueous solution (105 ml) And tetrakis- (triphenylphosphine) palladium (0.54 g, 0.47 mmol) was added thereto, 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 from 120 ml of tetrahydrofuran to obtain Compound 9 (8.42 g, yield 76%).

MS [M + H] < ⁺ > = 716

Manufacturing example  10

The 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 under a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (100 ml) And tetrakis- (triphenylphosphine) palladium (0.54 g, 0.46 mmol) was added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, and the water layer was removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 150 ml of tetrahydrofuran to obtain Compound 10 (8.46 g, yield 71%).

MS [M + H] < ⁺ > = 767

Manufacturing example  11

The compound D (11.32 g, 15.83 mmol) and (4-bromophenyl) diphenylphosphine oxide (4.90 g, 13.76 mmol) were dissolved in 220 ml of tetrahydrofuran in a 500 ml round bottom flask under nitrogen atmosphere, ml) was added, tetrakis- (triphenylphosphine) palladium (0.48 g, 0.41 mmol) was added, and the mixture was heated with 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 from 250 ml of acetone to obtain Compound 11 (7.78 g, yield 65%).

MS [M + H] < ⁺ > = 866

Manufacturing example  12

The compound E (10.61 g, 14.86 mmol) and (4-bromophenyl) diphenylphosphine oxide (4.60 g, 12.92 mmol) were completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask under a nitrogen atmosphere, and 2M potassium carbonate aqueous solution ml), and tetrakis- (triphenylphosphine) palladium (0.45 g, 0.39 mmol) was added thereto, 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 from acetone (220 ml) to obtain Compound 12 (6.47 g, yield 48%).

MS [M + H] < ⁺ > = 865

Manufacturing example  13

The compound F (9.92 g, 13.89 mmol) and (4-bromophenyl) diphenylphosphine oxide (4.30 g, 12.08 mmol) were completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask under nitrogen atmosphere, ml), and tetrakis- (triphenylphosphine) palladium (0.48 g, 0.41 mmol) was added thereto, 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 from 250 ml of acetone to obtain Compound 13 (5.95 g, yield 57%).

MS [M + H] < ⁺ > = 865

Manufacturing example  14

The 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-bottomed flask under nitrogen atmosphere and 2M potassium carbonate aqueous solution (110 ml) And tetrakis- (triphenylphosphine) palladium (0.62 g, 0.54 mmol) was added thereto, 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 from acetone (220 ml) to obtain Compound 14 (5.95 g, yield 57%).

MS [M + H] < ⁺ > = 689

Manufacturing example  15

The 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-bottomed flask under nitrogen atmosphere, and 2M aqueous potassium carbonate solution (90 ml) And tetrakis- (triphenylphosphine) palladium (0.52 g, 0.45 mmol) was added thereto, 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 from acetone (220 ml) to obtain the compound 15 (6.47 g, yield 48%).

MS [M + H] < ⁺ > = 689

Comparative Example  1-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was washed with ultrasonic waves in distilled water containing detergent. At this time, Fischer Co. product was used as a detergent, and distilled water, which was secondly filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

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

(4,4'- (9-phenyl-9H-carbazole-3,6-diyl) bis (N, N-diphenylaniline) which is a hole transporting material, which is a hole transporting material, To form a hole transporting layer.

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

Subsequently, the following compound BH and compound BD were vacuum deposited on the electron blocking layer at a weight ratio of 25: 1 at a film thickness of 200 ANGSTROM to form a light emitting layer.

On the above-described light emitting layer, the following compound HB 1 was vacuum deposited on the hole transport layer to a thickness of 50 Å to form a hole blocking layer.

Subsequently, an electron injection and transport layer having a thickness of 310 ANGSTROM was formed by vacuum depositing the following compound ET 1 and the following compound LiQ (Lithium Quinolate) at a weight ratio of 1: 1 on the hole blocking layer.

Lithium fluoride (LiF) and aluminum of thickness 1000 Å were sequentially deposited on the electron injecting and transporting layer to a thickness of 12 Å to form a cathode.

Was the deposition rate of the organic material in the above process, maintaining the range of 0.4 to 0.7 Å / sec, the flow of lithium fluoride of the cathode was 0.3 Å / sec, the aluminum is 2 Å / sec was maintained at a deposition rate of, During the deposition, a vacuum 2X10 ^-7 torr to 5 x 10 < ^-6 > torr to produce an organic light emitting device.

Example  1-1 to 1-10

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

Test Example  One

The voltage, efficiency, color coordinates and lifetime of the organic light-emitting device fabricated in Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-4 were measured. The results are shown in Table 1 Respectively. T95 means the time required for the luminance to decrease from the initial luminance (1300 nits) 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 Examples 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 Examples 1-4 Compound 4 4.64 46.98 (0.142, 0.046) 280 Examples 1-5 Compound 6 4.45 46.60 (0.140, 0.047) 275 Examples 1-6 Compound 8 4.51 46.31 (0.139, 0.047) 265 Examples 1-7 Compound 9 4.56 46.42 (0.141, 0.046) 260 Examples 1-8 Compound 10 4.5 46.57 (0.142, 0.044) 255 Examples 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, the organic light emitting device manufactured using the compound of the present invention as a hole blocking layer exhibits excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device.

High-efficiency, and long-life characteristics than organic light-emitting devices manufactured using HB2 to HB4 having spirobifluorene, 9,10-diphenylfluorene and 9,10-dimetylfluorene cores as hole blocking layers.

The core of the present invention has a higher electron content than spirobifluorene, 9,10-diphenylfluorene and 9,10-dimetylfluorene core, and has a stronger voltage and efficiency when used as a hole blocking layer, .

As shown in Table 1, it was confirmed that the compounds according to the present invention are excellent in hole blocking ability and applicable to organic light emitting devices.

Example  2-1 to 2-15

An organic light emitting device was prepared in the same manner as in Comparative Example 1-1 except that the compound described in the following Table 2 was used in place of the compound ET 1 for the formation of the electron transporting layer in Comparative Example 1-1.

Comparative Example  2-1 to 2-3

An organic light emitting device was prepared in the same manner as in Comparative Example 1-1 except that the compound described in the following Table 2 was used in place of the compound ET 1 for the formation of the electron transporting layer in Comparative Example 1-1. In the following Table 2, the compounds ET 2, ET 3 and ET 4 are as follows.

Test Example  2

The voltage, efficiency, color coordinates and lifetime of the organic light-emitting device fabricated in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3 were measured, and the results are shown in Table 2 below. Respectively. T95 means the time required for the luminance to decrease from the initial luminance (1300 nits) 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 Examples 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 Examples 2-6 Compound 6 4.54 46.65 (0.142, 0.044) 265 Examples 2-7 Compound 7 4.59 46.82 (0.140, 0.047) 310 Examples 2-8 Compound 8 4.48 45.74 (0.141, 0.044) 275 Examples 2-9 Compound 9 4.62 46.81 (0.142, 0.044) 285 Examples 2-10 Compound 10 4.43 46.46 (0.142, 0.045) 265 Examples 2-11 Compound 11 4.55 46.55 (0.142, 0.045) 295 Examples 2-12 Compound 12 4.48 45.81 (0.140, 0.046) 320 Examples 2-13 Compound 13 4.49 46.75 (0.142, 0.045) 330 Examples 2-14 Compound 14 4.41 45.52 (0.141, 0.046) 270 Examples 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, the organic light emitting device manufactured using the compound of the present invention as an electron transport layer shows excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device.

Comparative Example 4 of Spirobifluorene Core Comparative Examples 6 and 9 of 9,10-diphenylfluorene core The characteristics of low voltage, high efficiency and long life are lower than those of the organic light emitting device prepared by using the compound of Comparative Example 5 of 10-dimetylfluorene core as an electron transport layer see.

The core of the present invention has a higher electron content than Spirobifluorene, 9,10-diphenylfluorene and 9,10-dimetylfluorene core, and has a long life span of 20% to 30% when used as an electron transport layer, Results were obtained. In particular, when phosphine oxide-substituted compounds 7, 12, and 13 were used as the electron transport layer, the lifetime was the greatest.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

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

Claims (7)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
L ¹ and L ² are each independently a direct bond; Heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, an alkoxy group of C _1-30 alkyl group, a C _2-30 alkenyl, C _2-30 alkynyl, C _1-30 a, a C _6-30 aryloxy A C _6-50 arylene group which is unsubstituted or substituted with a C _6-30 aryl group; Or a C _2-60 heteroarylene group which contains at least one hetero atom selected from the group consisting of N, O and S and which is unsubstituted or substituted with a C _6-30 aryl group,
X ¹ , X ² and X ³ are each independently N or C (R ^a ), 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)
[Chemical Formula 2-a]

[Formula 2-b]

[Chemical Formula 2-c]

In the formula (2-a), m is 1, 2 or 3,
Formula 1) and (2-c in the ^{Ar 1, Ar 2, Ar 3} , and Ar ⁴ are each independently a heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _2-30 alkenyl C _6-50 aryl group which is unsubstituted or substituted with a C _1-6 alkyl 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 containing at least one hetero atom selected from the group consisting of N, O and S, and being substituted or unsubstituted with a C _6-30 aryl group.
The method according to claim 1,
Wherein the formula 1 is represented by the following formula 1 '
compound:
[Formula 1 ']

In the above formula (1 '),
L ¹ , L ² , X ¹ , X ² , X ³ , Ar ¹ , Ar ² and Y are each as defined in the above formula (1).
The method according to claim 1,
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, di Phenylfluorenyl, dibenzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl,
compound.
The method according to claim 1,
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently phenyl or biphenyl,
compound.
The method according to claim 1,
L ¹ and L ² are each independently a direct bond or any one group selected from the group consisting of

The method according to claim 1,
The compound represented by the formula (1) is any one selected from the group consisting of
compound.

1. An organic electroluminescent device comprising a first electrode, a second electrode opposite to the first electrode, and at least one organic material layer provided between the first electrode and the second electrode;
Wherein at least one layer of the organic material layer comprises a compound represented by the general formula (1).

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