KR20210008814A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The compound is represented by chemical formula 1 and can improve the efficiency of the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

In general, 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.

The 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 made 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.

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Formula 1,

X is each independently N or CH, provided that at least two of X are N,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

R ₁ to R ₄ are each independently hydrogen or deuterium, or two adjacent two of R ₁ to R ₄ are bonded to each other to form a C _6-60 aromatic ring unsubstituted or substituted with deuterium,

R ₅ to R ₇ are each independently hydrogen or deuterium,

a is an integer from 0 to 6,

b is an integer from 0 to 3,

c is an integer from 0 to 5,

When a, b and c are each 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an emission layer provided between the first electrode and the second electrode, wherein the emission layer includes a compound represented by Formula 1 above.

The compound represented by Formula 1 described above is used as a material of the organic material layer of the organic light emitting device, thereby improving the efficiency, low driving voltage, and/or lifetime characteristics of the organic light emitting device.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), an electron injection and transport layer (8) and a cathode (4). It shows an example of an organic light emitting device made of.

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

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano 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 heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified 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 connected with two phenyl groups.

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 straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In 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, a phenyl boron group, and the like, 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but 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 aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl 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, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, 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 ( phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

In the present specification, the aromatic ring refers to a condensed monocyclic or condensed polycyclic ring including only carbon as a ring-forming atom and having aromaticity in the entire molecule. The number of carbon atoms in the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. In addition, the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl 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-described description of heteroaryl 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 above-described heteroaryl 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 heteroaryl is not a monovalent group, and the description of the above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

(compound)

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

The compound represented by Formula 1 has a structure in which a triazinyl-based substituent and a benzocarbazolyl-based substituent are connected by a benzonaphthofuranylene linker. In these compounds, triazinyl-based substituents serve to transport electrons, and benzocarbazolyl-based substituents serve to transport holes, and are advantageous in balancing charge transport and charge in the light emitting layer compared to compounds that do not have them at the same time. In addition, compared to a compound having a structure in which the two substituents are connected by different linkers, the benzonaphthofuranylene linker spatially separates the two substituents, and has low triplet energy, so that it has suitable properties as a red light emitting layer host. Accordingly, the voltage, efficiency, and lifetime of the organic light emitting device employing such a compound may be improved.

The compound represented by Formula 1 has a structure in which a triazinyl-based substituent and a benzocarbazolyl-based substituent are connected by a benzonaphthofuranylene linker. An organic light-emitting device employing such a compound has a high efficiency and long lifespan compared to an organic light-emitting device employing a compound that does not have a triazinyl-based substituent and a benzocarbazolyl-based substituent at the same time, and a compound having a structure in which these two substituents are connected by different linkers. Characteristics.

The compound represented by Formula 1 is represented by any one of the following Formulas 1A to 1D, depending on the bonding position of the triazinyl-based substituent:

[Formula 1A]

[Formula 1B]

[Formula 1C]

[Formula 1D]

In Formulas 1A to 1D,

X, Ar ₁ , Ar ₂ , R ₁ to R ₇ , a, b and c are as defined in Chemical Formula 1.

Preferably, R ₁ to R ₄ are each independently hydrogen or deuterium; Or two adjacent ones of R ₁ to R ₄ may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.

More preferably, R ₁ to R ₄ are all hydrogen, or all deuterium; Alternatively, two adjacent ones of R ₁ to R ₄ may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium, and the remainder may be hydrogen or deuterium.

At this time, the fact that two adjacent ones of R ₁ to R ₄ are bonded to each other to form a benzene ring means that R ₁ and R ₂ are bonded to each other to form a benzene ring; R ₂ and R ₃ are bonded to each other to form a benzene ring; Or it means that R ₃ and R ₄ are bonded to each other to form a benzene ring.

Specifically, the compound may be represented by any one of 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,

R ₁ to R ₄ and R are each independently hydrogen or deuterium,

d is an integer from 0 to 4,

X, Ar ₁ , Ar ₂ , R ₅ to R ₇ , a, b and c are the same as defined in Formula 1,

When d is 2 or more, the substituents R in parentheses are the same as or different from each other.

Preferably, X is all N; Or two of X may be N, and the rest may be CH.

Preferably, Ar ₁ and Ar ₂ are each independently an unsubstituted or deuterium substituted C _6-20 aryl, or an unsubstituted or deuterium substituted heteroatom O or S containing C _2-60 hetero It can be aryl.

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with deuterium.

Most preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or all hydrogens may be substituted with deuterium.

In addition, at least one of Ar ₁ and Ar ₂ may be phenyl or phenyl substituted with deuterium.

이거나, 또는

일 수 있다.For example, at least one of Ar ₁ and Ar ₂ is

Or

Can be

Also, Ar ₁ and Ar ₂ may be the same as each other; Or Ar ₁ and Ar ₂ may be different.

In addition, a, b, and c refer to the number of substituents R ₅ , R ₆ and R ₇ in parentheses, respectively, and when a, b and c are each 2 or more, the substituents in parentheses are the same or different from each other.

In this case, a is 0, 1, 2, 3, 4, 5, or 6,

b is 0, 1, 2, or 3,

c is 0, 1, 2, 3, 4, or 5.

Preferably, a is 0 or 6, b is 0 or 3, and c may be 0 or 5.

Preferably, R ₅ to R ₇ may be all hydrogen or all deuterium.

Preferably, in Formulas 1-1 to 1-4, a may be 0 or 6, b may be 0 or 3, c may be 0 or 5, and d may be 0 or 4.

Preferably, in Formulas 1-1 to 1-4, R ₅ to R ₇ and R may be all hydrogen or all deuterium.

For example, the compound is any one selected from the group consisting of the following compounds:

.

On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example.

[Scheme 1]

In Reaction Scheme 1, each Z is independently halogen, preferably bromo or chloro, and definitions for other substituents are as described above.

The compound represented by Formula 1 can be prepared through steps 1 to 3. Specifically, in step 1, the starting material A1 is subjected to an amine substitution reaction with compound A2 to prepare an intermediate compound A3. Thereafter, in step 2, the intermediate compound A3 was reacted with compound A4 to prepare intermediate compound A5 into which a substituent for suzuki-coupling reaction was introduced, and then in step 3, the intermediate compound A5 and compound A6 were subjected to suzuki-coupling reaction. To prepare a compound represented by Formula 1. These amine substitution reactions and suzuki-coupling reactions are preferably carried out in the presence of a palladium catalyst and a base, respectively. In addition, the reactor for the amine substitution reaction and the suzuki-coupling reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(Organic light emitting device)

In addition, the present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And an emission layer provided between the first electrode and the second electrode, wherein the emission layer includes the compound represented by Formula 1 above.

In addition, the organic light-emitting device according to the present invention is 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 in which a first electrode is an anode and a second electrode is a cathode. Can be In addition, the organic light-emitting device according to the present invention has 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 in which the first electrode is the cathode and the second electrode is the anode. Can be 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 comprising 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 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), an electron injection and transport layer (8) and a cathode (4). It shows an example of an organic light emitting device made of. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

The organic light-emitting device according to the present invention can be manufactured by materials and methods known in the art, except that the emission layer includes the compound according to the present invention and is manufactured as described above.

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

In addition to 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; Conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are a multi-layered material such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from an 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 a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film 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 compounds, 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 the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The electron blocking layer is formed on the hole transport layer and is preferably provided in contact with the light emitting layer, thereby controlling hole mobility and preventing excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. It refers to the layer that plays a role in improving the value. The electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.

The emission layer may include a host material and a dopant material. As the host material, the compound represented by Formula 1 may be used. In addition, as the host material, a condensed aromatic ring derivative or a heterocyclic-containing compound may be additionally used in addition to the compound represented by Formula 1 above. 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.

Further, the dopant material includes an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. 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 an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, 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 injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As such an electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used together, but is not limited thereto.

The electron injection and transport layer may be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

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 thereto.

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

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

[Production Example]

Preparation A: Synthesis of Intermediate A

Step 1) Synthesis of Intermediate A-1

In a nitrogen atmosphere, 5-bromo-1-idonaphthalen-2-ol (15.0 g, 43.0 mmol) and (3-chloro-2-fluorophenyl) boronic acid (8.2 g, 47.3 mmol) were added to 300 ml of THF. Then, it was stirred and refluxed. Thereafter, potassium carbonate (23.8 g, 171.9 mmol) was dissolved in 71 ml of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (1.5 g, 1.3 mmol) was added. After reacting for 10 hours, the mixture 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of Intermediate A-1. (Yield 62%, MS: [M+H] ⁺ = 353)

Step 2) Synthesis of Intermediate A

In a nitrogen atmosphere, intermediate A-1 (15.0 g, 42.7 mmol) and potassium carbonate (11.8 g, 85.3 mmol) were added to 225 ml of NMP, followed by stirring and refluxing. After the reaction for 8 hours, the mixture was cooled to room temperature, and 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of Intermediate A. (Yield 70%, MS: [M+H] ⁺ = 333)

Preparation B: Synthesis of Intermediate B

In Preparation Example A, except that (3-chloro-2-fluorophenyl) boronic acid was changed to (4-chloro-2-fluorophenyl) boronic acid and used, Intermediate B was prepared. (MS: [M+H] ⁺ = 333)

Preparation C: Synthesis of Intermediate C

In Preparation Example A, except that (3-chloro-2-fluorophenyl) boronic acid was changed to (5-chloro-2-fluorophenyl) boronic acid and used, Intermediate C was prepared. (MS: [M+H] ⁺ = 333)

Preparation D: Synthesis of Intermediate D

In Preparation Example A, except that (3-chloro-2-fluorophenyl) boronic acid was changed to (2-chloro-6-fluorophenyl) boronic acid and used, Intermediate D was prepared. (MS: [M+H] ⁺ = 333)

Preparation Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-1

In a nitrogen atmosphere, intermediate A (15.0 g, 45.2 mmol) and 5H-benzo[b]carbazole (10.8 g, 49.8 mmol) were added to 300 ml of toluene, followed by stirring and refluxing. After this, sodium tert-butoxide (6.5 g, 67.9 mmol) and bis (tri-tert-butylphosphine) palladium (0) (0.7 g, 1.4 mmol) were added. After the reaction for 11 hours, the mixture was cooled to room temperature, and 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 1-1. (Yield 68%, MS: [M+H] ⁺ = 469)

Step 2) Synthesis of Compound 1-2

Compound 1-1 (15.0 g, 32.1 mmol) and bis(pinacolato)diborane (9 g, 35.3 mmol) were stirred in a nitrogen atmosphere while refluxing in 300 ml of 1,4-dioxane. After that, potassium acetate (4.7 g, 48.1 mmol) was added, stirred sufficiently, and then bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.0 mmol) and tricyclohexylphosphine (0.5 g, 1.9 mmol) were added. Was put in. After reacting for 7 hours, cooling 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-2. (Yield 72%, MS: [M+H] ⁺ = 560)

Step 3) Synthesis of Compound 1

In a nitrogen atmosphere, compound 1-2 (15.0 g, 26.8 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (7.9 g, 29.5 mmol) were added to 300 ml of THF and stirred and refluxed. . Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 ml of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 11 hours, the mixture 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, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 6.6 g of compound 1 was prepared through sublimation purification. (Yield 37%, MS: [M+H] ⁺ = 666)

Preparation Example 2: Synthesis of Compound 2

In Preparation Example 1, 5H-benzo[b]carbazole was replaced with 7H-dibenzo[b,g]carbazole, and 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-([ 1,1′-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine, except that the compound was used in the same manner as in the preparation method of Compound 2 Was prepared. (MS: [M+H] ⁺ = 792)

Preparation Example 3: Synthesis of Compound 3

In Preparation Example 1, compound 3 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate B and used. (MS: [M+H] ⁺ = 666)

Preparation Example 4: Synthesis of Compound 4

In Preparation Example 1, intermediate A to intermediate B, 5H-benzo[b]carbazole to 7H-dibenzo[b,g]carbazole, 2-chloro-4,6-diphenyl-1,3,5- Compound 4 was prepared in the same manner as the preparation method of Compound 1, except that triazine was changed to 2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3,5-triazine. Was prepared. (MS: [M+H] ⁺ = 766)

Preparation Example 5: Synthesis of Compound 5

In Preparation Example 1, compound 5 was prepared in the same manner as in the preparation method of Compound 1, except that Intermediate A was changed to Intermediate C and used. (MS: [M+H] ⁺ = 666)

Preparation Example 6: Synthesis of Compound 6

In Preparation Example 1, intermediate A to intermediate C, 5H-benzo[b]carbazole to 6H-dibenzo[b,h]carbazole, 2-chloro-4,6-diphenyl-1,3,5- Compound 6 was prepared in the same manner as in the preparation method of Compound 1, except that triazine was changed to 4-chloro-2,6-diphenylpyrimidine and used. (MS: [M+H] ⁺ = 715)

Preparation Example 7: Synthesis of Compound 7

In Preparation Example 1, compound 7 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate D and used. (MS: [M+H] ⁺ = 666)

Preparation Example 8: Synthesis of Compound 8

In Preparation Example 1, intermediate A to intermediate D, 5H-benzo[b]carbazole to 13H-dibenzo[a,h]carbazole, 2-chloro-4,6-diphenyl-1,3,5- Preparation method of compound 1, except that triazine was changed to 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine Compound 8 was prepared in the same manner as described above. (MS: [M+H] ⁺ = 822)

[Device example]

Example 1-1

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,400Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, 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 prepared ITO transparent electrode, the following HI-A and hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. The following HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and then EB-A was thermally vacuum-deposited to a thickness of 600 Å as an electron blocking layer.

Subsequently, the compound 1 prepared in Preparation Example 1 and 2wt% of the dopant RD were vacuum deposited as a light emitting layer to a thickness of 400Å.

Subsequently, as an electron transport and injection layer, the following ET-A and Liq were thermally vacuum deposited to a thickness of 360 Å at a ratio of 1:1, and then Liq was vacuum deposited to a thickness of 5 Å.

An organic light-emitting device was manufactured by sequentially depositing magnesium and silver on the electron injection layer to a thickness of 220 Å at a ratio of 10:1 and aluminum to a thickness of 1000 Å to form a cathode.

In the above process, the deposition rate of organic matter was maintained at 0.4 to 0.7 Å/sec, the deposition rate of magnesium and silver was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 2×10 ^-7 ~ 5×10 ^-6 torr, and organic light emission. The device was fabricated.

Examples 1-2 to 1-8

Except that the host compound of the light emitting layer in Example 1-1 was changed as shown in Table 1 instead of Compound 1, Examples 1-2 to 1-8 were used in the same manner as in Example 1-1. Each organic light emitting device was fabricated.

The compounds used in the examples of Table 1 are as follows.

Comparative Examples 1-1 to 1-4

In Example 1-1, the host compound of the light emitting layer was replaced with Compound 1 Organic light emitting devices of Comparative Examples 1-1 to 1-4 were each manufactured using the same method as in Example 1-1, except that the change as shown in Table 1 was used. The compounds of RH-A, RH-B, RH-C and RH-D used in the comparative examples of Table 1 are as follows.

Experimental Example 1

By applying a current to the organic light emitting device prepared in the above Examples and Comparative Examples, the driving voltage, efficiency, and life were measured, and the results are shown in Table 1 below. At this time, the driving voltage and efficiency were measured by applying a current density of 10 mA/cm ² , and LT97 refers to the time from the current density of 20 mA/cm ² until the initial luminance decreases to 97%.

Host @ 10 mA / cm ² @ 20 mA / cm ² Voltage
(V) efficiency
(cd/A) LT97 (hr) Example 1-1 Compound 1 5.06 21.6 100 Example 1-2 Compound 2 5.09 21.3 108 Example 1-3 Compound 3 4.96 20.7 106 Example 1-4 Compound 4 4.95 20.2 103 Example 1-5 Compound 5 5.14 19.5 96 Example 1-6 Compound 6 5.16 19.8 91 Example 1-7 Compound 7 5.06 21.9 111 Example 1-8 Compound 8 5.03 22.0 113 Comparative Example 1-1 RH-A 5.23 18.1 65 Comparative Example 1-2 RH-B 7.03 8.1 26 Comparative Example 1-3 RH-C 7.38 7.3 19 Comparative Example 1-4 RH-D 8.21 4.5 5

From the results of Table 1, the organic light-emitting device of the example in which the compounds having the structure of Formula 1 were used as the host of the red light-emitting layer of the organic electroluminescent device was applied to the organic light-emitting device of Comparative Example using the compounds not having the structure of Formula 1 as a host. In comparison, it can be seen that it exhibits the characteristics of low voltage, high efficiency, and long life.

In particular, the organic light-emitting device of the above embodiment has a lower driving voltage than the organic light-emitting device each employing compounds RH-B and RH-C having only one of the triazinyl-based substituent and benzocarbazolyl-based substituent of Formula 1 It can be seen that, as well as high efficiency, it shows remarkably improved lifespan characteristics.

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

Claims (8)

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

In Formula 1,
X is each independently N or CH, provided that at least two of X are N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
R ₁ to R ₄ are each independently hydrogen or deuterium, or two adjacent two of R ₁ to R ₄ are bonded to each other to form a C _6-60 aromatic ring unsubstituted or substituted with deuterium,
R ₅ to R ₇ are each independently hydrogen or deuterium,
a is an integer from 0 to 6,
b is an integer from 0 to 3,
c is an integer from 0 to 5.
The method of claim 1,
The compound is represented by any one of the following formulas 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
R ₁ to R ₄ and R are each independently hydrogen or deuterium,
d is an integer from 0 to 4,
X, Ar ₁ , Ar ₂ , R ₅ to R ₇ , a, b and c are as defined in claim 1.
The method of claim 1,
X is all N; or
Two of X are N, the rest are CH,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently an unsubstituted or deuterium substituted C _6-20 aryl, or an unsubstituted or deuterium substituted heteroatom O or S containing C _2-60 heteroaryl,
compound.
The method of claim 4,
At least one of Ar ₁ and Ar ₂ is phenyl, or phenyl substituted with deuterium,
compound.
The method of claim 1,
a is 0 or 6,
b is 0 or 3,
c is 0 or 5,
compound.
The method of claim 1,
The compound is any one selected from the group consisting of the following compounds,
compound:

.
A first electrode; A second electrode provided to face the first electrode; And an emission layer provided between the first electrode and the second electrode, wherein the emission layer comprises a compound according to any one of claims 1 to 7. .

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