KR102461122B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

Description

Organic light emitting device

The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

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 layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, 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.

In the organic light emitting device as described above, the development of an organic light emitting device having improved driving voltage, efficiency, and lifespan is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

The present invention provides the following organic light emitting device:

anode,

cathode,

a light emitting layer between the anode and the cathode;

The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

X is O or S;

Y ₁ to Y ₃ are each independently CH or N, provided that at least one of Y ₁ to Y ₃ is N,

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

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; 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 _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

R ₃ are each independently hydrogen; heavy hydrogen; 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 _2-60 heteroaryl including at least one selected from the group consisting of N, O and S, or two adjacent R ₃ are bonded to each other to form a C _6-60 aromatic ring; Or to form a C _2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

a1 and a2 are each independently an integer of 0 to 3,

a3 is an integer from 0 to 8,

[Formula 2]

In Formula 2,

Ar ₃ is C _2-60 heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar ₃ includes at least one or more N,

L ₁ is a single bond; substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene comprising any one or more selected from the group consisting of N, O and S,

R ₄ is a C _6-60 aromatic ring in which two adjacent R ₄ are bonded to each other; Or to form a C _2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

R ₅ are each independently hydrogen; heavy hydrogen; 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 _2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, or two or three adjacent R ₅ are bonded to each other to C _6-60 aromatic ring; Or to form a C _2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

a4 is 2,

a5 is an integer from 0 to 6.

In the above-described organic light emitting device, by controlling a compound included in the light emitting layer, efficiency, low driving voltage, and/or lifespan characteristics may be improved in the organic light emitting device.

FIG. 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 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 transport layer 8, an electron injection layer 9 ) and an example of an organic light emitting device composed of a cathode 4 is shown.

Hereinafter, it will be described in more detail to help the understanding of the present invention. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

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; imid; amino group; 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 aryl phosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, in which two or more substituents of the above-exemplified substituents are connected . 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, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In 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 a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron 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 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 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 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 phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 6 to 30 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 6 to 20 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. 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 heterocyclic group 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 of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

The present invention provides an organic light emitting device comprising an anode, a light emitting layer, and a cathode, wherein the light emitting layer includes the compound represented by Formula 1 and the compound represented by Formula 2 above.

In the organic light emitting device according to the present invention, by controlling a compound included in the light emitting layer, it is possible to improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

Hereinafter, the present invention will be described in detail for each configuration.

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

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 polymers 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; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

In addition, a hole injection layer may be additionally included on the anode. The hole injection layer is made of a hole injection material, and the hole injection material 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 the excitons generated in the light emitting layer A compound which prevents movement 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. organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may further include a hole injection layer between the anode and a hole transport layer to be described later, if necessary.

The hole injection material is a layer for injecting holes from the electrode, and the hole injection material 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 generated in the light emitting layer A compound that prevents the excitons from moving 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. organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

The hole transport layer used in the present invention is a layer that receives holes from the hole injection layer formed on the anode or the anode and transports them to the light emitting layer. As a material with high hole mobility, it is suitable. Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

electronic barrier layer

The electron blocking layer used in the present invention is a layer placed between the hole transport layer and the emission layer in order to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the emission layer, and is also called an electron blocking layer. For the electron blocking layer, a material having an electron affinity lower than that of the electron transport layer is preferable.

light emitting layer

The light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

In general, the emission layer includes a host material and a dopant material, and may include the compound represented by Chemical Formulas 1 and 2 as hosts. The weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 may be 99:1 to 1:99, or 90:10 to 20:80, but is not limited thereto.

In the present invention, a1 represents the number of R ₁ , and when a1 is 2 or more, two or more R ₁ may be the same or different from each other. Descriptions of a2 to a5 may be understood with reference to the description of a1 and the structures of Chemical Formulas 1 and 2 above.

Preferably, Y ₁ to Y ₃ may each be N.

Preferably, Ar ₁ and Ar ₂ may each independently be a substituted or unsubstituted C _6-20 aryl,

More preferably, Ar ₁ and Ar ₂ may each independently be phenyl, phenyl substituted with 5 deuterium, or biphenylyl.

Preferably, R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-10 alkyl; substituted or unsubstituted C _3-20 cycloalkyl; substituted or unsubstituted C _6-20 aryl; Or it may be a C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, R ₁ and R ₂ may each independently be hydrogen, deuterium, or phenyl.

Preferably, each R ₃ is independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-10 alkyl; substituted or unsubstituted C _3-20 cycloalkyl; substituted or unsubstituted C _6-20 aryl; Or it may be a C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, or two adjacent R ₃ are bonded to each other to form a C _6-20 aromatic ring ; Or it may form a C _2-20 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

,

, 또는

을 형성할 수 있다.More preferably, each R ₃ is independently hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium, or two adjacent R ₃ are bonded to each other

,

, or

can form.

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

.

.

The compound represented by Formula 1 may be prepared by, for example, a preparation method such as Scheme 1-1 or Scheme 1-2, and other compounds may be prepared similarly.

[Scheme 1-1]

[Scheme 1-2]

In Schemes 1-1 and 1-2, X, Y ₁ to Y ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ and a1 to a3 are as defined in Formula 1, and Z ₁ and Z ₂ are each is independently halogen, preferably Z ₁ and Z ₂ are each independently fluoro, chloro or bromo.

The Suzuki coupling reaction in Scheme 1-1 is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. In addition, Scheme 1-2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, Formula 2 may be represented by any one of Formulas 2-1 to 2-3 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

Ar ₃ , L ₁ , R ₅ and a5 are the same as defined in Formula 2 above.

Preferably, Ar ₃ may be C _2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar ₅ includes at least one or more N do,

일 수 있고, 상기 Ar₃는 비치환되거나, 또는 페닐, 비페닐릴, 나프틸, 디메틸플루오레닐, 디벤조퓨라닐, 디벤조티오페닐 및 페닐 카바졸릴로 구성되는 군으로부터 선택되는 1개 내지 3개의 치환기로 치환될 수 있고,More preferably, Ar ₃ is quinazolinyl, benzo[h]quinazolinyl, triazinyl, pyrimidinyl, quinoxalinyl, or

may be, wherein Ar ₃ is unsubstituted, or one selected from the group consisting of phenyl, biphenylyl, naphthyl, dimethyl fluorenyl, dibenzofuranyl, dibenzothiophenyl and phenyl carbazolyl may be substituted with three substituents,

Most preferably, Ar ₃ may be any one selected from the group consisting of:

.

.

Preferably, L ₁ is a single bond; substituted or unsubstituted C _6-20 arylene; Or it may be a C _2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L ₁ may be a single bond, phenylene, naphthylene, or dibenzofuranylene.

Preferably, each R ₅ is independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-10 alkyl; substituted or unsubstituted C _3-20 cycloalkyl; substituted or unsubstituted C _6-20 aryl; Or it may be C _2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, or two or three adjacent R ₅ are bonded to each other to C _{6- 20} aromatic rings; Or it may form a C _2-20 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

,

,

,

,

,

, 또는

을 형성할 수 있다.More preferably, R ₅ is each independently hydrogen, deuterium, phenyl, carbazolyl, phenyl carbazolyl, or two or three adjacent R ₅ are bonded to each other to form a benzene ring,

,

,

,

,

,

, or

can form.

Representative examples of the compound represented by Formula 2 are as follows:

.

.

The compound represented by Chemical Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below, and other compounds may be prepared similarly.

[Scheme 2]

In Scheme 2, Ar ₃ , L ₁ , R ₄ , R ₅ , a4 and a5 are as defined in Formula 2 above, Z ₃ is halogen, and preferably Z ₃ is chloro or bromo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples 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, and periflanthene having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and 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.

electron transport layer

The organic light emitting diode according to the present invention may include an electron transport layer between the light emitting layer and the cathode.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and inhibits the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable. As the electron transport material, a material capable of well injecting electrons from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable.

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes comprising Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

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. However, the present invention is not limited thereto.

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 . FIG. 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 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 transport layer 8, an electron injection layer 9 ) and an example of an organic light emitting device composed of a cathode 4 is shown.

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned layers 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 a cathode material, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

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

Meanwhile, 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.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

[Production Example]

Preparation Example 1: Preparation of compound 1-1

Step 1) Preparation of compound 1-1-a

In a nitrogen atmosphere, 8-bromo-1-chlorodibenzo[b,d]furan (15.0 g, 53.3 mmol) and 9H-carbazole (9.8 g, 58.6 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (7.7 g, 79.9 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.6 mmol) were added. After the reaction for 6 hours, the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.0 g of compound 1-1-a. (Yield 61%, MS: [M+H]+=369).

Step 2) Preparation of compound 1-1-b

Compound 1-1-a (15.0 g, 40.8 mmol) and bis(pinacolato)diboron (11.4 g, 44.9 mmol) were stirred in 300 ml of 1,4-dioxane under reflux in a nitrogen atmosphere. After that, potassium acetate (6.0 g, 61.2 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 7 hours, cooling to room temperature, and separating the organic layer using chloroform and water, 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 11.6 g of compound 1-1-b. (Yield 62%, MS: [M+H]+=460)

Step 3) Preparation of compound 1-1

In a nitrogen atmosphere, compound 1-1-b (15.0 g, 32.7 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (9.6 g, 35.9 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (18.1 g, 130.6 mmol) was dissolved in 54 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0)(1.1 g, 1.0 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, 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, 5.5 g of compound 1-1 was prepared through sublimation purification. (Yield 30%, MS: [M+H]+= 566)

Preparation Example 2: Preparation of compound 1-2

In Preparation Example 1, 8-bromo-1-chlorodibenzo[b,d]furan to 3-bromo-7-chlorodibenzo[b,d]furan, 9H-carbazole to 2-(phenyl-d5)-9H-carbazole Compound 1-2 was prepared in the same manner as in the preparation method of compound 1-1, except that it was changed and used. (MS[M+H] ⁺ = 647)

Preparation Example 3: Preparation of compound 1-3

Step 1) Preparation of compound 1-3-a

In a nitrogen atmosphere, 1-chloro-7-fluorodibenzo[b,d]furan (15.0 g, 68 mmol) and bis(pinacolato)diboron (19.0 g, 74.8 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Thereafter, potassium acetate (10.0 g, 102.0 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1.2 g, 2.0 mmol) and tricyclohexylphosphine (1.1 g, 4.1 mmol) were added. After reacting for 7 hours, cooling to room temperature, and separating the organic layer using chloroform and water, 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 15.9 g of compound 1-3a. (yield 75%, MS: [M+H]+= 313)

Step 2) Preparation of compound 1-3b

In a nitrogen atmosphere, compound 1-3a (15.0 g, 48.1 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (14.2 g, 52.9 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (26.6 g, 192.2 mmol) was dissolved in 80 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (1.7 g, 1.4 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, 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 14.8 g of compound 1-3b. (Yield 74%, MS: [M+H]+= 418)

Step 3) Preparation of compound 1-3

In a nitrogen atmosphere, compound 1-3b (20.0 g, 47.9 mmol) and 3-phenyl-9H-carbazole (12.8 g, 52.7 mmol) were added to 400 ml of DMF and stirred under reflux. After that, cesium carbonate (46.8 g, 143.7 mmol) was added and stirred. After 10 hours of reaction, the 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, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 15.3 g of compound 1-3 was prepared through sublimation purification. (Yield 50%, MS: [M+H]+= 642)

Preparation Example 4: Preparation of compound 1-4

In Preparation Example 3, 1-chloro-7-fluorodibenzo[b,d]furan to 1-chloro-6-fluorodibenzo[b,d]furan, 2-chloro-4,6-diphenyl-1,3,5- triazine to 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine and 3-phenyl-9H-carbazole to 9H-carbazole Compound 1-4 was prepared by the same preparation method as that of compound 3, except that it was used. (MS[M+H] ⁺ = 642)

Preparation Example 5: Preparation of compound 1-5

In Preparation Example 3, 1-chloro-7-fluorodibenzo[b,d]furan to 7-chloro-1-fluorodibenzo[b,d]furan, 2-chloro-4,6-diphenyl-1,3,5- triazine to 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine and 3-phenyl-9H-carbazole to 9H-carbazole Except for the use, Compound 1-5 was prepared in the same manner as that of Compound 5. (MS[M+H] ⁺ = 642)

Preparation Example 6: Preparation of compound 1-6

Step 1) Preparation of compound 1-6-a

300 ml of toluene with 4,6-dibromodibenzo[b,d]furan-1,2,3,7,8,9-d6 (15.0 g, 45.2 mmol) and 9H-carbazole (8.3 g, 49.7 mmol) in nitrogen atmosphere was added, stirred and refluxed. Then, sodium tert-butoxide (6.5 g, 67.8 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) were added. After the reaction for 7 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then 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 14.4 g of compound 1-6-a. (Yield 76%, MS: [M+H]+= 419)

Step 2) Preparation of compound 1-6-b

Compound 1-6-a (15.0 g, 35.9 mmol) and bis(pinacolato)diboron (10.0 g, 39.4 mmol) were stirred in 300 ml of 1,4-dioxane under reflux in a nitrogen atmosphere. After that, potassium acetate (5.3 g, 53.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 8 hours, cooling to room temperature, and separating the organic layer using chloroform and water, 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 10.7 g of compound 1-6-b. (Yield 64%, MS: [M+H]+= 466)

Step 3) Preparation of compound 1-6

In a nitrogen atmosphere, compound 1-6-b (15.0 g, 32.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (9.5 g, 35.5 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (17.8 g, 128.9 mmol) was dissolved in 53 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (1.1 g, 1.0 mmol) was added. After the reaction for 8 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, 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, 8.8 g of compound 1-6 was prepared through sublimation purification. (Yield 48%, MS: [M+H]+= 572)

Preparation Example 7: Preparation of compound 1-7

Step 1) Preparation of compound 1-7-a

In a nitrogen atmosphere, 3-bromodibenzo[b,d]thiophene (15.0 g, 57 mmol) and 7H-benzofuro[2,3-b]carbazole (16.1 g, 62.7 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (8.2 g, 85.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) were added thereto. After the reaction for 6 hours, the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 1-7-a. (yield 69%, MS: [M+H]+= 441)

Step 2) Preparation of compound 1-7-b

Compound 1-7-a (10.0 g, 22.8 mmol) and 100 ml of THF were placed in a flask and cooled to -78 °C. 1.6M n-butyllithium in hexane (15.0 ml, 23.9 mmol) was added dropwise, and the mixture was stirred at -78°C for 20 minutes. Triisopropyl borate (3.1 g, 29.6 mmol) was added and stirred at -78 °C for 1 hour, followed by further stirring at room temperature for 4 hours. Then, 1N HCl was added, stirred at room temperature for 1 hour, the reaction solution was concentrated, transferred to a separatory funnel, 200 ml of H ₂ O was added, and the mixture was extracted with CH ₂ Cl ₂ . Anhydrous magnesium sulfate was added to the extract, dried, filtered, concentrated, and recrystallized to prepare 6.6 g of compound 1-7-b. (Yield 60%, MS: [M+H] ⁺ = 484)

Step 3) Preparation of compound 1-7

Compound 1-7-b (15.0 g, 31 mmol) and 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine (9.5 g, 34.1 mmol) in THF 300 ml in a nitrogen atmosphere was added, stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.1 mmol) was dissolved in 51 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0)(1.1 g, 0.9 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, 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, 9.7 g of compound 1-7 was prepared through sublimation purification. (Yield 46%, MS: [M+H] + = 682)

Preparation 8: Preparation of compound 1-8

Step 1) Preparation of compound 1-8-a

In a nitrogen atmosphere, dibenzo[b,d]thiophen-4-ylboronic acid (15.0 g, 65.8 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 72.3 mmol) were mixed with THF 300 ml, stirred and refluxed. Thereafter, potassium carbonate (36.4 g, 263.1 mmol) was dissolved in 109 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2.0 mmol) was added. After the reaction for 8 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, 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 19.7 g of compound 1-8-a. (Yield 72%, MS: [M+H]+= 417)

Step 2) Preparation of compound 1-8-b

Compound 1-8-a (20.0 g, 48.1 mmol) and N-bromosuccinimide (9 g, 50.5 mmol) were added to 400 ml of dimethylformamide in a nitrogen atmosphere and stirred at room temperature. After the reaction for 6 hours, the organic layer was separated using chloroform and water, and then 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 15.7 g of compound 1-8-b. (Yield 66%, MS: [M+H]+= 495)

Step 3) Preparation of compounds 1-8

In a nitrogen atmosphere, compound 1-8-b (15.0 g, 30.3 mmol) and 5H-benzofuro[3,2-c]carbazole (8.6 g, 33.4 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (4.4 g, 45.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) were added. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then 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, 7.9 g of compound 1-8 was prepared through sublimation purification. (Yield 39%, MS: [M+H]+= 672)

Preparation Example 9: Preparation of compound 2-1

Step 1) Preparation of compound 2-1-a

In a nitrogen atmosphere, 10-bromo-7H-benzo[c]carbazole (15.0 g, 50.3 mmol) and (9-phenyl-9H-carbazol-3-yl)boronic acid (15.9 g, 55.3 mmol) were added to 300 ml of THF. Stirred and refluxed. After that, potassium carbonate (27.8 g, 201.2 mmol) was dissolved in 83 ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0)(1.7 g, 1.5 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, 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 14.8 g of compound 2-1-a. (Yield 64%, MS: [M+H]+= 460)

Step 2) Preparation of compound 2-1

In a nitrogen atmosphere, compound 2-1-a (15.0 g, 32.7 mmol) and 2-chloro-4-phenylquinazoline (8.7 g, 36.0 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (4.7 g, 49.1 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) were added thereto. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then 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, 10.0 g of compound 2-1 was prepared through sublimation purification. (Yield 46%, MS: [M+H]+= 664)

Preparation 10: Preparation of compound 2-2

In a nitrogen atmosphere, 7H-benzo[c]carbazole (15.0 g, 69.0 mmol) and 2-([1,1'-biphenyl]-4-yl)-3-chloroquinoxaline (24.1 g, 75.9 mmol) were dissolved in 300 ml of toluene. added, stirred and refluxed. Then, sodium tert-butoxide (10.0 g, 103.6 mmol) and bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) were added. After the reaction for 6 hours, the 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, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.0 g of compound 2-2 was prepared through sublimation purification. (Yield 32%, MS: [M+H]+= 499)

Preparation Example 11: Preparation of compound 2-3

Step 1) Preparation of compound 2-3-a

2-(4-chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (15.0 g, 45.6 mmol) and 2-chloro- 4,6-diphenyl-1,3,5-triazine (13.4 g, 50.2 mmol) was added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0)(1.6 g, 1.4 mmol) was added. After the reaction for 12 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, 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 12.9 g of compound 2-3-a. (Yield 65%, MS: [M+H]+= 435)

Step 2) Preparation of compound 2-3

Compound 2-3-a (15.0 g, 34.6 mmol) and 5H-benzo[b]carbazole (8.3 g, 38.0 mmol) were added to 300 ml of toluene in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.0 g, 51.9 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) were added thereto. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then 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, 10.4 g of compound 2-3 was prepared through sublimation purification. (Yield 49%, MS: [M+H]+= 616)

Preparation 12: Preparation of compound 2-4

12,12-dimethyl-12,14-dihydrobenzo[a]indeno[1,2-h]carbazole (15.0 g, 45 mmol) and 4-([1,1'-biphenyl]-4-yl) in nitrogen atmosphere -2-chlorobenzo[h]quinazoline (18.2 g, 49.5 mmol) was added to 300 ml of toluene, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (6.5 g, 67.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) were added. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then 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, 11.3 g of compound 2-4 was prepared through sublimation purification. (Yield 38%, MS: [M+H]+= 665)

Preparation 13: Preparation of compound 2-5

1H-14-oxa-1-aza-6,7-methanodibenzo[g,ij]naphtho[2,1,8-cde]azulene (15.0 g, 49.1 mmol) and 2-chloro-4-(naphthalen) under nitrogen atmosphere -1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (18.7 g, 54.0 mmol) was added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (7.1 g, 73.7 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.5 mmol) were added thereto. After the reaction for 6 hours, the 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, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.5 g of compound 2-5 was prepared through sublimation purification. (Yield 38%, MS: [M+H]+= 617)

[Example]

Example 1

A glass substrate coated with Indium Tin Oxide (ITO) to a thickness of 1400 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 washing 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 compound HI-A and hexanitrile hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. On it, the following compound HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and then the following compound EB-A was thermally vacuum-deposited to a thickness of 600 Å as an electron blocking layer.

Then, the light emitting layer was vacuum-deposited to a thickness of 400 Å by using Compound 1-1 and Compound 2-1 as a host of the light emitting layer in a weight ratio of 50:50 and Compound RD of 2 wt% of the host as a dopant.

Then, as an electron transport and injection layer, the following compound 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 weight 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 ~ 0.7 Å/sec, the mixture of magnesium and silver at the cathode maintained the deposition rate of 0.3 Å/sec, and the aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^- An organic light-emitting device was manufactured by maintaining ⁷ to 5×10 ^-6 torr.

Examples 2 to 24

Examples 2 to 1 using the same method as in Example 1, except that the host compound of the light emitting layer in Example 1-1 was changed as shown in Table 1 instead of Compound 1-1 and Compound 2-1. Each of the organic light emitting devices of Example 24 was fabricated.

Comparative Examples 1 to 13

In Example 1, the host compound of the light emitting layer was used instead of compound 1-1 and compound 2-1. Organic light emitting devices of Comparative Examples 1 to 13 were respectively manufactured using the same method as in Example 1, except that the host was changed to a single host as shown in Table 1.

Experimental example

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 .

Example 1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage (V) Efficiency (cd/A) LT97 (hr) Example 1 compound 1-1 compound 2-1 4.41 21.6 102 Example 2 compound 1-2 4.46 21.1 98 Example 3 compound 1-3 4.42 21.8 104 Example 4 compound 1-4 4.45 21.3 101 Example 5 compound 1-5 4.49 20.8 108 Example 6 compound 1-6 4.44 21.3 97 Example 7 compound 1-7 4.46 21.2 100 Example 8 compounds 1-8 4.50 20.6 105 Example 9 compound 1-1 compound 2-2 4.33 20.2 103 Example 10 compound 1-3 4.30 20.4 106 Example 11 compound 1-5 4.34 19.6 108 Example 12 compound 1-7 4.36 20.3 110 Example 13 compound 1-2 compound 2-3 4.35 21.3 123 Example 14 compound 1-4 4.31 21.7 121 Example 15 compound 1-6 4.37 21.9 119 Example 16 compounds 1-8 4.38 21.8 118 Example 17 compound 1-1 compound 2-4 4.40 20.3 112 Example 18 compound 1-2 4.47 20.4 103 Example 19 compound 1-3 4.43 20.9 111 Example 20 compound 1-4 4.41 20.1 108 Example 21 compound 1-5 compound 2-5 4.38 20.4 113 Example 22 compound 1-6 4.37 21.3 91 Example 23 compound 1-7 4.41 21.8 114 Example 24 compounds 1-8 4.60 20.9 107 Comparative Example 1 compound 1-1 - 6.21 7.3 10 Comparative Example 2 compound 1-2 6.33 8.4 31 Comparative Example 3 compound 1-3 6.08 6.7 22 Comparative Example 4 compound 1-4 6.17 6.5 18 Comparative Example 5 compound 1-5 6.72 7.0 36 Comparative Example 6 compound 1-6 6.93 7.9 10 Comparative Example 7 compound 1-7 6.12 8.1 37 Comparative Example 8 compounds 1-8 6.90 7.8 24 Comparative Example 9 compound 2-1 5.23 18.1 65 Comparative Example 10 compound 2-2 5.41 16.3 71 Comparative Example 11 compound 2-3 4.92 19.3 78 Comparative Example 12 compound 2-4 5.10 17.1 63 Comparative Example 13 compound 2-5 5.42 16.1 59

From the results of Table 1, the organic light emitting device of the Example using the compound having the structure of Formula 1 and the compound having the structure of Formula 2 as a light emitting layer host at the same time compared to the organic light emitting device of Comparative Example using each compound alone as a host It was confirmed that it exhibits the characteristics of low voltage, high efficiency, and long life.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: electron transport layer
9: electron injection layer

Claims (11)

anode,
cathode,
a light emitting layer between the anode and the cathode;
The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Formula 1,
X is O or S;
Y ₁ to Y ₃ are each independently CH or N, provided that at least one of Y ₁ to Y ₃ is N,
Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl,
R ₁ and R ₂ are each independently hydrogen, deuterium, or phenyl;
R ₃ is each independently hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium, or two adjacent R ₃ are bonded to each other

,

, or

to form,
a1 and a2 are each independently an integer of 0 to 3,
a3 is an integer from 0 to 8,
[Formula 2]

In Formula 2,
Ar ₃ is C _2-60 heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar ₃ includes at least one or more N,
L ₁ is a single bond; substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene comprising any one or more selected from the group consisting of N, O and S,
R ₄ is a C _6-60 aromatic ring in which two adjacent R ₄ are bonded to each other; Or to form a C _2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
R ₅ are each independently hydrogen; heavy hydrogen; 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 _2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, or two or three adjacent R ₅ are bonded to each other to C _6-60 aromatic ring; Or to form a C _2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
a4 is 2,
a5 is an integer from 0 to 6.
According to claim 1,
Y ₁ to Y ₃ are each N,
organic light emitting device.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, phenyl substituted with 5 deuterium, or biphenylyl;
organic light emitting device.
delete delete According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
Formula 2 is represented by any one of the following Formulas 2-1 to 2-3,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,
Ar ₃ , L ₁ , R ₅ and a5 are the same as defined in claim 1.
According to claim 1,
Ar ₃ is quinazolinyl, benzo [h] quinazolinyl, triazinyl, quinoxalinyl, pyrimidinyl, or

ego,
Wherein Ar ₃ is unsubstituted or 1 to 3 substituents selected from the group consisting of phenyl, biphenylyl, naphthyl, dimethyl fluorenyl, dibenzofuranyl, dibenzothiophenyl and phenyl carbazolyl substituted,
organic light emitting device.
According to claim 1,
L ₁ is a single bond, phenylene, naphthylene, or dibenzofuranylene,
organic light emitting device.
According to claim 1,
R ₅ is each independently hydrogen, deuterium, phenyl, carbazolyl, phenyl carbazolyl, or adjacent two or three R ₅ are bonded to each other to form a benzene ring,

,

,

,

,

,

, or

to form,
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

.

Images