KR102342248B1 - 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 a novel compound and an organic light emitting device comprising the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

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

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

Korean Patent Publication No. 10-2000-0051826

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,

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

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing 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 _{adjacent two of R 1} to R ₄ are bonded to each other to form an unsubstituted or deuterium-substituted C _6-60 aromatic ring,

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 the compound represented by Formula 1 above.

The compound represented by Chemical Formula 1 described above may be used as a material for the organic material layer of the organic light emitting device to improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light emitting device.

1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 is 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) An example of an organic light emitting device made of

Hereinafter, it will be described in more detail to help 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.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more . For example, "a substituent in 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 in which two phenyl groups are connected.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. 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 linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. 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 is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. 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. can be However, the present invention 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 carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, 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), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aromatic ring refers to a condensed monocyclic or condensed polycyclic ring having aromaticity as a whole while including only carbon as a ring-forming atom. The number of carbon atoms of 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, a pyrene ring, and the like, 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 above-described aryl group. 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 above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heteroaryl may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description regarding heteroaryl described above may be applied, except that it is formed by combining two substituents.

(compound)

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

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, the triazinyl-based substituent serves to transport electrons and the benzocarbazolyl-based substituent serves to transport holes, so it is advantageous in balancing the balance between charge transport and charge in the light emitting layer compared to compounds not having them at the same time. In addition, compared to a compound having a structure in which two substituents are linked by another linker, the benzonaphthofuranylene linker spatially separates the two substituents, and has low triplet energy, thereby making it suitable for a red light emitting layer host. Accordingly, the voltage, efficiency, and lifespan of an organic light-emitting device employing such a compound may be improved.

The compound represented by Formula 1 is represented by any one of Formulas 1A to 1D below depending on the bonding position of the benzocarbazolyl-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 Formula 1 above.

Preferably, R ₁ to R ₄ are each independently hydrogen or deuterium; Alternatively, _{two adjacent ones of R 1} to R ₄ may combine with each other to form an unsubstituted or deuterium-substituted benzene ring.

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 combined with each other to form a benzene ring unsubstituted or substituted with deuterium, and the remainder may be hydrogen or deuterium.

In this case, the fact _{that adjacent two 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 combine with each other to form a benzene ring; or R ₃ and R ₄ are combined with each other to form a benzene ring.

Specifically, the compound may be represented by any one of the following Chemical 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 as defined in Formula 1 above,

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

Preferably, all X are N; or two of X may be N and the other may be CH.

Preferably, Ar ₁ and Ar ₂ are each independently C _{6-20 aryl unsubstituted or substituted with deuterium, or C 2-60} heteroatoms O or S comprising heteroatoms O or S unsubstituted or substituted with deuterium. may 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}

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 _{mean the number of R 5} , R ₆ and R _{7 which} are substituents in parentheses, respectively, and when a, b and c are 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 may be 0 or 6, b may be 0 or 3, and c may be 0 or 5.

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

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

.

[Scheme 1]

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

The compound represented by Formula 1 may be prepared through steps 1 to 3. Specifically, in step 1, the starting material A1 is reacted with compound A2 to prepare an intermediate compound A3 into which a substituent for a suzuki-coupling reaction is introduced. Then, in step 2, the intermediate compound A3 and compound A4 were subjected to a suzuki-coupling reaction to prepare an intermediate compound A5, and in step 3, the intermediate compound A5 and the compound A6 were subjected to an amine substitution reaction to prepare a compound represented by Formula 1 do. The amine substitution reaction and the suzuki-coupling reaction are preferably performed 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 element)

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. In one 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 an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers and a cathode are sequentially stacked on a substrate 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 a first electrode is a cathode and a second electrode is an anode can be For example, the structure of the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

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

2 is 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) 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 light emitting layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that the light emitting 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 stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or a metal oxide having conductivity or an alloy thereof is deposited on a substrate to form an anode And, after forming an organic 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 this 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.

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

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive compounds, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The electron blocking layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling by increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving 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 Chemical Formula 1 may be used. In addition, as the host material, in addition to the compound represented by Formula 1, a condensed aromatic ring derivative or a hetero ring-containing compound may be additionally used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Further, examples of the dopant material include 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, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted in the arylamine, one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is 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 the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the 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 electron mobility is suitable. Specific examples of the electron injection and transport material include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

The electron injection and transport layer may be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting 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 the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives may be used.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. The present invention is not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side 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.

The compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are intended to illustrate 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 dissolved in 300 ml of THF added, stirred and refluxed. After that, potassium carbonate (23.8 g, 171.9 mmol) was dissolved in 71 ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (1.5 g, 1.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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

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 in a nitrogen atmosphere, and the mixture was stirred and refluxed. After the reaction for 8 hours, it 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, 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, (3-chloro-2-fluorophenyl) boronic acid was changed to (4-chloro-2-fluorophenyl) boronic acid, except for using the same preparation method as the preparation method of Intermediate A Intermediate B was prepared. (MS: [M+H] ⁺ = 333)

Preparation C: Synthesis of Intermediate C

In Preparation Example A, (3-chloro-2-fluorophenyl) boronic acid was changed to (5-chloro-2-fluorophenyl) boronic acid in the same preparation method as the preparation method of Intermediate A except that it was used Intermediate C was prepared. (MS: [M+H] ⁺ = 333)

Preparation D: Synthesis of Intermediate D

In Preparation Example A, (3-chloro-2-fluorophenyl) boronic acid was changed to (2-chloro-6-fluorophenyl) boronic acid in the same preparation method as the preparation method of Intermediate A except that it was used Intermediate D was prepared. (MS: [M+H] ⁺ = 333)

Preparation Example 1: Synthesis of Compound 1

Step 1) Synthesis of compound 1-1

Intermediate A (15.0 g, 45.2 mmol) and bis(pinacolato)diborane (12.6 g, 49.8 mmol) were refluxed in 300 ml of 1,4-dioxane under nitrogen atmosphere and stirred. After that, potassium acetate (6.7 g, 67.9 mmol) was added and sufficiently stirred, bis(dibenzylideneacetone)palladium(0) (0.8 g, 1.4 mmol) and tricyclohexylphosphine (0.8 g, 2.7 mmol) were added. was put in. After the reaction for 8 hours, it 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound 1-1. (Yield 73%, MS: [M+H] ⁺ = 380)

Step 2) Synthesis of compound 1-2

In a nitrogen atmosphere, compound 1-1 (15.0 g, 39.6 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (11.7 g, 43.6 mmol) were added to 300 ml of THF, stirred and refluxed. did After that, potassium carbonate (21.9 g, 158.5 mmol) was dissolved in 66 ml of water and thoroughly stirred, and then tetrakis (triphenylphosphine) palladium (0) (1.4 g, 1.2 mmol) was added. After the reaction for 11 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-2. (Yield 64%, MS: [M+H] ⁺ = 485)

Step 3) Synthesis of compound 1

Compound 1-2 (15.0 g, 31 mmol) and 5H-benzo[b]carbazole (7.4 g, 34.1 mmol) were added to 300 ml of toluene in a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (4.5 g, 46.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) were added thereto. After the reaction for 8 hours, it 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, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 8.2 g of compound 1 was prepared through sublimation purification. (Yield 40%, MS: [M+H] ⁺ = 666)

Preparation Example 2: Synthesis of compound 2

In Preparation Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl -1,3,5-triazine, 5H-benzo [b] carbazole to 7H-dibenzo [b, g] carbazole by the same preparation method as the preparation method of Compound 1, except that it was used 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, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-chloro-4-(naphthalen-2-yl)-6-phenyl- As 1,3,5-triazine, compound 4 was prepared in the same manner as in compound 1, except that 5H-benzo[b]carbazole was changed to 6H-dibenzo[b,h]carbazole. 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, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-chloro-4-(dibenzo[b,d]furan-1- Yl)-6-phenyl-1,3,5-triazine, 5H-benzo[b]carbazole to 6H-dibenzo[b,h]carbazole Compound 6 was prepared by the same preparation method. (MS: [M+H] ⁺ = 806)

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 8: Synthesis of compound 8

In Preparation Example 1, Intermediate A to Intermediate D, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-chloro-4,6-diphenylpyrimidine, 5H-benzo [ b] Compound 8 was prepared in the same manner as in the preparation method of Compound 1, except that carbazole was changed to 13H-dibenzo[a,h]carbazole. (MS: [M+H] ⁺ = 715)

[Element example]

Example 1-1

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-A and hexaazatripheylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. Thereafter, HT-A as a hole transport layer was vacuum deposited to a thickness of 800 Å, and then EB-A as an electron blocking layer was thermally vacuum deposited to a thickness of 600 Å.

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

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

On the electron injection layer, magnesium and silver were sequentially deposited at a ratio of 10:1 to a thickness of 220 Å and aluminum to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light emitting diode.

In the above process, the deposition rate of the organic material 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 2×10 ^-7 ~ 5×10 ^-6 torr, organic light emission The device was fabricated.

Examples 1-2 to 1-8

In Example 1-1, the host compound of the light emitting layer was replaced with Compound 1 Organic light emitting devices of Examples 1-2 to 1-8 were respectively manufactured in the same manner as in Example 1-1, except for the changes as shown in Table 1.

The compounds used in Examples of Table 1 below 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 respectively manufactured in the same manner as in Example 1-1, except for the changes as shown in Table 1. The compounds of RH-A, RH-B, RH-C and RH-D used in Comparative Examples of Table 1 are as follows.

Experimental Example 1

By applying a current to the organic light emitting diodes prepared in Examples and Comparative Examples, driving voltage, efficiency, and lifespan 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 means the time until the initial luminance decreases to 97% at a current density of 20 mA/cm ^{2 .}

host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) LT97
(hr) Example 1-1 compound 1 4.92 22.6 95 Example 1-2 compound 2 4.97 21.3 98 Examples 1-3 compound 3 5.07 20.0 107 Examples 1-4 compound 4 5.11 20.3 101 Examples 1-5 compound 5 5.16 19.3 100 Examples 1-6 compound 6 5.15 19.7 103 Examples 1-7 compound 7 5.03 21.6 114 Examples 1-8 compound 8 5.07 20.9 111 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 embodiment using the compounds having the structure of Formula 1 as the host of the red light emitting layer of the organic electroluminescent device is the organic light emitting device of the comparative example using the compounds not having the structure of Formula 1 as the host. In comparison, it can be seen that it exhibits characteristics of low voltage, high efficiency, and long life.

In particular, the organic light-emitting device of the embodiment has a lower driving voltage than the organic light-emitting device employing the compounds RH-B and RH-C having only one of the triazinyl-based substituent and the benzocarbazolyl-based substituent of Formula 1, respectively, and , it can be seen that not only the efficiency is high, but also the lifespan characteristics are significantly improved.

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)

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

In Formula 1,
each X is independently N or CH, provided that at least two of X are N;
Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing 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 _{adjacent two of R 1} to R ₄ are bonded to each other to form an unsubstituted or deuterium-substituted C _6-60 aromatic ring,
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;
According to 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.
According to claim 1,
X is all N; or
two of X are N and the other are CH;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently C _{6-20 aryl unsubstituted or substituted with deuterium, or C 2-60} heteroaryl comprising heteroatoms O or S unsubstituted or substituted with deuterium;
compound.
5. The method of claim 4,
At least one of Ar ₁ and Ar ₂ is phenyl or phenyl substituted with deuterium;
compound.
According to claim 1,
a is 0 or 6,
b is 0 or 3;
c is 0 or 5;
compound.
According to 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 a light emitting layer provided between the first electrode and the second electrode, wherein the light emitting layer comprises the compound according to any one of claims 1 to 7, the organic light emitting device .

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