KR102608810B1 - 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.

Description

Novel compound and organic light emitting device comprising the same}

The present invention relates to novel compounds and organic light-emitting devices using the same.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

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

Korean Patent Publication No. 10-2013-073537

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

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

Formula 1]

In Formula 1,

X ₁ is O or S,

X ₂ is O, S or CRR',

Here, R and R' are each independently substituted or unsubstituted C _1-60 alkyl or substituted or unsubstituted C _6-60 aryl,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or N, O and S. C _5-60 substituted or unsubstituted heteroaryl containing more than one hetero atom,

m and n are each independently integers from 0 to 7,

o is an integer from 0 to 3.

In addition, the present invention includes a first electrode; a second electrode provided opposite to 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 layer of the organic material layer includes the compound of the present invention described above.

The compound represented by the above-mentioned formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 shows an example of an organic light emitting device consisting 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), and a cathode (4). It was done.

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

(Explanation of terms)

In this specification, means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy 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 substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the oxygen of the ester group may be substituted with a straight-chain, branched-chain, or ring-chain 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, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

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

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

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups 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, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples 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, etc., but are not limited to these.

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 embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

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

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, It can be etc. However, it is not limited to this.

In the present specification, the heteroaryl group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and has aromaticity. The number of carbon atoms is not particularly limited, but the number of carbon atoms is 2 to 60. desirable. Examples of heteroaryl 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, and 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but is not limited to these.

In this 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 this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding the heterocyclic group described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of the heterocyclic group described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of the heterocyclic group described above can be applied, except that the heterocycle is not a monovalent group and is formed by combining two substituents.

(compound)

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

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

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

X ₁ , X ₂ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m, n and o are as previously defined.

Preferably,

X ₁ is O, X ₂ is O, or

X ₁ is O, X ₂ is S, or

X ₁ is O, X ₂ is CRR', or

X ₁ is S, X ₂ is O, or

X ₁ is S, X ₂ is S, or

X ₁ is S, X ₂ is CRR',

Here, R and R' are each independently substituted or unsubstituted C _1-10 alkyl or substituted or unsubstituted C _6-30 aryl. Preferably, R and R' are each independently substituted or unsubstituted C _1-10 alkyl.

Preferably, R and R' are each independently methyl, ethyl, propyl, butyl, phenyl, biphenylyl, terphenylyl or naphthyl. More preferably, it is methyl.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, or naphthyl, which may be substituted or unsubstituted with one or more deuterium. When substituted with deuterium, it may preferably contain at least two deuteriums per benzene ring.

Preferably, R ₁ and R ₂ are each independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl or dibenzothiophenyl, More preferably, it is phenyl. The phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl may each independently be substituted or unsubstituted with one or more deuterium groups.

When R ₁ and R ₂ are each independently deuterium, preferably, m and n are each independently 7.

R ₁ and R ₂ are each independently, if not deuterium, preferably m and n are each independently an integer of 0 to 2.

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

.

.

The compound represented by Formula 1 according to the present invention has a triazine-based ring group with excellent electron transport ability connected to the 3-position of dibenzofuran or dibenzothiophene through the meta position of the phenyl group, and a condensed ring at the other meta position. contains a connected structure. This structure has excellent electron injection characteristics in the light-emitting layer, and when the electron transport ability is applied to an organic light emitting device, it can realize the characteristics of low aperture voltage, high efficiency, and long lifespan. In particular, position 3 of dibenzofuran or dibenzothiophene is advantageous for conjugation with a triazine-based substituent, and when connected to a biphenyl group rather than a phenyl group, this effect is halved because the distance between the two substituents is long. In addition, in the case of having a nitrogen-containing hetero ring other than a triazine-based substituent, the electron transfer positions within the molecule are dispersed, which may be disadvantageous to electron transport.

The compound represented by Formula 1 can be prepared through Scheme 1 below.

[Scheme 1]

In the above reaction formula, the definition of each substituent is as described above.

The above reaction formula is a Suzuki coupling reaction, and the reaction is preferably performed in the presence of a palladium catalyst and a base. Additionally, the reactor, catalyst, solvent, etc. used for the above reaction can be changed to suit the desired product. The method for producing the compound of Formula 1 may be more detailed in the production examples that will be described later.

(Organic light emitting device)

Additionally, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to 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 layer of the organic material layer includes a compound represented by Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer 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 that includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Chemical Formula 1. In the light-emitting layer, the compound represented by Formula 1 is used as a host material.

Preferably, the light-emitting layer containing the compound represented by Formula 1 may further include a compound represented by Formula 2, and when the two compounds are used in combination as a host material in the light-emitting layer, an exciplex is formed. This is advantageous, and thus the characteristics of low voltage, high efficiency, and long life can be further improved when applied to organic light-emitting devices:

[Formula 2]

In Formula 2,

Ar ₃ and Ar ₄ are each independently, substituted or unsubstituted C _6-60 aryl or substituted or unsubstituted C _5-60 hetero atom containing one or more heteroatoms selected from the group consisting of N, O and S. It's Aryl,

R ₃ and R ₄ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S. ego,

p and q are each independently integers from 0 to 7.

Preferably, Ar ₃ and Ar ₄ may each independently be phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or dimethylfluorenyl.

Preferably, R ₃ and R ₄ may each independently be hydrogen or deuterium, more preferably hydrogen.

Preferably, p and q may each independently be an integer of 0 to 3 or an integer of 0 to 2. More preferably, it may be 0 or 1.

Preferably, the compound represented by Formula 2 may be any one selected from the group consisting of:

.

.

Additionally, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or electron injection layer includes the compound represented by Formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron injection and electron transport includes the compound represented by Formula 1. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, high triple energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic material layer capable of simultaneous electron injection and electron transport, n-type dopants used in the art can be mixed and used.

Additionally, the organic layer includes a light-emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by Formula 1.

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

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

Figure 2 shows an example of an organic light emitting device consisting 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), and a cathode (4). It was done. In this structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport layer.

The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Formula 1 above. Additionally, 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 can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can be made 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 when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

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

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode 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; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic 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, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that 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 material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-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, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. do. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. 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 with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer. A compound that prevents movement to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. Complex compounds and nitrogen-containing five-membered ring derivatives are included, but are not limited thereto.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

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

[Manufacturing example]

Preparation Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-1

In a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (15.0g, 55.5mmol) and dibenzo[b,d]furan-3-ylboronic acid (25.9g, 122.1mmol) were added to 300ml of THF, stirred and refluxed. Afterwards, potassium carbonate (30.7g, 221.9mmol) was dissolved in 92ml of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.9g, 1.7mmol) was added. After 9 hours of reaction, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound 1-1. (Yield 79%, MS: [M+H]+= 446)

Step 2) Synthesis of Compound 1-2

Compound 1-1 (15.0 g, 33.7 mmol) and bis(pinacolato)diboron (9.4 g, 37.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred in a nitrogen atmosphere. Afterwards, potassium acetate (5.0g, 50.6mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.0mmol) and tricyclohexylphosphine (0.6g, 2.0mmol) were added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9 g of compound 1-2. (Yield 66%, MS: [M+H]+= 537)

Step 3) Synthesis of Compound 1

In a nitrogen atmosphere, compound 1-2 (15.0 g, 28 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (9.0 g, 33.6 mmol) were added to 300 ml of THF, stirred and refluxed. Afterwards, potassium carbonate (15.5g, 111.9mmol) was dissolved in 46ml of water and stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.0g, 0.8mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, and then 5.6 g of Compound 1 was prepared through sublimation purification. (Yield 31%, MS: [M+H]+= 643)

Preparation Example 2: Synthesis of Compound 2

Step 1) Synthesis of Compound 2-1

In a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (15.0g, 47.3mmol) and dibenzo[b,d]furan-3-ylboronic acid (12.0g, 56.7mmol) were added to 300ml of THF, stirred and refluxed. Afterwards, potassium carbonate (26.1g, 189.1mmol) was dissolved in 78ml of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.6g, 1.4mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound 2-1. (Yield 80%, MS: [M+H]+= 359)

Step 2) Synthesis of Compound 2-2

In a nitrogen atmosphere, compound 2-1 (15.0 g, 41.9 mmol) and 2-(dibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.8 g, 50.3 mmol) was added to 300 ml of THF, stirred and refluxed. Afterwards, potassium carbonate (23.2g, 167.8mmol) was dissolved in 70ml of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.5g, 1.3mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 2-2. (Yield 79%, MS: [M+H]+= 446)

Step 3) Synthesis of compounds 2-3

Compound 2-2 (15.0 g, 33.7 mmol) and bis(pinacolato)diboron (9.4 g, 37.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred in a nitrogen atmosphere. Afterwards, potassium acetate (5.0g, 50.6mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.0mmol) and tricyclohexylphosphine (0.6g, 2.0mmol) were added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 2-3. (Yield 75%, MS: [M+H]+= 537)

Step 4) Synthesis of Compound 2

Compound 2-3 (15.0g, 28.0mmol) and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (11.5g) in a nitrogen atmosphere. , 33.6 mmol) was added to 300 ml of THF, stirred and refluxed. Afterwards, potassium carbonate (15.5g, 111.9mmol) was dissolved in 46ml of water and stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.0g, 0.8mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, and then 7.6 g of Compound 2 was prepared through sublimation purification. (Yield 38%, MS: [M+H]+= 719)

Preparation Example 3: Synthesis of Compound 3

In Preparation Example 2, 2-(dibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was reacted with (6-phenyldibenzo[b,d]thiophen- 4-yl)boronic acid, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine is converted to 2-chloro-4,6-diphenyl Compound 3 was prepared using the same method as that of Compound 2, except that it was changed to -1,3,5-triazine. (MS: [M+H] ⁺ = 735)

Preparation Example 4: Synthesis of Compound 4

In Preparation Example 2, 2-(dibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was reacted with dibenzo[b,d]thiophen-4-ylboronic With acid, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine is converted to 2-chloro-4-phenyl-6-(phenyl-d5 ) Compound 4 was prepared using the same method as that of compound 2, except that it was changed to -1,3,5-triazine. (MS: [M+H] ⁺ = 664)

Preparation Example 5: Synthesis of Compound 5

In Preparation Example 2, dibenzo[b,d]furan-3-ylboronic acid is converted to (7-phenyldibenzo[b,d]furan-3-yl)boronic acid, 2-(dibenzo[b,d]furan-1- yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane is converted to 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine, 2-chloro-4,6-diphenyl Compound 5 was prepared using the same method as that of Compound 2, except that it was changed to -1,3,5-triazine. (MS: [M+H] ⁺ = 745)

Preparation Example 6: Synthesis of Compound 6

In Preparation Example 2, dibenzo[b,d]furan-3-ylboronic acid is converted to dibenzo[b,d]thiophen-3-ylboronic acid, 2-(dibenzo[b,d]furan-1-yl)-4, 4,5,5-tetramethyl-1,3,2-dioxaborolane With dioxaborolane, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine is converted to 2-chloro-4,6-diphenyl-1,3, Compound 6 was prepared using the same method as that of Compound 2, except that it was changed to 5-triazine. (MS: [M+H] ⁺ = 735)

Preparation Example 7: Synthesis of Compound 7

In Preparation Example 2, dibenzo[b,d]furan-3-ylboronic acid is converted to dibenzo[b,d]thiophen-3-ylboronic acid, 2-(dibenzo[b,d]furan-1-yl)-4, 4,5,5-tetramethyl-1,3,2-dioxaborolane to (2-phenyldibenzo[b,d]thiophen-4-yl)boronic acid, 2-([1,1'-biphenyl]-3-yl )-4-chloro-6-phenyl-1,3,5-triazine was used in the same manner as the preparation method of compound 2, except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used. Compound 7 was prepared using the preparation method. (MS: [M+H] ⁺ = 751)

Preparation Example 8: Synthesis of Compound 8

In Preparation Example 2, dibenzo[b,d]furan-3-ylboronic acid is converted to dibenzo[b,d]thiophen-3-ylboronic acid, 2-(dibenzo[b,d]furan-1-yl)-4, 4,5,5-tetramethyl-1,3,2-dioxaborolane was converted to 2-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine as 2-chloro-4,6-diphenyl- Compound 8 was prepared using the same method as that of Compound 2, except that it was changed to 1,3,5-triazine. (MS: [M+H] ⁺ = 761)

[Example]

Example 1: Preparation of organic light emitting device

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) with a thickness of 1400 Å was placed in distilled water with a detergent dissolved in it and washed with ultrasonic waves. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, 95% by weight of HT-A and 5% by weight of PD were thermally vacuum deposited to a thickness of 100Å to form a hole injection layer, and then only the HT-A material was deposited to a thickness of 1150Å to form a hole transport layer. was formed. On top of this, the following HT-B was thermally vacuum deposited to a thickness of 450 Å as an electron blocking layer.

Next, Compound 1 prepared in Preparation Example 1 as a host material and GD as a dopant material were vacuum deposited on the electron blocking layer to a thickness of 350 Å at a weight ratio of 92:8 to form a light emitting layer.

Next, the following ET-A was vacuum deposited to a thickness of 50 Å as a hole blocking layer. Next, as an electron transport layer, ET-B and Liq were thermally vacuum deposited to a thickness of 300 Å at a ratio of 1:1, and then Yb was vacuum deposited to a thickness of 10 Å as an electron injection layer.

Magnesium and silver were deposited on the electron injection layer at a ratio of 1:4 to a thickness of 150 Å to form a cathode, thereby manufacturing an organic light emitting device.

In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of magnesium and silver was maintained at 2Å/sec, and the vacuum degree during deposition was maintained at 2x10 ^-7 ~ 5x10 ^-6 torr, producing organic light emission. The device was manufactured.

Examples 2 to 8

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1.

Examples 9 to 12

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1. In Table 1 below, the ratio of each compound refers to the weight ratio, and compounds PGH-1 and PGH-2 are respectively as follows.

Comparative Examples 1 to 4

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1. In Table 1 below, compounds GH-A, GH-B, GH-C and GH-D are respectively as follows.

Comparative Examples 5 to 8

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1. In Table 1 below, the ratio of each compound refers to the weight ratio, and compounds GH-A, GH-D, PGH-1, and PGH-2 are as described above.

[Experimental example]

The organic light-emitting devices manufactured in the above examples and comparative examples were stored in an oven at 110° C. for 30 minutes and heat-treated, and then current was applied to measure voltage, efficiency, and lifespan (T95), and the results are shown in Table 1 below. . At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² . Additionally, T95 in Table 1 below refers to the time measured until the initial luminance decreases to 95% at a current density of 20 mA/cm ² .

division Emissive layer (host) Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 1 Compound 1 4.83 57.5 74 Example 2 compound 2 4.84 58.9 84 Example 3 Compound 3 4.80 59.6 86 Example 4 Compound 4 4.80 59.3 95 Example 5 Compound 5 4.83 55.9 81 Example 6 Compound 6 4.93 57.7 89 Example 7 Compound 7 4.97 56.1 84 Example 8 Compound 8 4.96 54.3 78 Example 9 PGH-1: Compound 1 (60:40) 4.14 70.4 126 Example 10 PGH-1: Compound 3 (60:40) 4.09 72.1 139 Example 11 PGH-2: Compound 6 (60:40) 4.10 70.2 141 Example 12 PGH-2: Compound 8 (60:40) 4.11 67.0 135 Comparative Example 1 GH-A 5.31 36.0 48 Comparative Example 2 GH-B 5.83 27.1 52 Comparative Example 3 GH-C 5.10 51.6 66 Comparative Example 4 GH-D 6.24 12.3 5 Comparative Example 5 PGH-1:GH-A(60:40) 5.01 50.2 53 Comparative Example 6 PGH-1:GH-B(60:40) 5.53 48.8 61 Comparative Example 7 PGH-2:GH-C(60:40) 4.92 66.3 77 Comparative Example 8 PGH-2:GH-D(60:40) 5.90 38.1 27

The compound represented by Formula 1 according to the present invention has a triazine-based ring group with excellent electron transport ability connected to the 3-position of dibenzofuran or dibenzothiophene through the meta position of the phenyl group, and a condensed ring at the other meta position. contains a connected structure. This structure has excellent electron injection characteristics in the light-emitting layer, and when the electron transport ability is applied to an organic light emitting device, it can realize the characteristics of low aperture voltage, high efficiency, and long lifespan. In particular, position 3 of dibenzofuran or dibenzothiophene is advantageous for conjugation with a triazine-based substituent, and when connected to a biphenyl group rather than a phenyl group, this effect may be halved due to the long distance between the two substituents.

When the GH-B compound of Comparative Example 2 was used, it was confirmed that the driving voltage was higher and the efficiency and lifespan characteristics were significantly lower than in the Example, as it is a compound with a structure linked to a biphenyl group.

In addition, when the GH-C compound of Comparative Example 3, which has a nitrogen-containing heterocycle other than the triazine-based substituent, is used, the electron transfer positions in the molecule are dispersed, which is unfavorable for electron transport, and thus all properties are deteriorated compared to the Example. You can check that.

On the other hand, the compound represented by Formula 1 can be used as a host together with the compound represented by Formula 2 to further improve the characteristics of low voltage, high efficiency, and long life, and the devices of Examples 9 and 10 are comparative examples. It can be seen that the efficiency is higher compared to devices 5 to 8, and in particular, the lifespan characteristics are greatly 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

Claims (12)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
X ₁ is O, X ₂ is O, or
X ₁ is O, X ₂ is CRR', or
X ₁ is S, X ₂ is S, or
X ₁ is S, X ₂ is CRR',
Here, R and R' are each independently C _1-60 alkyl,
Ar ₁ and Ar ₂ are each independently C _6-60 aryl substituted or unsubstituted with one or more deuterium,
R ₁ and R ₂ are each independently hydrogen, deuterium, C _1-60 alkyl, or C _6-60 aryl unsubstituted or substituted with one or more deuterium,
m and n are each independently integers from 0 to 7,
o is an integer from 0 to 3.
According to clause 1,
The compound represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
X ₁ , X ₂ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m, n and o are as defined in claim 1.
delete According to clause 1,
R and R' are each independently methyl, ethyl, propyl or butyl.
According to clause 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, or naphthyl,
These compounds are each independently substituted or unsubstituted with one or more deuterium.
According to clause 1,
R ₁ and R ₂ are each independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, phenyl, biphenylyl, terphenylyl, or naphthyl,
The phenyl, biphenylyl, terphenylyl or naphthyl is each independently substituted or unsubstituted with one or more deuterium groups.
According to clause 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
first electrode; a second electrode provided opposite to 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 layer of the organic material layer is any of claims 1, 2, 4 to 7. An organic light-emitting device comprising the compound according to one clause.
According to clause 8,
An organic light-emitting device, wherein the organic material layer containing the compound is a light-emitting layer.
According to clause 9,
An organic light-emitting device wherein the light-emitting layer further includes a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
Ar ₃ and Ar ₄ are each independently, substituted or unsubstituted C _6-60 aryl or substituted or unsubstituted C _5-60 hetero atom containing one or more heteroatoms selected from the group consisting of N, O and S. It's Aryl,
R ₃ and R ₄ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S. ego,
p and q are each independently integers from 0 to 7.
According to clause 10,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or dimethylfluorenyl,
Organic light emitting device.
According to clause 10,
An organic light-emitting device in which the compound represented by Formula 2 is any one selected from the group consisting of:

.