KR20190122547A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The compound represented by chemical formula 1 can be used as a material of an organic material layer of the organic light emitting device, and can improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

A, B, and C are each independently benzene or pyridine,

One of R is -X-M, the other is hydrogen,

X is O, or S,

M is an alkali metal or alkaline earth metal,

n1, n2, and n3 are each independently an integer of 0 to 3,

R ₁ and R ₂ are each independently hydrogen, deuterium; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S; Or _one of R ₁ and one of R ₂ are connected to each other to form -L-,

L is S, O, SO ₂ , P (= 0) -Ar ₁ , or N-Ar ₁ ,

Ar ₁ is substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more selected from the group consisting of substituted or unsubstituted N, O and S,

R ₃ is hydrogen, pyridinyl, or —PO (Ar ₂ ) (Ar ₃ ),

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more selected from the group consisting of substituted or unsubstituted N, O and S,

Provided that at least one of A, B, and C is pyridine; L is S, O, SO ₂ , or P (= 0) -Ar ₁ ; Or R ₃ is pyridinyl.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes an electron injection layer, and the electron injection layer is represented by Chemical Formula 1. Provided is an organic light emitting device comprising the compound.

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as an electron injection material.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
FIG. 2 shows 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, an electron injection layer 9 and a cathode 4 An example of an organic light emitting element is shown.

Hereinafter, the present invention will be described in more detail to help understand the present invention.

The present invention provides a compound represented by Chemical Formula 1.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, and the like.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched chain, carbon number 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, cyclohexylmethyl, 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 is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the carbon number 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 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, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

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 so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group 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, acridil 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, thiadia There are a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

Preferably, M is Li.

Preferably, R ₁ and R ₂ are both hydrogen; Or _one of R ₁ and one of R ₂ are connected to each other to form —L—, and all others are hydrogen.

Preferably, Ar ₁ is phenyl. In this case, one hydrogen of the phenyl may combine with R ₁ to form a single bond.

Preferably, Ar ₂ and Ar ₃ are phenyl.

Preferably, Formula 1 is represented by the following Formula 1-1, 1-2, or 1-3:

[Formula 1-1]

In Chemical Formula 1-1,

R is -X-M

X is O, or S,

M is an alkali metal or alkaline earth metal,

L is S, O, SO ₂ , or P (= 0) -Ar ₁ ,

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-2 and 1-3,

R is -X-M

X is O, or S,

M is an alkali metal or alkaline earth metal,

L is S, O, SO ₂ , P (= 0) -Ar ₁ , or N-Ar ₁ .

Preferably, Formula 1 is represented by the following Formula 1-4, or 1-5:

[Formula 1-4]

In Chemical Formula 1-4,

One of R is -X-M, the other is hydrogen,

X is O, or S,

M is an alkali metal or alkaline earth metal,

One of Y ₂ and Y ₃ is CH, the other is N,

[Formula 1-5]

In Chemical Formula 1-5,

R is -X-M,

X is O, or S,

M is an alkali metal or alkaline earth metal,

One of Y ₂ and Y ₃ is CH and the other is N.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the present invention provides a method for producing a compound represented by the formula (1), for example Reaction Scheme 1 below.

Scheme 1

In Reaction Scheme 1, except for R ′, the remaining definitions are as defined above, and R ′ is —OH or —SH.

The reaction is a reaction of reacting the compound represented by Formula 1 'with an organolithium compound. The organolithium compound that can be used in the reaction may be appropriately selected depending on the compound to be prepared, and n-butyl lithium may be used as an example. The manufacturing method may be more specific in the production examples to be described later.

The present invention also provides an organic light emitting device including the compound represented by Chemical Formula 1. In one embodiment, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes an electron injection layer, and the electron injection layer is represented by Formula 1 above. Provided is an organic light emitting device comprising the compound represented.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting 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 layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type 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 light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.

2 is composed of 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, an electron injection layer 9 and a cathode 4 An example of an organic light emitting element is shown. In such a structure, the compound represented by Formula 1 may be included in the electron injection layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except for including the compound represented by Chemical Formula 1 in the electron injection layer. In addition, when the organic light emitting 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 light emitting 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, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition to the above method, an organic light emitting 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 layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into 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), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, and has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and is produced in the light emitting layer The compound which prevents the excitons from moving to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic 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, and perylene-based Organic substances, anthraquinone and polyaniline and polythiophene-based 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 light emitting layer. The hole transport layer is a material that can transport holes from an anode or a hole injection layer to a light emitting layer. This is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; 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 containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and 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, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As an electron transporting material, a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; 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 in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or silver layer in each case.

The organic light emitting device according to the present invention may be 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 included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Preparation of the compound represented by Chemical Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

[ Example ]

Example  1: Preparation of Compound 1

Under a stream of nitrogen, spiro [fluorene-9,9'-xanthene] -4'-ol (10 g, 28.7 mmol) was placed in anhydrous THF solvent and cooled to -78 ° C. When the temperature of the solution reached -78 ℃ n-butyl lithium solution (in Hexane 2.5 M) (11.48 mL, 28.7 mmol) was slowly added dropwise. Then, it was slowly raised to room temperature and stirred for 2 hours. After completion of the reaction, the solvent was distilled to solidify and then purified by ethanol to obtain Compound 1 (6.5 g, 64% yield).

MS: [M + H] ⁺ = 355

Example  2: Preparation of Compound 2

The same method as for preparing compound 1, except that spiro [fluorene-9,9'-xanthene] -4'-thiol is used instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 2 was prepared.

MS: [M + H] ⁺ = 371

Example  3: Preparation of Compound 3

Same as the preparation method for compound 1, except that spiro [fluorene-9,9'-thioxanthene] -4'-ol was used instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 3 was prepared by the method.

MS: [M + H] ⁺ = 371

Example  4: Preparation of Compound 4

Same as the preparation method for Compound 1, except that spiro [fluorene-9,9'-thioxanthene] -4'-thiol was used instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 4 was prepared by the method.

MS: [M + H] ⁺ = 387

Example  5: Preparation of Compound 5

Except for using 4'-hydroxyspiro [fluorene-9,9'-thioxanthene] -10 ', 10'-dioxide instead of spiro [fluorene-9,9'-xanthene] -4'-ol , Compound 5 was prepared in the same manner as in the preparation of compound 1.

MS: [M + H] ⁺ = 403

Example  6: Preparation of Compound 6

2-hydroxy-5'-phenylspiro [fluorene-9,10'-phosphinolino [3,2-c] pyridine]-instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 6 was prepared in the same manner as in the preparation of compound 1, except that 5′-oxide was used.

MS: [M + H] ⁺ = 464

Example  7: Preparation of compound 7

Compound 1, except 3- (9- (pyridin-3-yl) -9H-fluorene-9-yl) phenol was used instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 7 was prepared in the same manner as in the preparation method of.

MS: [M + H] ⁺ = 342

Example  8: Preparation of Compound 8

Spiro [fluorene-9,5 '-[1,6] naphthyridino [3,2,1-jk] carbazole] -2 instead of spiro [fluorene-9,9'-xanthene] -4'-ol Compound 8 was prepared by the same method as the method for preparing compound 1, except that -ol was used.

MS: [M + H] ⁺ = 429

[ Experimental Example ]

Experimental Example  One

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 500 kPa was put in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as the detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as the distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The following compound HAT was thermally vacuum deposited to a thickness of 50 kPa on the prepared ITO transparent electrode to form a hole injection layer. The following compound NPB was vacuum deposited on the hole injection layer to a thickness of 1100 kPa to form a hole transport layer. The following compound HT-A was vacuum deposited to a thickness of 200 kPa on the hole transport layer to form an electron blocking layer. The following compound BH and the following compound BD were vacuum-deposited at a weight ratio of 25: 1 on the electron blocking layer to form a light emitting layer. The following compound ET-A and the compound 1 prepared in Example 1 were vacuum-deposited on the emission layer in a 1: 1 weight ratio to form a first electron transport layer having a thickness of 200 μs. The following compounds ET-B and Li (lithium) were vacuum deposited on the first electron transport layer at a weight ratio of 100: 1 to form a second electron transport layer at a thickness of 100 μs. Aluminum was deposited to have a thickness of 1,000 2 on the second electron transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.9 Å / sec, the lithium fluoride of the cathode was maintained at 0.3 Å / sec, and the aluminum was maintained at a deposition rate of 2 Å / sec. The organic light emitting device was manufactured by maintaining 10 ⁻⁷ to 5 × 10 ⁻⁸ torr.

Experimental Example  2 to 8

The organic light emitting device was manufactured by the same method as Experimental Example 1, but using Compound shown in Table 1 below instead of Compound 1.

Comparative Experiment  1 to 3

The organic light emitting device was manufactured by the same method as Experimental Example 1, but using Compound shown in Table 1 below instead of Compound 1. In Table 1 below, compounds Liq, CGL A and CGL B are the following compounds, respectively.

For the organic light emitting diodes manufactured in the Experimental and Comparative Experimental Examples, the driving voltage, the luminous efficiency and the color coordinate were measured at a current density of 10 mA / cm ² , and 90% of the initial luminance at a current density of 20 mA / cm ² . The time to become (T90) was measured. The results are shown in Table 1 below.

compound Voltage
(V) efficiency
(cd / A) Color coordinates
(x, y) Life (T90)
(hr) Experimental Example 1 Compound 1 4.13 6.19 (0.138, 0.112) 233 Experimental Example 2 Compound 2 4.15 6.01 (0.138, 0.110) 251 Experimental Example 3 Compound 3 4.11 6.12 (0.138, 0.111) 246 Experimental Example 4 Compound 4 4.16 6.05 (0.138, 0.112) 248 Experimental Example 5 Compound 5 4.12 6.22 (0.138, 0.112) 258 Experimental Example 6 Compound 6 4.02 6.27 (0.138, 0.111_ 242 Experimental Example 7 Compound 7 3.98 5.99 (0.138, 0.112) 244 Experimental Example 8 Compound 8 4.08 6.09 (0.138, 0.112) 250 Comparative Experimental Example 1 Liq 4.66 4.32 (0.138, 0.115) 213 Comparative Experimental Example 2 CGL A 4.72 4.48 (0.138, 0.113) 222 Comparative Experiment 3 CGL B 4.85 4.14 (0.138, 0.115) 198

As shown in Table 1, the organic light emitting device using the compound according to the present invention, it was confirmed that the driving voltage is lower than the comparative example, the luminous efficiency is high, the life is improved.

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
9: electron injection layer

Claims (8)

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

In Chemical Formula 1,
A, B, and C are each independently benzene or pyridine,
One of R is -XM, the other is hydrogen,
X is O, or S,
M is an alkali metal or alkaline earth metal,
n1, n2, and n3 are each independently an integer of 0 to 3,
R ₁ and R ₂ are each independently hydrogen, deuterium; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S; Or _one of R ₁ and one of R ₂ are connected to each other to form -L-,
L is S, O, SO ₂ , P (= 0) -Ar ₁ , or N-Ar ₁ ,
Ar ₁ is substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more selected from the group consisting of substituted or unsubstituted N, O and S,
R ₃ is hydrogen, pyridinyl, or —PO (Ar ₂ ) (Ar ₃ ),
Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more selected from the group consisting of substituted or unsubstituted N, O and S,
Provided that at least one of A, B, and C is pyridine; L is S, O, SO ₂ , or P (= 0) -Ar ₁ ; Or R ₃ is pyridinyl.
The method of claim 1,
M is Li,
compound.
The method of claim 1,
R ₁ and R ₂ are both hydrogen or
_One of R ₁ and one of R ₂ are connected to each other to form -L-, the others are hydrogen,
compound.
The method of claim 1,
Ar ₂ and Ar ₃ are phenyl,
compound.
The method of claim 1,
Formula 1 is represented by the following formula 1-1, 1-2, or 1-3,
compound:
[Formula 1-1]

In Chemical Formula 1-1,
R is -XM
X is O, or S,
M is an alkali metal or alkaline earth metal,
L is S, O, SO ₂ , or P (= 0) -Ar ₁ ,
[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-2 and 1-3,
R is -XM
X is O, or S,
M is an alkali metal or alkaline earth metal,
L is S, O, SO ₂ , P (= 0) -Ar ₁ , or N-Ar ₁ .
The method of claim 1,
Formula 1 is represented by the following formula 1-4, or 1-5,
compound:
[Formula 1-4]

In Chemical Formula 1-4,
One of R is -XM, the other is hydrogen,
X is O, or S,
M is an alkali metal or alkaline earth metal,
One of Y ₂ and Y ₃ is CH, the other is N,
[Formula 1-5]

In Chemical Formula 1-5,
R is -XM,
X is O, or S,
M is an alkali metal or alkaline earth metal,
One of Y ₂ and Y ₃ is CH and the other is N.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes an electron injection layer, and the electron injection layer is one of the first to second embodiments. An organic light-emitting device comprising the compound according to claim 7.

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