WO2018101691A1 - Organic light-emitting element - Google Patents

Abstract

The present invention provides an organic light-emitting element having improved driving voltage, effectiveness and lifespan.

Description

 [Name of invention]

 Organic light emitting device

 Technical Field

 Cross Citation with Related Application (s)

 This application is filed with the Korean Patent Application No. 10-2016- filed on November 29, 2016.

It claims the benefit of priority based on the 01603 and Korean Patent Application No. 10-2017-0154011 dated November 17, 2017, and all the contents disclosed in the literature of those Korean patent applications are incorporated as part of this specification. The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifetime.

 Background Art

 In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy 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, and fast response time. Many studies have been conducted because of excellent luminance, driving voltage, and stepping speed characteristics. The organic light emitting device generally has a structure including an anode and a cathode and an organic 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. It may be composed of an electron transport layer, an electron injection layer and the like. When the voltage is applied between the two electrodes in the structure of the organic light emitting diode, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes meet the electrons. When the axtone falls back to the ground, it glows. In the organic light emitting device as described above, there is a continuous demand for the development of an organic light emitting device having improved driving voltage, efficiency and lifetime.

Prior Art Documents [Patent Documents]

 (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

 [Content of invention]

 [Problem to solve]

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

 [Measures of problem]

 The present invention provides the following organic light emitting device:

 cathode; anode; And at least one light emitting layer between the cathode and the anode,

 The emission layer includes a first host compound represented by the following Chemical Formula 1 and a second host compound represented by the following Chemical Formula 2,

 Organic light emitting device:

 In Chemical Formula 1,

¾ is substituted or unsubstituted d-60 alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Substituted or unsubstituted C _{6 -60} aryl; Or substituted or unsubstituted 0, N. C _{2 -60} heteroaryl comprising at least one of Si and S,

¾ and R ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted alkyl; Or substituted or unsubstituted C _{3 -60} cycloalkyl, n is an integer from 0 to 4,

 m is an integer of 0 to 3,

Y is 0, S, or CR ₄ R ₅ ,

R ₄ and ¾ are each independently hydrogen; heavy hydrogen; halogen; Cyano; substitution Or unsubstituted d-60 alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Or substituted or unsubstituted C _{6 -60} aryl,

 Ar is represented by the following formula 1 ',

L is a single bond; A substituted or unsubstituted C ₆ - ₆₀ arylene; Or C ₂ — ₆₀ heteroarylene including one or more of 0, N, Si, and substituted or unsubstituted,

Xi to ¾ are each independently N, or CR ₆ , provided that at least one of ¾ is N,

Each R ₆ is independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted d— ₆₀ alkyl; Substituted or unsubstituted d-60 haloalkyl; Substituted or unsubstituted d-60 haloalkoxy; 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 0, N. C _{2 -60} heteroaryl comprising at least one of Si and S,

An and Ar ₂ are each independently substituted or unsubstituted C _{6 -60} aryl; Or substituted or unsubstituted C _{2 -60} heteroaryl including one or more of 0, N, Si, and S,

 [Formula 2]

 In Formula 2

R 'r ^ substituted or unsubstituted C ₆ -60 aryl, R ' ₂ and R' ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted d-60 alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Substituted or unsubstituted C _{6 -60} aryl; Or substituted or unsubstituted C _{2 -60} heteroaryl including one or more of 0, N, Si, and S,

 n 'and m' are each independently an integer of 0 to 4,

L 'is a single bond; And ₆₀ arylene, substituted or unsubstituted C ₆

 Y 'is 0, S, NR', or CR'R ",

R ′ and R ″ are each independently substituted or unsubstituted d-eo alkyl; substituted or unsubstituted C _{3 -60} cycloalkyl; substituted or unsubstituted C _{6 -60} aryl; or substituted or unsubstituted 0, C _{2 -60} heteroaryl comprising at least one of N, Si and S, or R 'and R''together form a substituted or unsubstituted C _{6 -60} aromatic ring.

 [Effects of the Invention]

 The organic light emitting device described above is excellent in driving voltage, efficiency and lifespan.

 [Brief Description of Drawings]

 FIG. 1 shows an example of an organic light emitting element consisting of 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, and a light emitting layer 7. The example of the organic light emitting element which consists of the electron carrying layer 8 and the cathode 4 is shown.

 [Specific contents to carry out invention]

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

In this specification. Means a bond connected to another substituent. As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; .Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, 0 and S atoms. It means that the substituted or unsubstituted two or more substituents of the substituents exemplified above. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent to which two sonyl groups are linked. Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, 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 carbon number of the imide group is not particularly limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group. Propyl dimethyl silyl group, triphenyl silyl group. Diphenylsilyl group, phenylsilyl group and the like, but is not limited thereto. In the present specification, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, etc. It is not limited to this. Examples of halogen groups in the present specification include fluorine, chlorine, bromine and iodine. In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n ᅳ Pentyl, isopentyl, neopentyl, tert-pentyl, nuclear chamber, n-nuclear chamber, 1-methylpentyl. 2-methylpentyl, 4-methyl-2-pentyl, 3,3—dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl. 1-methylnuclear chamber ， Cyclopentylmethyl, cyclonukylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylnuclear, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl ᅳ 1, 1-dimethyl-propyl, isonuclear chamber, 2'methylpentyl, 4-methylnuclear chamber, 5-methylnuclear chamber, and the like, but is not limited thereto. In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl and isopropenyl. 1-butenyl, 2′butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3 ᅳ methyl—1-butenyl, 1, 3-butadienyl, allyl, 1- Phenylvinyl-1-yl, 2—phenylvinyl-1-yl, 2, 2-diphenylvinyl-1-yl, 2-phenyll.2- (naphthyl-1-yl) vinyl-1-yl, 2 , 2-bis (diphenyl-1-yl) vinyl— 1-yl, stilbenyl group, styrenyl group, and the like, but is not limited to these. In the present specification _; The cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl. Cyclonuclear chamber, 3-methylcyclonuclear chamber, 4 'methylcyclonuclear chamber, 2,3-dimethylcyclonuclear chamber, 3, 4, 5-trimethylcyclonuclear chamber, 4-tert-butylcyclonuclear chamber, cycloheptyl, cyclooctyl, etc. It is not limited to this. 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 aryl group has 6 to 30 carbon atoms. Work According to the exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. In the case of the fluorenyl group,

And so on. However, the present invention is not limited thereto. In the present specification, the heterocyclic group is a heterocyclic group containing one or more of 0, N, Si, and S as a dissimilar element, and the number of carbons is not particularly limited, but it is preferable that the number of carbon atoms? To 60. Examples of the heterocyclic group are thiophene group, furan group, pyrrole group. Imidazole group, thiazole group, oxazole group oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group Quinoxalinyl group, pragurazinyl group, pyrido pyrimidinyl group pyrido pyrazinyl group. Pyrazino pyrazinyl groups. Isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group benzofuranyl group, phenanthrol group (phenanthrol ine), iso An oxazolyl group thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group, etc. are mentioned, but it is not limited to these. In the present specification, an aralkyl group and an aralkenyl group. The aryl group in an alkylaryl group and an arylamine group is the same as the example of the aryl group mentioned above. In the present specification, the alkyl group of the aralkyl group, alkylaryl group, alkylamine group of the alkyl group described above Same as the example. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, except that the arylene is a divalent group, the description of the aryl group described above may be applied. In the present specification, except that the heteroarylene is a divalent group, the description of the aforementioned heterocyclic group may be applied. In the present specification, the hydrocarbon ring is not a monovalent group, and the description about the aryl group or cycloalkyl group described above may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding. The present invention provides the following organic light emitting device:

 cathode; anode; And at least one emission layer between the cathode and the anode, wherein the emission layer includes a first host compound represented by Formula 1 and a second host compound represented by Formula 2. Hereinafter, the present invention for each configuration will be described in detail. Cathode and anode

The anode and cathode used in the present invention means an electrode used in the organic light emitting device. As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, rhythm oxide, tin oxide (Π (), indium zinc oxide (IZ0); ΖηΟ: A1 or SN0 ₂ : A combination of a metal and an oxide such as Sb; Poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene KPED0T), polypy and Conductive polymers such as polyaniline, and the like, but are not limited thereto. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or Li / Al, and the like, but are not limited thereto. In addition, a hole injection layer may be further included on the anode. The hole injection layer is made of a hole injection material, has a capability of transporting holes as a hole injection material has a hole injection effect at the anode, excellent hole injection effect to the light emitting layer or the light emitting material, and The compound which prevents the movement to an electron injection layer or an electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injecting materials include metal porphyr, ligothiophene, arylamine-based organics, nucleonitrile-nuclear azatriphenylene-based organics, and quinacridone-based organics, perylene (perylene) organic materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto. Light emitting layer

The light emitting layer according to the present invention includes a first host compound represented by Chemical Formula 1 and a second host compound represented by Chemical Formula 2. Preferably, Formula 1 is represented by the following Formula 1-1, -2, or 1-3 Is displayed:

 Preferably, ¾ is phenyl; Or biphenylyl. Preferably, ¾ and ¾ are hydrogen.

Preferably, Y is S or 0. Preferably, L is a single bond or phenylene. Preferably, A and Ar ₂ are each independently phenyl, phenyl substituted with cyano, biphenylyl, dimethylfluorenyl. Naphthyl, phenanthrenyl, pyridinyl, dibenzofuranyl, or dibenzothiophenyl. Representative examples of the compound represented by Formula 1 are as follows.





The compound represented by Formula 1 may be prepared by, for example, the same method as in Banung Formula 1 below.

(Step 1-2) Scheme 1 is a Suzuki coupling reaction, where each reaction is palladium It is preferable to carry out in the presence of a catalyst and a base, and the reaction group for Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in the production examples to be described later. In Chemical Formula 2, preferably,? Is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthreryl, triphenylenyl, dimethylfluorenyl, pyridinyl, di-substituted with cyclonuclear chamber, phenyl, cyano Benzofuranyl, dibenzothiophenyl or 9-phenyl-carbazolyl. Preferably, n 'is 1 and R'2 is hydrogen or phenyl. Preferably, m 'is one. R'3 is hydrogen. Tert-butyl, cyano, phenyl, phenyl substituted by cyano, or pyridinyl. Preferably, γ 'is 0, S, or NR', and R 'is phenyl or biphenylyl. Preferably, Y 'is CR'R ", R' and R" are methyl, or R 'and R "together form a fluorene ring. Preferably, L' is a single bond, or phenylene Representative examples of the compound represented by Formula 2 are as follows: 61

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The reaction form 2 is a Suzuki coupling reaction, each reaction is preferably carried out in the presence of a paralysis catalyst and a base, the reaction group for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in the production examples to be described later. Preferably, the weight ratio of the first host compound and the second host compound is 1:99 to 99: 1. In addition, the light emitting layer may include a dopant material in addition to the host compound. The dopant material is not particularly limited as long as it is used in an organic light emitting device, and examples thereof include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and the styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted in the substituted arylamine .

As the compound, a substituent selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group is substituted or unsubstituted. Specifically, styryl amine, styryl diamine, styryl triamine, styryl tetraamine and the like, but is not limited thereto. In addition, the metal complex includes an rhythm complex and a platinum complex, but are not limited thereto. Other floor

 In addition, the organic light emitting device according to the present invention may include a hole injection layer, a hole transport layer, an electron transport layer, and / or an electron transport layer, if necessary. The hole injection layer is a layer for injecting holes from the electrode, the hole injection material has the ability to transport holes to have a hole injection effect at the anode, has an excellent hole injection effect to the light emitting layer or the light emitting material, The compound which prevents the excitons from moving to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. It is preferable that the HOMOOiighest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injecting materials include metal porphyr (in), oligothiophene, arylamine-based organics, nucleonitrile-nucleated azatriphenylene-based organics, quinacridone-based organics, and perylene ) Organic materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto. The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. The hole transport layer is a material that can transport holes from an anode or a hole injection layer to a light emitting layer. This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.

22

SUBSTITUTE SHEET RULE 26 RO / KR .

The electron transport layer is a layer that receives electrons from the electron injection layer or the cathode and transports the electrons to the light emitting layer, and the electron transport material is a material that can inject electrons well from the cathode to the light emitting layer and has high mobility to the electrons. The material is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically, it is sesame, barium, kalmsium ytterbium and samarium, each followed by an aluminum or silver layer. The electron injection layer is a layer for injecting electrons from an electrode, has a capability of transporting electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or the light emitting material, and the hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole oxadiazole, triazole, ^• imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto. Examples of the metal complex compound include 8-hydroxyquinolinatolium, 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) ( 0-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphlato) aluminum, bis (2-methyl-8-quinolinato) (2-naphlato) gallium, etc. However, the present invention is not limited thereto.

23

SUBSTITUTE SHEET RULE 26 RO / KR Organic light emitting device

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 insect includes a first host and a second host. 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. In this case, a metal oxide or a metal oxide having a conductivity on the substrate or a metal oxide on the substrate using a method of physical vapor deposition (PVD), such as sputtering or e-beam evaporation Deposit an alloy to form an anode. After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and / or an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to the above 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. The first host compound and the second host compound may be formed as a light emitting layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading ink ink printing, screen printing, spray method, coating coating, but is not limited to these. 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 on a substrate from a cathode material (TO 2003/012890). However, the manufacturing method is not limited thereto. The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used. Hereinafter, preferred examples will be presented to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

[Production example]

 A-2 A-3 A

 Step 1) Preparation of Compound A-1

3 il bromobenzene-1,2-diol (100 g, 529 隱 ol) and cyclonucleanone (54.5 g, 555 隱 ol) were added to toluene, followed by engraving. Phosphorus trichloride (PC1 ₃ ) (29 g, 211.7 mniol) was slowly added at 0 ^° C and stirred at room temperature. When the reaction was completed, the reaction was added to excess water, extracted with chloroform, washed with saturated aqueous sodium hydrogen carbonate solution, the organic layer was separated, slurried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Nucleic acid was added to the concentrated compound, followed by stirring. The resulting solid was filtered to give Compound A-K92.6 g, yield 65%). Step 2) Preparation of Compound A-2

100 g of Compound A-K, 371) ol) and (2-chloro-6 페닐 fluorophenyl) boronic acid (68 g, 390 睡 ol) were added to 1000 mL of tetrahydrofuran, followed by stirring. 2M aqueous potassium carbonate solution (aq. K ₂ C0 ₃ ) (370 mL, 743 隱 ol) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (4.3 g, 1 mol%) was added 6 It was stirred at reflux for an hour. After completion of the reaction, lower the temperature to room temperature and remove the water layer. The organic layer was removed under reduced pressure, the concentrated compound was dissolved in 500 mL of chloroform, washed with water, separated, and the organic layer was filtered with anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure and slurried with an excess of nucleic acid and a small amount of ethyl acetate to prepare Compound A-2 (86.5 g, yield 73%). Step 3) Preparation of Compound A-3

 Compound A-2 (60 g, 188 μl ol) was dispersed in 200 mL of N-methyl-2-pyridone. 60 mL of hydrochloric acid was added to warm. After reacting for about 2 hours, the mixture was cooled to room temperature, poured into 1 L of water, and extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate, and then washed once more with water. The organic insects were slurried with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Excess nucleic acid was added to the concentrated compound to produce a solid, which was filtered to prepare Compound A-3 (36 ᅳ 4 g, yield 81%). Step 4) Preparation of Compound A

Compound A-3 (50 g, 210 Pa) was added to 100 mL of N-methyl-2-pyridone in a nitrogen atmosphere, followed by stirring. Then potassium carbonate (58 g, 420 誦 o!) Was added and then heated to 80 ^° C and stirred. After the reaction was completed, the silver was lowered to silver, and the reaction product was poured into 1 L of water and extracted with ethyl acetate. The extracted mixture was poured into anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The concentrated compound was purified by silica column chromatography with nucleic acid and ethyl acetate to give the compound A (34.4 g, yield 75%).

MS: [M + H] + = 219 Preparation Example 2 Preparation of Intermediate B

B-3 ^a

 Intermediate compound B was prepared in the same manner as in the preparation of intermediate A using compound A-1 and (5-chloro-2-fluorophenyl) boronic acid. Preparation Example 3 Preparation of Intermediate C

Using the compound A-1 and (4-chloro-2—fluorophenyl) boronic acid, the experiment was carried out in the same manner as in the preparation of A, to prepare the intermediate compound C. Preparation Example 4 Preparation of Intermediate D

 D-3

 Step 1) Preparation of Compound D-1

(2，4 ᅳ dichlorophenyl) boronic acid (100 g, 524 隱 ol) and 2-bromo-6-iodoaniline (234 g, 785.5 隱 ol) were added to 1500 mL of toluene, followed by potassium carbonate (217 g, 1517 μl) was dissolved in 500 mL of water, and tetrakistriphenylphosphinopall [Pd (PPh ₃ ) ₄ ] (30.3 g, 5 mol¾>) was added thereto, followed by heating to reflux. After completion of the reaction, the temperature was lowered to room temperature, the water worms were removed, the organic worms were concentrated under reduced pressure, and the concentrated compound was dissolved in 500 mL of chloroform and treated with anhydrous magnesium sulfate: and filtered. The filtrate was concentrated under reduced pressure, and purified by silica column chromatography with nucleic acid and ethyl acetate to obtain Compound D-1 (101.3 g, 61% yield). Step 2) Preparation of Compound D-2

Compound D— l (101 g, 319.5 μl ol) was added to methane and the temperature was reduced to 0 ^° C. in cone. HC1 was slowly added dropwise. Sodium nitrite (NaN0 ₂ ) (22 g. 319.5 隱 ol) was slowly added dropwise while cooling, followed by potassium thiocyanate (KSCNK99.3 g, 1022 瞧 ol) and iron chloride (FeCl ₃ ) (36.3 g, 223.6 mmol). Was added and stirred at room temperature. After completion of the reaction, the mixture was neutralized with an aqueous 2 M NaOH solution. The mixture was extracted with chloroform, separated, dried over anhydrous magnesium sulfate, concentrated, and purified through a silica column to give compound D-2 (79 g, 69% yield). .

Step 3) Preparation of Compound D-3

Compound D-2 (79 g, 220 μL) was added to tetrahydrofuran, cooled to 0 ^° C, and slowly added dropwise to lithium aluminum hydride (LiAlH4) (1 M in THF) (240 mL, 240 mmol) and stirred It was. When the reaction was completed, water was slowly added thereto and stirred. Then, 2 M HC1 aqueous solution was added thereto, and extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain compound D-3 (64 g, yield 87%). Step 4) Preparation of Compound D

Compound D-3 (64 g, 191 mmol) was added to an acetonitrile solvent, cesium carbonate (93.7 g, 287.6 mmol) was added, and the mixture was stirred at 130 ^° C with microwave irradiat ion. After the reaction was completed, washed twice with water, extracted with chloroform and the organic layer was stirred with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The concentrated compound was purified through a silica column to give intermediate compound D (47 g, 83% yield).

S: [+ H] ⁺ = 296

 29

SUBSTITUTE SHEET RULE 26 RO / KR .

Step 1) Preparation of Compound 1-1-1

Compound A (21 g, 95 μL) was dispersed in 200 mL of acetonitrile, potassium carbonate (26.3 g, 190 mmol) and 40 mL of water were added thereto, and nonafluorobutanesulfonyl fluoride (43 g, 142.5 μL) was added. ol) was added and warmed to 80 ^° C. After reaction for 6 hours, the mixture was cooled to room temperature and the solvent was removed by concentration under reduced pressure. The concentrated compound was dissolved in ethyl acetate and washed once with water. The organic layer was separated, treated with anhydrous magnesium sulfate, filtered and concentrated to prepare compound 1-1-1 (35.1 g, yield 73%). Step 2) Preparation of Compound 1-1-2

 Compound 1-1-1 (27 g, 54 mmol), Bis (pinacolato) diborone (16.4 g, 64.7x01), Potassium acetate (10.5 g, 107 mmol ) Was added to 150 mL of 1,4-dioxane, and dibenzylideneacetonepalladium (0.9 g, 3 mol%) and tricyclonucleosilphosphine (0.9 g, 6 mol%) were added under reflux stirring for 12 hours. It was stirred at reflux. After completion of the reaction, the mixture was cooled to room temperature and filtered through celite. The filtrate was concentrated under reduced pressure, chloroform was added to the residue, and the residue was dissolved, washed with water to separate an organic layer, and dried over anhydrous magnesium sulfate. This was filtered and distilled under reduced pressure, and stirred with ethyl acetate and ethanol to give compound 1-1 '2 (15.2 g, yield 86 «.) Step 3) Preparation of compound 1—1-3

Compound 1-1-2 (25 g, 76 mmol) and 2-chloro-4, 6-diphenyl-1,3, 5-triazine (20.3 g, 76 mmol) were dispersed in 200 mL of tetrahydrofuran. 2 M aqueous potassium carbonate solution (aq. K ₂ C0 ₃ ) (57 mL, 114 μl) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (0.88 g, 1 mol «) was added. The mixture was stirred under reflux for 6 hours, cooled to 6 ° C. The aqueous layer was separated, the aqueous layer was separated, and the organic layer was concentrated under reduced pressure, and the concentrated compound was dissolved in ethyl acetate, washed twice with water, separated, anhydrous magnesium sulfate, filtered and concentrated. A small amount of ethyl acetate and excess nucleic acid are added to the concentrated residue.

30

SUBSTITUTE SHEET RULE 26 RO / KR .

The mixture was added and stirred to precipitate a solid. The mixture was stirred for 1 hour, and then filtered to prepare compound 1-1-3 (26.7 g, yield 81%). Step 4) Preparation of Compound 1-1

Compound 1-1-3 (22 g, 50 μl ol) and (9-phenyl-9H-carbazol-3-yl) boronic acid (15.2 g, 53 mmol) were dispersed in tetrahydrofuran (200 mL) , 2 M aqueous potassium carbonate solution (aq. K ₂ C0 ₃ ) (75 mL, 151 μl) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (0.6 g, 1 mol%) was added. After stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, concentrated under reduced pressure, ethyl acetate was added thereto, the mixture was stirred for 3 hours, and the precipitated solid was filtered. The obtained solid was dissolved in chloroform again, washed with water, separated, treated with anhydrous magnesium sulfate and acid clay, and filtered. The filtrate was concentrated under reduced pressure to remove about half, and then ethyl acetate was added to the compound .1-1 (26.3 g, yield 81%) through recrystallization.

MS: [M + H] ⁺ = 641

 Using Compound B, Compound 1-2 was prepared in the same manner as in Preparation Example of Compound 1-1.

MS: [M + H] ⁺ = 641

 31

SUBSTITUTE SHEET RULE 26 RO / KR .

In the same manner as in the preparation of compound 1-1 using compound C

Compound 1-3 was prepared.

MS: [M + H] ⁺ = 641

 Using Compound D, the same experiment as in Preparation Example of Compound 1-1 except for Step 1 of Example 1, was carried out to prepare Compound 1-4.

S: [M + H] ⁺ = 657

32

SUBSTITUTE SHEET RULE 26 RO / KR

 Step 1) Preparation of Compound 2— 1-1

3-bromo-9H-carbazole (15 g, 61 μl ol) and (9-phenyl-9H-carbazol-3-yl) boronic acid (18.4 g, 64 μl ol) are dispersed in 150 iii L of tetrahydrofuran After addition, 2 M aqueous carbonic acid: aqueous potassium solution (aq. K ₂ CO ₃ ) (60 mL, 120 miio) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (1.03 g. 1 mo) was added. The mixture was stirred at reflux for 8 hours. When the reaction was completed, the temperature was lowered to room temperature, the water worms were removed, the organic worms were concentrated under reduced pressure, and ethyl acetate was added thereto and stirred. The resulting solid was filtered to give compound 2-1-1 (30 g, yield 82%). Step 2) Preparation of ^"Compound 2-1

Dissolve compound 2-1-1 (12 g, 30 μl) and 2-bromo-9-phenyl-9H-carbazole (9.5 g, 30 mmol) in 150 mL of toluene. Side (5.6 g, 59 mmol) was added to warm. Bis (tri-butylphosphine) palladium (0.15 g, 1 mol%) was added thereto, and the mixture was stirred under reflux for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, and the produced solid was filtered. The pale yellow solid is dissolved in chloroform and washed twice with water. After that, the organic layer was separated, anhydrous magnesium sulfate and acidic clay were added thereto, stirred, and filtered and concentrated under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to give the compound 2-1 (14.5 g, 76% yield) as a white solid compound.

MS: [M + H] ⁺ = 650

 9-([1,1'-biphenyl] -3-yl) -3-bromo- -carbazole (16 g, 40 ol) 9- ([1,1'-biphenyl]-3-yl) -911—carbazol-3-yl) boronic acid (14.6 g, 40 mmol) was tested in the same manner as in the preparation of compound 2-1-1 to give compound 2-2 (19.7 g, yield 77%). Prepared.

MS: [M + H] ⁺ = 637

 Using the compound 2-1-1 (20 g, 49 ol) and 2-bromo [b, d] thiophene (12.9 g, 49 mmol) in the same manner as in the preparation of compound 2-1 Compound 2-3 (23.1 g, yield 80%) was prepared.

MS: [M + H] ⁺ = 591 Experimental Example

 Experimental Example 1

A glass substrate coated with a thin film of I0 (indium t in oxide) having a thickness of 1, 300 A was placed in distilled water in which a detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water was filtered secondly with a filter (Fi lter) of Millipore Co., Ltd. (MU l ipore Co.). After washing IT0 for 30 minutes, the ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water was washed, isopropyl alcohol, acetone, and methane were ultrasonically washed with a solvent, dried, and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator. The following HI-1 compound was thermally vacuum deposited to a thickness of 50 A on the πΌ transparent electrode prepared as above to form a hole injection layer. A hole transport layer is formed by thermal vacuum deposition of the following HT-—1 compound at a thickness of 250 A on the hole injection layer; and an electron blocking layer is formed by vacuum deposition of the following HT-2 compound at a thickness of 50 A on a HT-1 deposition film. It was. Subsequently, the above-described compound 1-1 and the above-described compound 2-1 were deposited on the HT-2 deposited film by co-evaporation at the weight ratio of Table 1 below, wherein the weight ratio of Table 1 (1; Compound 1-1) , Compound 2-1, and YGD compound) were co-deposited as a phosphorescent dopant to form a light emitting layer having a thickness (400A) of Table 1 below. The following ET-1 compound was vacuum deposited to a thickness of 250 A on the light emitting layer, and the following ET-2 compound was co-deposited with Li in a 2% weight ratio to a thickness of 100 A to form an electron transporting layer and an electron injection layer. Aluminum was deposited to a thickness of 1000 A on the electron injection layer to form a cathode.

The deposition rate of the organic material in the above process, 0.4 to 0.7 A / sec: was maintained, aluminum is 2 A / sec was maintained at a deposition rate of, During the deposition, a vacuum 1 X 10- ⁷ - 10- ⁸ torr maintain 5X It was. Experimental Examples 2 to Ί

 Prepared in the same manner as in Experimental Example 1. An organic light emitting diode was manufactured according to the same method as Experimental Example 1, except that the phosphorescent host material and the dopant content were changed as shown in Table 1 when forming the emission layer. Comparative Experimental Examples 1 to 10

The organic light emitting device was manufactured by the same method as Experimental Example 1, except that the phosphorescent host material and the dopant content were changed as in Table 1 when forming the emission layer. Each was produced. The host materials A to C used at this time are as follows.

The current was applied to the organic light emitting diodes manufactured in the Experimental Example and Comparative Experimental Example, and the voltage, efficiency, brightness, color coordinate, and lifetime were measured, and the results are shown in Table 1 below. In this case, T95 means the time required to reduce the luminance to 95% when the initial luminance at the current density of 50 niA / cm ² is 100%.

Table 11

 Voltage efficiency) 1 A∑r

 (V) (Cd / A)

 (x.y)

(@ 10mA / cm ² ) (@ 10mA / cm ² )

 (Compound 1-1: Compound 2- Experimental Example 1 D / YGD 3.73 23.8 (0.470, 0.522) 138

 (200: 200) / 15%

 (Compound 1-1: Compound 2)

 Experimental Example 2 3) / YGD 3.37 22.8 (0.469,0..523) 150

 (120: 280) / 12%

 (Compound 1-2: Compound 2 一

 Experimental Example 3 D / YGD 3.58 24.0 (0.464.0.527) 118

 (200: 200) / 15%

 (Compound 1-2: Compound 2- Experimental Example 4 3) / YGD 3.78 24.7 (0.455,0.537) 131

 (280: 120) / 12%

 (Compound 1-3: Compound 2 一

 Experimental Example 5 D / YGD 3.69 24.4 (0.460.0.532) 134

 (200 ： 200) / 12%

 (Compound 1-3: Compound 2- Experimental Example 6 3.49 24.0 (0.462, 0.529) 90

2) / YGD

[Explanation of code]

 1 ： Substrate 2: 2 ：

 ᄋ ᅳ ᄋ That

3: light emitting layer 4: ^" α ^{" a}

5 ： ^^^ Tzu is very small.

 7 ： ᄇ "Tsu

 s 3 ᄋ 8 ： Electron Transport Layer

Claims

[Patent Claims]

 [Claim 1]

 cathode; anode; And at least one light emitting insect between the cathode and the anode,

 The emission layer includes a first host compound represented by Formula 1 and a second host compound represented by Formula 2,

 Organic light emitting device:

 In Chemical Formula 1,

¾ is substituted or unsubstituted d-60 alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Substituted or unsubstituted C ₆ — _{6 ′} aryl; Or substituted or unsubstituted C _{2 -60} heteroaryl containing one or more of 0, N, Si, and S,

R ₂ and R ₃ are each independently hydrogen; Deuterium; halogen; Cyano; Substituted or unsubstituted d-eo alkyl; Or substituted or unsubstituted C _{3 -60} cycloalkyl, n is an integer from 0 to 4,

 m is an integer of 0 to 3,

Y is 0, S, or CR ₄ R ₅ ,

R ₄ and ¾ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted d-so alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Or substituted or unsubstituted C _{6 -60} aryl,

 Ar is represented by the following Chemical Formula 1 ′,

[Formula Γ]

L is a single bond; Substituted or unsubstituted C ₆ — ₆₀ arylene; Or substituted or unsubstituted C _{2 -60} heteroarylene comprising one or more of 0, N, Si and S,

Xi to ¾ are each independently N or CR ₆ , provided that at least one of d to ¾ is N,

Each ¾ is independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted d-60 alkyl; Substituted or unsubstituted ₍₆₀ haloalkyl ring; a substituted or unsubstituted d- ₆₀ haloalkoxy; a substituted or unsubstituted C ₃ - ₆₀ cycloalkyl; substituted or unsubstituted C ₂ - ₆₀ alkenyl al .; Chi ring or unsubstituted Substituted C ₆ — _{6 ′} aryl; or C _{2 -60} heteroaryl including one or more of substituted or unsubstituted 0, Ν, Si, and S,

An and Ar ₂ are each independently substituted or unsubstituted C _{6 -60} aryl; Or substituted or: unsubstituted C _{2 -60} heteroaryl including one or more of 0, N, Si and S,

 In Formula 2 above.

Is a substituted or unsubstituted C ₆ -6o aryl,

R ' ₂ and R' 3 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted d-60 alkyl; Substituted or unsubstituted C _{3 -60} cycloalkyl; Substituted or unsubstituted C _{6 -60} aryl; Or substituted or unsubstituted C _{2 -60} heteroaryl including one or more of 0, N, Si, and S; n 'and m' are each independently an integer of 0 to 4,

L 'is a single bond; Substituted or unsubstituted C _{6 -60} arylene, Y 'is 0, S, NR', or CR'R ",

R ′ and R ″ are each independently substituted or unsubstituted d- ₆₀ alkyl; substituted or unsubstituted C _{3 -60} cycloalkyl; substituted or unsubstituted C _{6 -60} aryl; or substituted or unsubstituted 0, C _{2 -60} heteroaryl comprising at least one of N, Si, and S, or R 'and R''together form a substituted or unsubstituted C _{6 -60} aromatic ring.

[Claim 2]

 The method of claim 1,

 Formula 1 is represented by the following Formula 1-1, 1-2, or 1-3, an organic light emitting substrate ":

[Formula 1-2]

[Claim 3]

 The method of claim 1,

 Ri is phenyl; Or biphenylyl.

[Claim 4]

 The method of claim 1,

2 and R ₃ are hydrogen ^

 Organic light emitting device.

[Claim 5]

 In that U term,

 Y is S, or 0

 Organic light emitting device.

[Claim 6] The method of claim 1,

 L is a single bond or phenylene

 Organic light emitting device.

[Claim 7]

 In that U term,

An and Ar ₂ are each independently phenyl, cyano phenyl, biphenylyl, dimethylfluorenyl naphthyl, phenanthrenyl, pyridinyl, dibenzofuranyl or dibenzothiophenyl;

 Organic light emitting device.

[Claim 8]

 The method of claim 1,

 The compound represented by Formula 1 is any one selected from the group consisting of

Organic light emitting device:

44

45

47

[Claim 9]

 The method of claim 1,

 R'r ^ cyclonuclear, phenyl, cyano-substituted phenyl, biphenylyl, terphenylyl, naphthyl, phenanthreryl, triphenylenyl, dimethylfluorenyl, pyridinyl dibenzofuranyl, dibenzothiophenyl ., Or 9-phenyl—carbazolyl,

 Organic light emitting device.

[Claim 10]

 The method of claim 1,

 n 'is 1,

 R'2 is hydrogen or phenyl

 Organic light emitting device.

[Claim 11]

 The method of claim 1,

 m 'is 1,

R ' ₃ is hydrogen, tert-butyl, cyano, phenyl, phenyl substituted by cyano, or pyridinyl Organic light emitting device.

[Claim 12]

 The method of claim 1,

 Y 'is 0, S, or NR',

 R 'is phenyl or biphenylyl,

 Organic light emitting device.

[Claim 13]

 The method of claim 1,

 Y 'is CR' R "，

 R 'and R "are methyl or R' and R" together form a fluorene ring,

 Price light emitting device.

[Claim 14]

 In that U term.

 ^ Is a single bond, or phenylene

 Organic light emitting device.

[Claim 15]

 The method of claim 1,

 The compound represented by Formula 2 is any one selected from the group consisting of

Organic light emitting device: 09

Ϊ69Ϊ0Ϊ / 8Ϊ0Ζ OAV