KR102145539B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel heterocyclic compound and an organic light emitting device using the same.

Description

Heterocyclic compound and organic light emitting device using the same {HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to a heterocyclic compound and an organic light emitting 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. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light-emitting 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 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 formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting 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 it falls back to the ground.

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

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

In one embodiment of the present invention, a compound represented by the following formula (1) is provided:

Compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ and R _2, C ₁ each independently represent a substituted or unsubstituted - ₆₀ alkyl; Or, a substituted or unsubstituted C ₆ - ₆₀ aryl group, or is bonded to each other to form a C _6-60 aromatic ring,

Y ₁ is hydrogen; A substituted or unsubstituted C _6-60 aryl group; Or, it is a C _2-60 heterocyclic group containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S,

Y ₂ is represented by the following formula 2 or 3,

[Formula 2]

[Chemical Formula 3]

In Formulas 2 and 3,

L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene group including at least one of O, N, Si and S,

Ar ₁ to Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl group including at least one of O, N, Si and S,

X ₁ to X ₃ are each independently N or CH, but at least one of X ₁ to X ₃ is N.

In addition, in another embodiment of the present invention, the first electrode; A second electrode provided to face the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a 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 light-emitting device, according to an embodiment of the present invention, and improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device. I can.

In particular, the compound represented by Formula 1 may be used as a material for a hole injection layer, a hole transport layer, an electron suppression layer, an electron injection layer, an electron transport layer, a hole suppression layer, or a green light emitting layer in another embodiment of the present invention. have.

1 shows an example of an organic light-emitting device including a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
FIG. 2 shows an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, and a cathode 4 It shows an example.

Advantages and features of the embodiments of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, only the present embodiments are intended to complete the disclosure of the present invention, and are common in the technical field to which the present invention pertains. It is provided to fully inform those skilled in the art of the scope of the invention, and the invention is only defined by the scope of the claims.

Hereinafter, before a detailed description of embodiments of the present invention, expressions, terms, and the like commonly used in the present specification are defined.

Hereinafter, it will be described in more detail to aid the understanding of the present invention.

및

는 각각, 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Each means a bond connected to another substituent.

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 number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

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

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 a linear or branched chain, 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 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 is preferably 3 to 60 carbon atoms, and according to an exemplary 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 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 heterocyclic group containing at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it 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 aryl group among 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 aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the above description of the heterocyclic group may be applied. In the present specification, the alkenyl group of 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 aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that the heterocycle is formed by bonding of two substituents.

Compound represented by formula 1

Hereinafter, a compound represented by the following Formula 1 provided in an embodiment of the present invention will be described in detail. However, the definition of a substituent or the like, which is not described in detail below, will be clearly understood by referring to the above contents:

[Formula 1]

In Formula 1,

R ₁ and R _2, C ₁ each independently represent a substituted or unsubstituted - ₆₀ alkyl; Or, a substituted or unsubstituted C ₆ - ₆₀ aryl group, or is bonded to each other to form a C _6-60 aromatic ring,

Y ₁ is hydrogen; A substituted or unsubstituted C _6-60 aryl group; Or, it is a C _2-60 heterocyclic group containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S,

Y ₂ is represented by the following formula 2 or 3,

[Formula 2]

[Chemical Formula 3]

In Formulas 2 and 3,

L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene group including at least one of O, N, Si and S,

Ar ₁ to Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl group including at least one of O, N, Si and S,

X ₁ to X ₃ are each independently N or CH, but at least one of X ₁ to X ₃ is N.

The compound represented by Chemical Formula 1 includes cyclopentaphenanthrene, and two different substituents (Y ₁ and Y ₂ ) are bonded to the central benzene ring.

In the unsubstituted cyclopentaphenanthrene, the benzene ring adjacent to the central benzene ring has a carbon-carbon length and thus reactivity almost the same as the generally known benzene.

However, in the unsubstituted cyclopentaphenanthrene, in the case of the central benzene ring, it is inferred that the carbon-carbon length is longer than that of commonly known benzene, and thus the reactivity is relatively large.

In this regard, when unsubstituted cyclopentaphenanthrene is applied to an organic material layer of an organic light-emitting device, its central benzene ring is attacked by radicals, other compounds, etc., and is denatured, and may cause performance degradation of the organic light-emitting device. .

On the other hand, in the compound represented by Formula 1, two different substituents (Y ₁ and Y ₂ ) are bonded to the central benzene ring having a relatively high reactivity, so that the electrochemical stability and compared to the unsubstituted cyclopentaphenanthrene and It may be that durability is improved. In particular, when the compound represented by Formula 1 is applied to an organic material layer of an organic light-emitting device, attack by radicals and other compounds may be suppressed, thereby contributing to stable driving of the device.

Specifically, in Formula 1, R ₁ and R ₂ are the same as or different from each other, and methyl; Or it may be a phenyl group.

More specifically, R ₁ and R ₂ are methyl; Alternatively, the phenyl group is the same as each other, and in the case of a phenyl group, they are independent of each other or may be bonded to each other to form a ring. Accordingly, Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The following descriptions are applied irrespective of whether Formula 1 is represented by any one of Formulas 1-1 to 1-3. In addition, each of the following descriptions is independent, and only shows specific examples of one embodiment of the present invention, and one embodiment of the present invention is not limited by each description.

In Formulas 2 and 3, Ar ₁ to Ar ₄ may be the same or different, and each independently may be any one selected from the group consisting of the following.

In Formulas 2 and 3, L ₁ is a bond; Phenyl; Biphenylyl; Terphenylyl; Quarterphenylyl; Naphthyl; Anthracenyl; Fluorenyl; Phenanthrenyl; Pyrenyl; Or it may be triphenylenyl. Specifically, the structure when L ₁ is not a bond is as follows.

In Formula 1, Y ₁ may be (1) hydrogen, or (2) any one selected from the group consisting of: This is optional and is not limited to any one.

(Wherein, L ₂ to L ₅ are each a bond; substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroaryl including at least one of O, N, Si and S And R ₃ is hydrogen; substituted or unsubstituted C _1-60 alkyl; Or, substituted or unsubstituted C _2-60 aryl group.)

For example, when Y ₁ is (1) hydrogen, the compound represented by Formula 1 may be any one selected from the group consisting of the following.

Meanwhile, when Y ₁ is not (2) hydrogen, the compound represented by Formula 1 may be any one selected from the group consisting of the following.

Hereinafter, a method of preparing the compound represented by Chemical Formula 1 will be described. However, in general, it may be prepared using other methods known in the art, and the method of preparing the compound represented by Formula 1 is not limited by the following description.

For example, the compound represented by Chemical Formula 1 may be formed by forming a basic skeleton other than Y ₂ and then introducing Y ₂ into the basic skeleton.

First, the rest of the basic skeleton except for Y ₂ may be formed according to the following Schemes 1-1 to 1-3. Reaction Schemes 1-1 to 1-3 below each form the basic skeleton of Formulas 1-1 to 1-3.

[Reaction Scheme 1-1]

[Scheme 1-2]

[Scheme 1-3]

Thereafter, in the basic skeleton formed according to Schemes 1-1 to 1-3, Y ₂ may be introduced according to Schemes 2-1 to 3-3 below. Specifically, according to the following Reaction Schemes 2-1 to 2-3, the aforementioned Formula 2 may be introduced as Y ₂ . In addition, according to the following Reaction Schemes 3-1 to 3-3, the aforementioned Formula 3 may be introduced as Y ₂ .

[Scheme 2-1]

[Reaction Scheme 2-2]

[Scheme 2-3]

[Reaction Scheme 3-1]

[Reaction Scheme 3-2]

[Reaction Scheme 3-3]

More specifically, it may be more specific in the intermediate to be described later and the preparation example using the intermediate.

Organic light-emitting device using the compound represented by Formula 1

Hereinafter, an organic light emitting device provided in another embodiment of the present invention will be described in detail. This is an organic light-emitting device including the compound represented by Formula 1 in at least one of the organic material layers, and the rest of the composition, structure, etc. except for the compound represented by Formula 1 may be the same as those generally known in the art. .

For example, 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 material 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 material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports 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 the layer that simultaneously transports electrons and injects electrons includes the compound represented by Formula 1 above.

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

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

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

2 is a diagram of an organic light-emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 3, an electron transport layer 7, and a cathode 4 It shows an example. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

The organic light-emitting 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 contains the compound represented by Chemical Formula 1. 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 PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or alloy thereof is deposited on the substrate to form an anode. 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 such a 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 material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting 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 light-emitting 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). However, the manufacturing method is not limited thereto.

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 SNO ₂ :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 layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that 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 from the light emitting layer. A compound that prevents the movement of excitons 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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 emission layer, and is a material capable of transporting holes from the anode or the hole injection layer to the emission layer as a hole transport material. This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in the visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); 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 layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer. Suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes containing 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 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 hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. 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. It is not limited to this.

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.

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

Intermediate Manufacturing example

As an intermediate for preparing compounds 1 to 39 represented by Formula 1 (Preparation Examples 1 to 39), the following compounds A-1, B-1, C-1, D-1, E-1, and F Each -1 was prepared.

Specifically, Wangsheng Liu, et al., CuBr ₂ -promoted cyclization and bromination of arene-alkynes: C-Br bond formation via reductive elimination of Cu(III) species, Org. Chem. Front. Referring to Scheme 1 and Table 1 of 2016,3,852 documents, the compounds A-1, B-1, C-1, D-1, E-1, and F-1 were prepared, respectively.

More specifically, the reaction formula of Scheme 1 (excerpt of the relevant document) is used, but MeNO ₂ is used as a solvent in Table 1 (excerpt of the relevant document), and 3 equivalents (eq) of CuBr ₂ and 0.5 equivalents Each intermediate compound was prepared by applying the conditions of Entry 15 using (eq) of K ₂ PO ₄ .

Manufacturing example 1 (Preparation of compound 1)

Compound A-1 (9.14g, 26.58mmol), 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5- in a 500 ml round bottom flask in a nitrogen atmosphere. After completely dissolving triazine (8.25g, 23.11mmol) in 280 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (140 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.80 g, 0.69 mmol) was added. Heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 240 ml of ethyl acetate to prepare the compound 1 (7.44 g, yield: 60%).

MS[M+H] ⁺ = 540

Manufacturing example 2 (Preparation of compound 2)

Compound A-1 (8.02g, 23.30mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (6.95g, 20.26mmol) in a 500ml round bottom flask in a nitrogen atmosphere and 260 mL of tetrahydrofuran After completely dissolved in 2M potassium carbonate aqueous solution (130 mL) was added, tetrakis-(triphenylphosphine)palladium (0.70 g, 0.61 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 180 ml of acetonitrile to prepare Compound 2 (6.27 g, yield: 59%).

MS[M+H] ⁺ = 526

Manufacturing example 3 (Preparation of compound 3)

질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 A-1 (6.79g, 19.74mmol), 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (5.87g, 17.16mmol)을 테트라하이드로퓨란 240 mL에 완전히 녹인 후 2M 탄산칼륨수용액(120 mL)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.59 g, 0.51 mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 필터링(filtering)하여 베이스(base)를 제거한 후에 THF을 완전히 감압농축하고 에틸아세테이트 230ml으로 재결정하여 상기 화합물 3 (5.09g, 수율: 56%)를 제조하였다.

Compound A-1 (6.79g, 19.74mmol), 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (5.87g, 17.16mmol) in a 500ml round bottom flask in a nitrogen atmosphere ) Was completely dissolved in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, tetrakis-(triphenylphosphine) palladium (0.59 g, 0.51 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 230 ml of ethyl acetate to prepare the compound 3 (5.09 g, yield: 56%).

MS[M+H] ⁺ = 525

Manufacturing example 4 (Preparation of compound 4)

Compound A-1 (5.69g, 16.55mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (5.57g, 14.39mmol) in a 500ml round-bottom flask in a nitrogen atmosphere. After completely dissolving in 300 mL of hydrofuran, 2M aqueous potassium carbonate solution (150 mL) was added, tetrakis-(triphenylphosphine) palladium (0.50 g, 0.43 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of tetrahydrofuran to prepare Compound 4 (6.17 g, yield: 81%).

MS[M+H] ⁺ = 526

Manufacturing example 5 (Preparation of compound 5)

Compound B-1 (8.37g, 17.89mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (6.02g, 15.56mmol) in a 500ml round-bottom flask in a nitrogen atmosphere. After completely dissolving in 250 mL of hydrofuran, 2M aqueous potassium carbonate solution (125 mL) was added, tetrakis-(triphenylphosphine) palladium (0.54 g, 0.47 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with tetrahydrofuran (180 ml) to prepare Compound 5 (5.36 g, yield: 53%).

MS[M+H] ⁺ = 650

Manufacturing example 6 (Preparation of compound 6)

Compound C-1 (15.45g, 33.15mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (7.64g, 28.83mmol) in a 500ml round bottom flask in a nitrogen atmosphere and 200 mL of tetrahydrofuran After completely dissolved in 2M potassium carbonate aqueous solution (100 mL) was added, tetrakis-(triphenylphosphine)palladium (1.00 g, 0.86 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 150 ml of ethyl acetate to prepare Compound 6 (7.66 g, yield: 46%).

MS[M+H] ⁺ = 570

Manufacturing example 7 (Preparation of compound 7)

Compound C-1 (8.46g, 18.16mmol), 2-chloro-4-(dibenzo[b,d]thiophen-2-yl)-6-phenyl-1,3,5- in a 500ml round bottom flask in nitrogen atmosphere. After completely dissolving triazine (5.89g, 15.79mmol) in 220 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (110 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.55 g, 0.47 mmol) was added. The mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 180 ml of ethyl acetate to prepare compound 7 (5.36 g, yield: 50%). I did.

MS[M+H] ⁺ = 678

Manufacturing example 8 (Preparation of compound 8)

Compound B-1 (5.76g, 16.75mmol), 4'-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-[1,1' in a 500 ml round bottom flask in a nitrogen atmosphere. -biphenyl]-4-carbonitrile (5.36g, 14.57mmol) was completely dissolved in 260 mL of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (130 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.50 g, 0.44 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 220 ml of ethyl acetate, and the compound 8 (8.85 g, yield) : 77%) was prepared.

MS[M+H] ⁺ = 675

Manufacturing example 9 (Preparation of compound 9)

Compound C-1 (6.30g, 13.52mmol), 3-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9-phenyl-9H- in a 500ml round bottom flask in nitrogen atmosphere After completely dissolving carbazole (5.08g, 11.76mmol) in 210 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (105 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.41 g, 0.35 mmol) was added. The mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of ethyl acetate to prepare Compound 9 (4.08 g, yield: 47%). I did.

MS[M+H] ⁺ = 737

Manufacturing example 10 (Preparation of compound 10)

Compound A-1 (9.53g, 20.44mmol), 2-(3'-bromo-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1, in a 500 ml round bottom flask in a nitrogen atmosphere 3,5-triazine (8.23g, 17.78mmol) was completely dissolved in 280 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (140 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.62 g, 0.53 mmol) ) And then heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of tetrahydrofuran to prepare Compound 10 (7.79 g, yield 73%).

MS[M+H] ⁺ = 602

Manufacturing example 11 (Preparation of compound 11)

Compound A-1 (6.49g, 18.85mmol), 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-4,6-diphenylpyrimidine (8.23g) in a 500ml round bottom flask in a nitrogen atmosphere. , 16.39mmol) was completely dissolved in 200 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (100 mL) was added, tetrakis-(triphenylphosphine) palladium (0.57 g, 0.49 mmol) was added, and then heated for 3 hours. Stirred. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of tetrahydrofuran to prepare Compound 11 (7.79 g, yield 74%).

MS[M+H] ⁺ = 641

Manufacturing example 12 (Preparation of compound 12)

Compound A-1 (7.66g, 22.28mmol), 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine (7.11g, 19.37mmol) in a 500ml round bottom flask under nitrogen atmosphere ) Was completely dissolved in 180 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (90 mL) was added, tetrakis-(triphenylphosphine) palladium (0.67 g, 0.58 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 220 ml of acetonitrile to prepare Compound 12 (6.42g, yield: 60%).

MS[M+H] ⁺ = 550

Manufacturing example 13 (Preparation of compound 13)

Compound B-1 (8.39g, 17.93mmol), 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3, in a 500ml round bottom flask in a nitrogen atmosphere After completely dissolving 5-triazine (5.97g, 15.59mmol) in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.54 g, 0.47 mmol) was added. After adding, the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 190 ml of ethyl acetate to prepare Compound 13 (5.27 g, yield: 49%).

MS[M+H] ⁺ = 690

Manufacturing example 14 (Preparation of compound 14)

Compound E-1 (11.41g, 20.98mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.97g, 15.59mmol) in a 500ml round bottom flask in a nitrogen atmosphere and 240 mL of tetrahydrofuran After completely dissolved in 2M potassium carbonate aqueous solution (120 mL) was added, tetrakis-(triphenylphosphine)palladium (0.63 g, 0.55 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 240 ml of ethyl acetate to prepare the compound 14 (8.47 g, yield: 71%).

MS[M+H] ⁺ = 650

Manufacturing example 15 (Preparation of compound 15)

Compound D-1 (7.79g, 18.55mmol), 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5- in a 500ml round bottom flask in a nitrogen atmosphere. After completely dissolving triazine (5.76g, 16.13mmol) in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.56 g, 0.48 mmol) was added. Heated and stirred for 6 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 200 ml of ethyl acetate to prepare the compound 15 (7.11 g, yield: 72%).

MS[M+H] ⁺ = 692

Manufacturing example 16 (Preparation of compound 16)

Compound F-1 (12.12g, 17.14mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.98g, 14.91mmol) in a 500ml round bottom flask in a nitrogen atmosphere and 240 mL of tetrahydrofuran After completely dissolved in 2M potassium carbonate aqueous solution (120 mL) was added, tetrakis-(triphenylphosphine) palladium (0.52 g, 0.45 mmol) was added, followed by heating and stirring for 2 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 240 ml of ethyl acetate to prepare the compound 16 (7.60 g, yield: 63%).

MS[M+H] ⁺ = 813

Manufacturing example 17 (Preparation of compound 17)

Compound E-1 (10.65g, 19.65mmol), 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (5.86g, 17.08mmol) in a 500ml round bottom flask in a nitrogen atmosphere. ) Was completely dissolved in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, tetrakis-(triphenylphosphine) palladium (0.59 g, 0.51 mmol) was added, followed by heating and stirring for 2 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of ethyl acetate to prepare the compound 17 (7.68 g, yield: 62%).

MS[M+H] ⁺ = 725

Manufacturing example 18 (Preparation of compound 18)

Compound D-1 (10.90 g, 25.95 mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5 in a 500 ml round bottom flask in a nitrogen atmosphere. -triazine (8.27g, 22.56mmol) was completely dissolved in 260 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (130 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.78 g, 0.68 mmol) was added. After heating and stirring for 4 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 250 ml of ethyl acetate to prepare the compound 18 (10.06 g, yield: 71%).

MS[M+H] ⁺ = 702

Manufacturing example 19 (Preparation of compound 19)

Compound D-1 (12.04g, 28.67mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5 in a 500 ml round bottom flask in a nitrogen atmosphere. After -triazine (8.55g, 24.93mmol) was completely dissolved in 280 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (140 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.86 g, 0.75 mmol) was added. Then, it was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 220 ml of ethyl acetate to prepare Compound 19 (10.06 g, yield: 71%).

MS[M+H] ⁺ = 678

Manufacturing example 20 (Preparation of compound 20)

Compound D-1 (7.50g, 17.86mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (6.01g, 15.53mmol) in a 500ml round-bottom flask in a nitrogen atmosphere was tetra-treated After completely dissolving in 300 mL of hydrofuran, 2M aqueous potassium carbonate solution (150 mL) was added, tetrakis-(triphenylphosphine) palladium (0.54 g, 0.47 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 230 ml of tetrahydrofuran to prepare Compound 20 (7.39 g, yield: 79%).

MS[M+H] ⁺ = 678

Manufacturing example 21 (Preparation of compound 21)

Compound D-1 (7.91g, 18.84mmol), 2-(4-chloronaphthalen-1-yl)-4,6-diphenyl-1,3,5-triazine (6.44g, 16.39) in a 500ml round bottom flask under nitrogen atmosphere mmol) was completely dissolved in 260 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (130 mL) was added, tetrakis-(triphenylphosphine) palladium (0.57 g, 0.49 mmol) was added, followed by heating and stirring for 8 hours. . After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with tetrahydrofuran (250 ml) to prepare the compound 21 (5.42 g, yield: 55%).

MS[M+H] ⁺ = 728

Manufacturing example 22 (Preparation of compound 22)

Compound E-1 (9.65g, 17.74mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (5.97g, 15.43mmol) in a 500ml round-bottom flask in a nitrogen atmosphere. After completely dissolving in 300 mL of hydrofuran, 2M aqueous potassium carbonate solution (150 mL) was added, tetrakis-(triphenylphosphine) palladium (0.53 g, 0.46 mmol) was added, followed by heating and stirring for 7 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of tetrahydrofuran to prepare Compound 22 (8.71 g, yield: 78%).

MS[M+H] ⁺ = 726

Manufacturing example 23 (Preparation of compound 23)

Compound E-1 (9.35g, 17.19mmol), 4-(3-bromophenyl)-2,6-diphenylpyrimidine (5.77g, 14.95mmol) was completely dissolved in 220 mL of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then completely dissolved in 220 mL of tetrahydrofuran. 2M aqueous potassium carbonate solution (110 mL) was added, tetrakis-(triphenylphosphine)palladium (0.52 g, 0.45 mmol) was added, followed by heating and stirring for 6 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of tetrahydrofuran to prepare Compound 23 (7.63 g, yield: 71%).

MS[M+H] ⁺ = 725

Manufacturing example 24 (Preparation of compound 24)

Compound B-1 (8.39g, 17.93mmol), 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3, in a 500ml round bottom flask in a nitrogen atmosphere After completely dissolving 5-triazine (5.97g, 15.59mmol) in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.54 g, 0.47 mmol) was added. After adding, the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 190 ml of ethyl acetate to prepare Compound 24 (5.27 g, yield: 49%).

MS[M+H] ⁺ = 690

Manufacturing example 25 (Preparation of compound 25)

Compound A-1 (7.15g, 13.88mmol), N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl in a 500ml round bottom flask in a nitrogen atmosphere. -9H-fluoren-2-amine (5.49g, 15.97mmol) was completely dissolved in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.48 g) , 0.42 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 190 ml of ethyl acetate to prepare the compound 25 (5.27 g, yield: 49%).

MS[M+H] ⁺ = 654

Manufacturing example 26 (Preparation of compound 26)

Compound C-1 (10.30g, 22.11mmol), 4-bromo-N,N-diphenylaniline (6.21g, 19.23mmol) was completely dissolved in 240 mL of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added, tetrakis-(triphenylphosphine)palladium (0.67 g, 0.58 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 210 ml of ethyl acetate to prepare the compound 26 (6.84 g, yield: 61%).

MS[M+H] ⁺ = 584

Manufacturing example 27 (Preparation of compound 27)

Compound A-1 (10.14g, 19.54mmol), N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl in a 500ml round bottom flask in a nitrogen atmosphere. -9H-fluoren-2-amine (7.73g, 22.47mmol) was completely dissolved in 240 mL of tetrahydrofuran, and 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.68 g) , 0.59 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and filtering to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 220 ml of ethyl acetate to prepare Compound 27 (6.96 g, yield: 54%).

MS[M+H] ⁺ = 658

Manufacturing example 28 (Preparation of compound 28)

Compound C-1 (10.46g, 22.45mmol), 4'-bromo-N,N-diphenyl-[1,1'-biphenyl]-4-amine (7.79g, 19.52mmol) in a 500ml round bottom flask in nitrogen atmosphere Was completely dissolved in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, tetrakis-(triphenylphosphine) palladium (0.68 g, 0.59 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 230 ml of ethyl acetate to prepare compound 28 (6.84 g, yield: 61%).

MS[M+H] ⁺ = 660

Manufacturing example 29 (Preparation of compound 29)

Compound C (8.16 g, 19.52 mmol), and compound di([1,1'-biphenyl]-4-yl)amine (7.21 g, 22.45 mmol) were completely added to 180 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere. After dissolving, NaOtBu (2.44 g, 25.38 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.10 g, 0.20 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 180 mL of ethyl acetate to prepare Preparation Example 29 (5.58 g, yield: 57%).

MS[M+H] ⁺ = 660

Manufacturing example 30 (Preparation of compound 30)

Compound B (8.29 g, 19.83 mmol), and compound N-phenyl-[1,1':4',1''-terphenyl]-4-amine (7.32 g, 22.81 mmol) in a 500 mL round bottom flask in a nitrogen atmosphere ) Was completely dissolved in 180 mL of Xylene, NaOtBu (2.48 g, 25.78 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.10 g, 0.20 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 200 mL of ethyl acetate to prepare Preparation Example 30 (6.96 g, yield: 53%).

MS[M+H] ⁺ = 662

Manufacturing example 31 (Preparation of compound 31)

Compound A (8.32 g, 28.11 mmol), and compound N-phenyl-[1,1':4',1''-terphenyl]-4-amine (14.06 g, 32.32 mmol) in a 500 mL round bottom flask in a nitrogen atmosphere ) Was completely dissolved in 180 mL of Xylene, NaOtBu (3.51 g, 36.54 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.14 g, 0.28 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature, filtering the base to remove the base, Xylene was concentrated under reduced pressure, and recrystallized with 270 mL of tetrahydrofuran to prepare Preparation Example 21 (13.27 g, yield: 72%).

MS[M+H] ⁺ = 662

Manufacturing example 32 (Preparation of compound 32)

Compound B (7.59 g, 18.07 mmol), and compound N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine in a 500 mL round bottom flask in a nitrogen atmosphere. (6.67 g, 20.78 mmol) was completely dissolved in 180 mL of Xylene, NaOtBu (2.26 g, 23.49 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.09 g, 0.18 mmol) was added, and then 3 Heated and stirred for hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare Preparation Example 22 (6.96 g, yield: 53%).

MS[M+H] ⁺ = 662

Manufacturing example 33 (Preparation of compound 33)

Compound A (8.32 g, 28.11 mmol), and compound N-phenyl-[1,1':4',1''-terphenyl]-4-amine (14.06 g, 32.32 mmol) in a 500 mL round bottom flask in a nitrogen atmosphere ) Was completely dissolved in 180 mL of Xylene, NaOtBu (3.51 g, 36.54 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.14 g, 0.28 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 270 mL of tetrahydrofuran to prepare Preparation Example 33 (13.27 g, yield: 72%).

MS[M+H] ⁺ = 614

Manufacturing example 34 (Preparation of compound 34)

Compound A-1 (5.40g, 15.70mmol), N,N-di([1,1'-biphenyl]-4-yl)-7-bromo-9,9-dimethyl- in a 500 ml round bottom flask in a nitrogen atmosphere. After completely dissolving 9H-fluoren-2-amine (8.07g, 13.65mmol) in 240 mL of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.47g, 0.41 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 230 ml of ethyl acetate to prepare the compound 34 (7.36 g, yield: 74%).

MS[M+H] ⁺ = 730

Manufacturing example 35 (Preparation of compound 35)

Compound E (8.46 g, 17.06 mmol), and compound di([1,1'-biphenyl]-4-yl)amine (5.20 g, 16.20 mmol) were completely added to 180 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere. After dissolving, NaOtBu (2.46 g, 25.58 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.10 g, 0.20 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 180 mL of ethyl acetate to prepare Preparation Example 35 (6.95 g, yield: 57%).

MS[M+H] ⁺ = 738

Manufacturing example 36 (Preparation of compound 36)

Compound E (7.52 g, 15.16 mmol), and compound N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2- in a 500 mL round bottom flask in a nitrogen atmosphere. After completely dissolving amine (5.20 g, 14.40 mmol) in 180 mL of Xylene, NaOtBu (2.46 g, 25.58 mmol) was added, and Bis (tri- tert- butylphosphine) palladium (0) (0.15 g, 0.30 mmol) was added. Heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering (filtering) to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare Preparation Example 36 (7.13 g, yield: 61%).

MS[M+H] ⁺ = 778

Manufacturing example 37 (Preparation of compound 37)

Compound D (6.94 g, 15.49 mmol), and compound di([1,1'-biphenyl]-4-yl)amine (4.72 g, 14.72 mmol) were completely added to 180 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere. After dissolving, NaOtBu (2.23 g, 23.24 mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.60 g, 0.57 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature, filtering the base to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare Preparation Example 37 (7.72 g, yield: 72%).

MS[M+H] ⁺ = 690

Manufacturing example 38 (Preparation of compound 38)

Compound F-1 (9.63g, 17.76mmol), 4-bromo-N,N-diphenylaniline (8.88g, 18.69mmol) was completely dissolved in 240 mL of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added, tetrakis-(triphenylphosphine)palladium (0.65 g, 0.56 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 260 ml of ethyl acetate to prepare the compound 38 (10.25 g, yield: 68%).

MS[M+H] ⁺ = 825

Manufacturing example 39 (Preparation of compound 39)

Compound D-1 (9.63g, 17.76mmol), N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1' in a 500 ml round bottom flask in a nitrogen atmosphere. -biphenyl]-4-amine (8.88g, 18.69mmol) was completely dissolved in 240 mL of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (120 mL) was added, and tetrakis-(triphenylphosphine)palladium (0.65 g, 0.56 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering the base to remove the base, THF was completely concentrated under reduced pressure and recrystallized with 260 ml of ethyl acetate to prepare the compound 39 (10.25 g, yield: 68%).

MS[M+H] ⁺ = 766

< Electron suppression layer Application example >

In Reference Examples 1-1 to 1-16 below, each of the compounds of Preparation Examples 24 to 39 was applied to an electron suppressing layer of an organic light-emitting device, and the effects thereof were confirmed.

Comparative example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000Å 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, a compound represented by the following formula HAT was thermally vacuum deposited to a thickness of 50Å to form a hole injection layer. A hole transport layer was formed by vacuum depositing a compound (1300Å) represented by the following formula HT1 on the hole injection layer. Subsequently, EB1 was formed on the hole transport layer with a thickness of 150Å. Then, a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200Å were vacuum-deposited at a weight ratio of 25:1 to form a light emitting layer. A hole blocking layer was formed by vacuum depositing a compound represented by the following Chemical Formula HB1 with a film thickness of 50Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ 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 310Å. Lithium fluoride (LiF) at a thickness of 12Å and aluminum at a thickness of 1,000Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ An organic light emitting device was manufactured by maintaining 5x10 ^-6 torr.

Comparative example 1-2 to 1-3

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 1 below was used instead of EB1 in forming the electron suppressing layer. The compounds of EB2 and EB3 used in Table 1 are as follows.

Reference Example 1-1 to Reference Example 1-16

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 EB1 in forming the electron suppressing layer.

Experimental example One

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

compound
(Electronic suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Comparative Example 1-1 EB1 4.82 5.92 (0.143, 0.046) 225 Reference Example 1-1 Manufacturing Example 24 4.51 6.31 (0.143, 0.046) 255 Reference Example 1-2 Manufacturing Example 25 4.59 6.31 (0.144, 0.046) 250 Reference Example 1-3 Manufacturing Example 26 4.68 6.22 (0.143, 0.046) 255 Reference Example 1-4 Manufacturing Example 27 4.65 6.25 (0.144, 0.044) 265 Reference Example 1-5 Manufacturing Example 28 4.56 6.37 (0.145, 0.046) 255 Reference Example 1-6 Preparation 29 4.68 6.26 (0.143, 0.044) 250 Reference Example 1-7 Manufacturing Example 30 4.67 6.27 (0.145, 0.044) 250 Reference Example 1-8 Manufacturing Example 31 4.65 6.25 (0.144, 0.046) 265 Reference Example 1-9 Manufacturing Example 32 4.56 6.37 (0.145, 0.044) 265 Reference Example 1-10 Manufacturing Example 33 4.57 6.38 (0.141, 0.046) 255 Reference Example 1-11 Manufacturing Example 34 4.58 6.33 (0.146, 0.046) 265 Reference Example 1-12 Manufacturing Example 35 4.46 6.58 (0.144, 0.046) 285 Reference Example 1-13 Production Example 36 4.39 6.62 (0.145, 0.044) 295 Reference Example 1-14 Production Example 37 4.46 6.51 (0.144, 0.046) 285 Reference Example 1-15 Preparation 38 4.49 6.60 (0.145, 0.044) 295 Reference Example 1-16 Manufacturing Example 39 4.34 6.66 (0.145, 0.046) 295 Comparative Example 1-2 EB2 5.12 5.66 (0.149, 0.053) 180 Comparative Example 1-3 EB3 4.91 5.84 (0.148, 0.051) 205

In Table 1, it can be seen that the Reference Examples 1-1 to 1-16 exhibit excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device. On the other hand, in Table 1, in Comparative Examples 1-1 to 1-3, compared to Reference Examples 1 to 1-16, the voltage of the organic light-emitting device was increased by 8 to 10%, and the efficiency was 5 to 10. % Decreased, and the lifespan decreased significantly.

Specifically, Reference Examples 1-1 to 1-16 are obtained by applying the compounds of Preparation Examples 24 to 39 represented by Chemical Formula 1 to an electron suppressing layer. On the other hand, in the compound of Comparative Example 1-2, in the compound represented by Chemical Formula 1, in which an arylamine group is substituted at positions 2 and 6 in the central benzene ring of the core (ie, cyclopentaphenanthrene). will be. On the other hand, in the compound of Comparative Example 1-2, an arylamine group is substituted at the second position of the core.

From this, in the compound represented by Formula 1, the most reactive positional substituent in the cyclopentaphenanthrene-centered benzene ring is linked (positional substitution at any one of 4 and 5, or simultaneous substitution at both positions) As a result, it is inferred that it has excellent stability and allows the organic light emitting device to be stably driven when applied to the electron suppression layer.

Further, it can be seen that when the compound represented by Formula 1 is applied to the electron-suppressing layer of an organic light-emitting device as in Reference Examples 1-1 to 1-16, it can contribute to realization of low voltage and high efficiency.

< Hole transport layer Application example >

In the following Reference Examples 2-1 to 2-16, each of the compounds of Preparation Examples 24 to 39 was applied to the hole transport layer of the light emitting device, and the effects thereof were confirmed.

Comparative example 2-1 and 2-2

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 HT1 in forming the hole transport layer. In Table 2 below, compounds represented by HT2 and HT3 are as follows.

Reference Examples 2-1 to 2-16

In forming the hole transport layer, an organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that the compound shown in Table 2 was used instead of HT1 and EB1 was used as the electron suppressing layer.

Experimental example 2

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

compound
(Hole transport layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Reference Example 2-1 Manufacturing Example 24 4.51 6.01 (0.142, 0.047) 220 Reference Example 2-2 Manufacturing Example 25 4.55 6.22 (0.143, 0.045) 255 Reference Example 2-3 Manufacturing Example 26 4.54 6.24 (0.143, 0.044) 250 Reference Example 2-4 Manufacturing Example 27 4.46 6.33 (0.143, 0.047) 265 Reference Example 2-5 Manufacturing Example 28 4.57 6.24 (0.143, 0.046) 255 Reference Example 2-6 Preparation 29 4.48 6.35 (0.142, 0.046) 260 Reference Example 2-7 Manufacturing Example 30 4.46 6.24 (0.141, 0.044) 260 Reference Example 2-8 Manufacturing Example 31 4.55 6.33 (0.142, 0.047) 255 Reference Example 2-9 Manufacturing Example 32 4.67 6.24 (0.143, 0.046) 255 Reference Example 2-10 Manufacturing Example 33 4.43 6.35 (0.142, 0.046) 250 Reference Example 2-11 Manufacturing Example 34 4.54 6.26 (0.143, 0.044) 255 Reference Example 2-12 Manufacturing Example 35 4.35 6.49 (0.145, 0.044) 280 Reference Example 2-13 Production Example 36 4.36 6.53 (0.144, 0.047) 275 Reference Example 2-14 Production Example 37 4.37 6.48 (0.144, 0.046) 275 Reference Example 2-15 Preparation 38 4.38 6.55 (0.144, 0.046) 280 Reference Example 2-16 Manufacturing Example 39 4.37 6.56 (0.143, 0.047) 285 Comparative Example 2-1 HT2 4.82 5.87 (0.143, 0.046) 215 Comparative Example 2-2 HT3 4.78 5.91 (0.143, 0.046) 190

In Table 2, it can be seen that Reference Examples 2-1 to 2-16 exhibit excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device. On the other hand, in Comparative Examples 2-1 and 2-1, compared to the Reference Examples 2-1 to 2-16, the voltage of the organic light emitting device was increased by 8-10%, and the efficiency was decreased by 5-10%. , The lifespan was significantly reduced.

Specifically, Reference Examples 2-1 to 2-16 are obtained by applying the compounds of Preparation Examples 24 to 39 represented by Chemical Formula 1 to the hole transport layer. From this, in the compound represented by Formula 1, the most reactive positional substituent in the cyclopentaphenanthrene-centered benzene ring is linked (positional substitution at any one of 4 and 5, or simultaneous substitution at both positions) As a result, it is inferred that it has excellent stability and enables the organic light emitting device to be stably driven when applied to the hole transport layer.

Further, it can be seen that when the compound represented by Formula 1 is applied to a hole transport layer of an organic light emitting device as in Reference Examples 2-1 to 2-16, it contributes to low voltage and high efficiency.

< Hole blocking layer Application example >

In Examples 3-1 to 3-13 below, each of the compounds of Preparation Examples 1, 2, 7 to 10, 12 to 15, and 18 to 20 was applied to the hole blocking layer of the light-emitting device, and the effects thereof were Confirmed.

Comparative example 3-1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made 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 50Å to form a hole injection layer.

[HAT]

The following compound 4,4'-(9-phenyl-9H-carbazole-3,6-diyl)bis(N,N-diphenylaniline) [HT 4](1150Å) as a material for transporting holes on the hole injection layer was vacuum By vapor deposition, a hole transport layer was formed.

[HT 4]

Subsequently, the following compound [EB 4] with a film thickness of 100Å was vacuum deposited on the hole transport layer to form an electron blocking layer.

[EB 4]

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

[BH]

[BD]

[HB 2]

[ET 2]

[LiQ]

The compound HB 2 was vacuum-deposited on the light-emitting layer with a film thickness of 50 Å on the hole transport layer to form a hole blocking layer (hole blocking layer).

Subsequently, the compound ET 2 and the 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 310Å. Lithium fluoride (LiF) at a thickness of 12Å and aluminum at a thickness of 1,000Å 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 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7. An organic light emitting device was manufactured by maintaining ~5 x10 ^-6 torr.

Comparative example 3-1 and 3-2

An organic light-emitting device was manufactured in the same manner as in Comparative Example 3-1, except that the compound shown in Table 3 below was used instead of HB2 in forming the hole blocking layer. In Table 3 below, compounds represented by HB3 and HB4 are as follows.

Example 3-1 to 3-13

An organic light-emitting device was manufactured in the same manner as in Comparative Example 3-1, except that the compound shown in Table 3 below was used instead of HB2 in forming the hole blocking layer.

Experimental example 3

When a current was applied to the organic light emitting devices manufactured according to Examples 3-1 to 13 and Comparative Examples 3-1 to 3-3, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 3 below. Indicated. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1300nit) to 95%.

compound
(Hole Blocking Layer) Voltage
(V@10Ma
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Comparative Example 3-1 HB2 4.81 5.89 (0.143, 0.046) 235 Example 3-1 Manufacturing Example 1 4.53 6.23 (0.143, 0.045) 265 Example 3-2 Manufacturing Example 2 4.54 6.22 (0.143, 0.044) 270 Example 3-3 Manufacturing Example 7 4.45 6.35 (0.143, 0.047) 275 Example 3-4 Manufacturing Example 8 4.54 6.24 (0.143, 0.046) 275 Example 3-5 Manufacturing Example 9 4.48 6.35 (0.142, 0.046) 280 Example 3-6 Manufacturing Example 10 4.47 6.25 (0.141, 0.044) 280 Example 3-7 Manufacturing Example 12 4.55 6.37 (0.142, 0.047) 265 Example 3-8 Manufacturing Example 13 4.69 6.25 (0.143, 0.046) 265 Example 3-9 Manufacturing Example 14 4.43 6.35 (0.142, 0.046) 280 Example 3-10 Manufacturing Example 15 4.54 6.26 (0.143, 0.044) 280 Example 3-11 Manufacturing Example 18 4.35 6.48 (0.145, 0.044) 275 Example 3-12 Manufacturing Example 19 4.35 6.53 (0.144, 0.047) 275 Example 3-13 Manufacturing Example 20 4.32 6.48 (0.144, 0.046) 275 Comparative Example 3-2 HB 3 4.93 5.81 (0.142, 0.046) 185 Comparative Example 3-3 HB 4 5.04 5.60 (0.143, 0.047) 170

In Table 3, it can be seen that Examples 3-1 to 3-13 exhibit excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device. On the other hand, in Table 3, in Comparative Examples 3-1 to 3-3, compared to Example 3 and Examples 3-1 to 3-13, the voltage of the organic light emitting device was increased by 8 to 10%, and , The efficiency was reduced by 5-10%, and the lifespan was significantly reduced.

Specifically, Examples 3-1 to 3-13 are obtained by applying the compounds of Preparation Examples 1, 2, 7 to 10, 12 to 15, and 18 to 20 represented by Formula 1 above to the hole blocking layer. From this, in the compound represented by Formula 1, the most reactive positional substituent in the cyclopentaphenanthrene center benzene ring is linked (position substitution at any one of 4 and 5, or simultaneous substitution at both positions) As a result, it is inferred that it has excellent stability and enables the organic light emitting device to be stably driven when applied to the hole blocking layer.

Further, it can be seen that when the compound represented by Formula 1 is applied to the hole blocking layer of an organic light-emitting device as in Examples 3-1 to 3-13, it contributes to realization of low voltage and high efficiency.

< Electron transport layer Application example >

In Examples 4-1 to 4-13 below, each of the compounds of Preparation Examples 1 to 6, 12 to 14, 17, and 21 to 23 was applied to the electron transport layer of an organic light-emitting device, and the effects thereof were confirmed.

Comparative example 4-1 and 4-2

An organic light-emitting device was manufactured in the same manner as in Comparative Example 3-1, except that the compound shown in Table 4 below was used instead of ET2 in forming the electron transport layer. In Table 4 below, compounds represented by ET3 and ET4 are as follows.

Example 4-1 to 4-13

An organic light-emitting device was manufactured in the same manner as in Comparative Example 3-1, except that the compound shown in Table 4 below was used instead of ET2 in forming the electron transport layer.

Experimental example 4

When a current was applied to the organic light-emitting devices fabricated in Examples 4-1 to 4-13, the results of Table 4 were obtained. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1300nit) to 95%.

compound
(Electron transport layer) Voltage
(V@10Ma
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 4-1 Manufacturing Example 1 4.50 6.24 (0.143, 0.045) 255 Example 4-2 Manufacturing Example 2 4.51 6.25 (0.143, 0.044) 260 Example 4-3 Manufacturing Example 3 4.40 6.31 (0.143, 0.047) 255 Example 4-4 Manufacturing Example 4 4.53 6.25 (0.143, 0.046) 265 Example 4-5 Manufacturing Example 5 4.45 6.39 (0.142, 0.046) 260 Example 4-6 Manufacturing Example 6 4.49 6.28 (0.141, 0.044) 270 Example 4-7 Manufacturing Example 12 4.51 6.36 (0.142, 0.047) 255 Example 4-8 Manufacturing Example 13 4.67 6.27 (0.143, 0.046) 265 Example 4-9 Manufacturing Example 14 4.45 6.35 (0.142, 0.046) 260 Example 4-10 Manufacturing Example 17 4.58 6.24 (0.143, 0.044) 270 Example 4-11 Manufacturing Example 21 4.34 6.45 (0.145, 0.044) 290 Example 4-12 Manufacturing Example 22 4.35 6.51 (0.144, 0.047) 285 Example 4-13 Manufacturing Example 23 4.35 6.48 (0.144, 0.046) 280 Comparative Example 4-1 ET3 4.72 5.92 (0.144, 0.045) 165 Comparative Example 4-2 ET4 4.86 5.81 (0.144, 0.046) 80

In Table 4, it can be seen that Examples 4-1 to 4-13 exhibit excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.

Specifically, Examples 4-1 to 4-13 are obtained by applying the compounds of Preparation Examples 1 to 6, 12 to 14, 17, and 21 to 23 represented by Chemical Formula 1 to the electron transport layer.

In Table 4, in Comparative Examples 4-1 to 4-2, compared to Examples 4-1 to 4-13, the voltage of the organic light emitting device was increased by 6 to 9%, and the efficiency was decreased by 10 to 12%. And the lifespan was significantly reduced.

From this, in the compound represented by Formula 1, the most reactive positional substituent in the cyclopentaphenanthrene center benzene ring is linked (position substitution at any one of 4 and 5, or simultaneous substitution at both positions) As a result, it is inferred that it has excellent stability and, when applied to an electron transport layer, enables the organic light emitting device to be stably driven.

Furthermore, it can be seen that when the compound represented by Formula 1 is applied to the electron transport layer of an organic light emitting device as in Examples 4-1 to 4-13, it contributes to low voltage and high efficiency.

Preferred embodiments of the present invention (hole transport layer, electron suppression layer, hole suppression layer, electron transport layer) have been described above, but the present invention is not limited thereto, but within the scope of the claims and detailed description of the invention. It is possible to change and implement it, 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: electron transport layer

Claims (8)

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

In Formula 1,
R ₁ and R _2, C ₁ each independently represent a substituted or unsubstituted - ₆₀ alkyl; Or, a substituted or unsubstituted C ₆ - ₆₀ aryl group, or is bonded to each other to form a C _6-60 aromatic ring,
Y ₁ is hydrogen; A substituted or unsubstituted C _6-60 aryl group; Or, it is a C _2-60 heterocyclic group containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S,
Y ₂ is represented by the following formula (3),
[Chemical Formula 3]

In Chemical Formula 3,
L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene group including at least one of O, N, Si and S,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl group including at least one of O, N, Si and S,
Each of X ₁ to X _{3 is} independently N or CH, but at least one of X ₁ to X ₃ is N.
The method of claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-3,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The method of claim 1,
Ar ₃ and Ar ₄ are the same or different, each independently any one selected from the group consisting of,
compound:

The method of claim 1,
L ₁ is a bond; Phenyl; Biphenylyl; Terphenylyl; Quarterphenylyl; Naphthyl; Anthracenyl; Fluorenyl; Phenanthrenyl; Pyrenyl; Or triphenylenyl,
compound.
The method of claim 1,
Y ₁ is hydrogen,
compound.
The method of claim 1,
Y ₁ is any one selected from the group consisting of,
compound:

here,
L ₂ to L ₅ are each a bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene group including at least one of O, N, Si and S,
R ₃ is hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or, it is a substituted or unsubstituted C _2-60 aryl group.
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 an organic material layer of at least one layer provided between the first electrode and the second electrode,
The organic material layer includes a hole blocking layer and an electron transport layer, and at least one of the hole blocking layer and the electron transport layer includes the compound according to any one of claims 1 to 7.

Images