KR101227126B1 - Light-emitting compound and organic light-emitting device using the same - Google Patents

Abstract

An organic light emitting compound is disclosed in which two different luminescent aromatic substituents are linked to each other without being conjugated to each other through a linking group. At least one of the two other luminescent aromatic substituents is an aryl amine substituent. The compound according to the present invention is useful as a hole injection material, a hole transport material and a light emitting layer material because of its excellent hole transporting ability and luminescent properties and excellent thermal stability. Using the compound according to the present invention, it is possible to provide an organic electroluminescent device with high efficiency, low voltage, high brightness and long life.

Description

Organic light-emitting compound and organic light-emitting device using the same

The present invention relates to an organic light emitting compound and an organic electroluminescent device using the same, and more particularly, to an arylamine-based organic light emitting compound useful as a hole injection material, a hole transport material or a light emitting material and an organic electroluminescent device using the same.

Recently, due to the rapid growth of the optical communication and multimedia fields, the development of a highly information society has been accelerated. Accordingly, optoelectronic devices using the photon-to-electron conversion or the electron-to-photon conversion are the core of the modern information electronics industry.

The organic electroluminescent device sandwiches a thin film containing a fluorescent organic compound or a phosphorescent organic compound between an anode and a cathode, and electrons and holes injected from each electrode generate excitons of the fluorescent or phosphorescent compound, and the exciton is a base. It is an element using the emitted light when returning to the state.

The electroluminescence of these organic materials was reported by Pope et al. In 1963. In 1987, by Tang et al., Eastman Kodak, alumina-quinone conjugates with a multilayer structure of 1% quantum efficiency and luminance of 1000 cd / m ² were used at 10V or less. Since structural light emitting devices have been reported, many studies have been conducted. They have the advantage of easy synthesis and synthesis of various types of materials and simple color tuning.

Recent advances in organic electroluminescent devices have been remarkable. The characteristics of the present invention include high brightness, low emission wavelength, high speed response, and light emitting device having a thin and light form. This suggests the possibility of use for research purposes.

The structure of a general organic electroluminescent device includes a hole injection layer that receives holes from a substrate, an anode, and an anode, a hole transport layer that transports holes, an electron blocking layer that prevents electrons from entering the hole transport layer from a light emitting layer, and a combination of holes and electrons. It consists of a light emitting layer that emits light, a hole blocking layer that blocks holes from entering the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode.

The organic layer except for the substrate, the anode, and the cathode may be configured in various forms in order to increase the lifetime or efficiency.

Conventionally, examples of hole transport materials used in organic electroluminescent devices include U.S. Patent 4,720,432, U.S. Patent 5,061,569, U.S. Patent 6,242,115, Japanese Patent Application Laid-Open No. 11-144873, Japanese Patent Application Laid-Open No. 2000-302756, Japan And Japanese Patent Application Laid-Open No. 2006-151979, Japanese Patent Laid-Open No. 2005-290000, Japanese Patent Laid-Open No. 2003-133075, Japanese Patent Laid-Open No. 2004-079265, and Korean Patent Publication No. 2009-0035729.

Compounds having arylamine substituents as luminescent materials are well known. Examples thereof include distyrylamine derivatives, pyrene derivatives substituted with arylamines, and anthracene derivatives substituted with arylamines, but there is a need for improvement in efficiency and lifespan for high brightness and large area display. In addition, as can be seen in the examples of the above patent documents, the performance of the material has been improved a lot, but the organic electroluminescent device currently requires higher efficiency and longer life, and to meet this need to greatly improve the performance of the existing material There is this.

Accordingly, an object of the present invention is to provide an arylamine-based organic light emitting compound which is excellent in electrical properties and thermal stability and useful as a hole injection material, a hole transport material or a light emitting material.

Still another object of the present invention is to provide an organic electroluminescent device having high efficiency and / or long life by employing the organic light emitting compound.

Another object of the present invention is to provide an organic electroluminescent display device employing the organic electroluminescent device.

In order to achieve the above object, an aspect of the present invention,

It provides an organic light emitting compound represented by the formula (1):

[Formula 1]

Wherein Y is carbon or silicon; A and B are different from each other and are C18 to C60 substituted or unsubstituted arylamine substituents; R ₁ And R ₂ , which may be the same or different, is hydrogen, a substituted or unsubstituted alkyl group of C1 to C8, a substituted or unsubstituted aryl group of C6 to C30, a substituted or unsubstituted heteroaryl group of C4 to C30; And R ₁ And R ₂ may be linked to each other to form a fused ring.

In order to achieve the above object, another aspect of the present invention,

It provides an organic light emitting compound represented by the formula (2):

[Formula 2]

Wherein Y is carbon or silicon; A is a substituted or unsubstituted arylamine substituent of C18 to C60; R ₁ And R ₂ , which may be the same or different, is hydrogen, a substituted or unsubstituted alkyl group of C1 to C8, a substituted or unsubstituted aryl group of C6 to C30, a substituted or unsubstituted heteroaryl group of C4 to C30; E is an aromatic substituent of C10 to C60 that does not contain a nitrogen atom; And R ₁ And R ₂ may be linked to each other to form a fused ring.

According to another embodiment of the present invention, E ₁ , E ₂ or E ₃ in Formula 2a, 2b or 2c are each independently substituted or unsubstituted biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenane Triyl, pyrenyl, fluorenyl, perrylenyl or triphenylene groups.

In order to achieve the above object, another aspect of the present invention,

Anode; Cathode; An organic electroluminescent device comprising; and an organic layer interposed between the anode and the cathode.

It provides an organic electroluminescent device characterized in that the organic layer comprises an organic light emitting compound according to the present invention described above.

According to an embodiment of the present invention, the organic layer may be a hole injection layer, a hole transport layer or a light emitting layer.

In order to achieve the above another object, another aspect of the present invention,

An organic electroluminescent display device including the organic electroluminescent device according to the present invention is provided.

The arylamine-based organic light emitting compounds represented by Formulas 1 and 2 according to the present invention have excellent thermal stability, luminescence properties, and electrical properties. This compound is therefore useful as a hole injection material, hole transport material and / or luminescent material in organic electroluminescent devices. An organic electroluminescent device comprising such a compound in a hole injection layer, a hole transport layer and / or a light emitting layer can achieve high efficiency, high brightness and long life.

1 is a view schematically showing the structure of an organic EL device according to an embodiment of the present invention.

Hereinafter, the arylamine-based organic light emitting compound, the organic electroluminescent device, and the organic electroluminescent display of the present invention will be described in more detail.

The organic light emitting compound according to the present invention has two different aromatic substituents connected asymmetrically without being conjugated through a linking group. At least one of these aromatic substituents is an arylamine substituent. Thus, a compound having a high thermal stability while maintaining the functional properties of each functional group in a state in which the influence between two different aromatic substituents is minimized can be provided. This means that in the organic electroluminescent device, heat resistance to joule heat generated between the organic layer and the organic layer and between the organic layer and the electrode and the resistance at high temperature can be increased. The organic light emitting compound according to the present invention may be used as a material for forming a hole injection layer, a material for forming a hole transport layer, and / or a material for forming a light emitting layer, thereby providing an organic electroluminescent device having high efficiency and long life.

As already described, the organic light emitting compound according to the present invention may be represented by the following formula (1) or (2):

[Formula 1]

Wherein Y is carbon or silicon; A and B are different from each other and are C18 to C60 substituted or unsubstituted arylamine substituents; R ₁ And R ₂ , which may be the same or different, is hydrogen, a substituted or unsubstituted alkyl group of C1 to C8, a substituted or unsubstituted aryl group of C6 to C30, a substituted or unsubstituted heteroaryl group of C4 to C30; And R ₁ And R ₂ may be linked to each other to form a condensed ring.

[Formula 2]

Wherein Y is carbon or silicon; A is a substituted or unsubstituted arylamine substituent of C18 to C60; R ₁ And R ₂ , which may be the same or different, is hydrogen, a substituted or unsubstituted alkyl group of C1 to C8, a substituted or unsubstituted aryl group of C6 to C30, a substituted or unsubstituted heteroaryl group of C4 to C30; E is an aromatic substituent of C10 to C60 that does not contain a nitrogen atom; And R ₁ And R ₂ may be linked to each other to form a condensed ring.

According to an embodiment of the present invention, the compound of Formula 1 may be represented by the following Formula 1a:

[Formula 1a]

Where R ₁ And R ₂ is a substituted or unsubstituted phenyl group, and can be linked to each other to form a condensed ring; Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are substituted or unsubstituted phenyl group, naphthyl group, biphenyl group or terphenyl group; L ₁ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, terphenylene group, pyrenylene group, triphenylene group or peryleneyl group; Ar ₃ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group or terphenylene group; Ar ₁ , Ar ₂ and L ₁ Any two of which may be linked to each other to form a condensed ring; And Ar ₃ , Ar _4, and Ar ₅ may be connected to each other to form a condensed ring.

According to another embodiment of the present invention, the compound of Formula 1 may be represented by the following Formula 1b:

[Chemical Formula 1b]

Where R ₁ And R ₂ is a substituted or unsubstituted phenyl group, and can be linked to each other to form a condensed ring; Ar ₁ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ are substituted or unsubstituted phenyl group, naphthyl group, biphenyl group or terphenyl group; L ₁ And L ₂ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, terphenylene group, pyrenylene group, triphenylene group or peryleneyl group; Ar ₃ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group or terphenylene group; Any two of L ₂ , Ar ₆ and Ar ₇ may be linked to each other to form a condensed ring; And Ar ₃ , Ar _4, and Ar ₅ may be connected to each other to form a condensed ring.

According to another embodiment of the present invention, the compound of Formula 1 may be represented by the following Formula 1c:

[Chemical Formula 1c]

Where R ₁ And R ₂ is a substituted or unsubstituted phenyl group, and can be linked to each other to form a condensed ring; Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ are substituted or unsubstituted phenyl group, naphthyl group, biphenyl group or terphenyl group; L ₁ , L ₂ and L ₃ are a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, terphenylene group, pyrenylene group, triphenylene group or peryleneyl group; Ar ₃ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group or terphenylene group; Any two of L ₂ , Ar ₆ and Ar ₇ may be linked to each other to form a condensed ring; Any two of Ar ₃ , Ar ₄ and Ar ₅ may be linked to each other to form a condensed ring; Some of Ar ₆ , Ar ₇ and L ₂ may be linked to each other to form a condensed ring; And Ar ₈ , Ar _9, and L ₃ may be connected to each other to form a condensed ring.

According to one embodiment of the present invention, the compound of Formula 2 may be represented by the following Formula 2a:

(2a)

Wherein Ar ₁ and Ar ₂ are a substituted or unsubstituted phenyl group, naphthyl group, biphenyl group or terphenyl group; L ₁ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, terphenylene group, or pyrenylene group; E ₁ is an aromatic substituent of C10 to C60 that does not contain a nitrogen atom; And Ar ₁ , Ar ₂ and L ₁ Either of which may be connected to each other to form a condensed ring.

According to another embodiment of the present invention, the compound of Formula 2 may be represented by the following Formula 2b:

[Formula 2b]

Wherein Ar ₁ , Ar ₆ and Ar ₇ are a phenyl group, naphthyl group, biphenyl group or terphenyl group substituted or unsubstituted with an alkyl group; L ₁ And L ₂ is a substituted or unsubstituted phenylene group, naphthylene group, biphenylene group or terphenylene group with an alkyl group; E ₂ is an aromatic substituent of C10 to C60 that does not contain a nitrogen atom; And any one of L ₂ , Ar _6, and Ar ₇ may be connected to each other to form a condensed ring.

According to another embodiment of the present invention, the compound of Formula 2 may be represented by the following Formula 2c:

[Formula 2c]

Wherein Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ are a phenyl group, naphthyl group, biphenyl group or terphenyl group substituted or unsubstituted with an alkyl group; L ₁ , L ₂ and L ₃ are a phenylene group, a naphthylene group, a biphenylene group or a terphenylene group substituted or unsubstituted with an alkyl group; E ₃ is an aromatic substituent of C10 to C60 that does not contain a nitrogen atom; Any two of L ₂ , Ar ₆ and Ar ₇ may be linked to each other to form a condensed ring; And Ar ₈ , Ar _9, and L ₃ may be connected to each other to form a condensed ring.

Specific examples of the compound represented by Formula 1 or 2 include the following compounds:

,

,

    (Compound 1) (Compound 2)

,

,

       (Compound 3) (Compound 4)

,

,

   (Compound 5) (Compound 6)

,

,

    (Compound 7) (Compound 8)

,

,

      (Compound 9) (Compound 10)

,

,

           (Compound 11) (Compound 12)

,

,

            (Compound 13) (Compound 14)

,

,

           (Compound 15) (Compound 16)

,

,

            (Compound 17) (Compound 18)

,

,

         (Compound 19) (Compound 20)

,

,

        (Compound 21) (Compound 22)

,

,

        (Compound 23) (Compound 24)

,

,

        (Compound 25) (Compound 26)

,

,

      (Compound 27) (Compound 28)

,

,

         (Compound 29) (Compound 30)

,

,

          (Compound 31) (Compound 32)

,

,

,

,

     (Compound 33) (Compound 34) (Compound 35)

,

,

             (Compound 36) (Compound 37)

,

,

,

          (Compound 38) (Compound 39)

Non-limiting methods of preparing the compound represented by Formula 1 or Formula 2 include the following Schemes 1, 2 and 3.

[Reaction Scheme 1]

Step 1:

Step 2:

Third step:

Scheme 1 can be used primarily when the compounds of Formula 1 differ from each other as substituents A and B and include substituted or unsubstituted arylamine substituents of C18 to C60.

First, a dibromo aromatic compound as a starting material is converted to tertiary alcohol through lithium lithiation of an aromatic group using n-butyl lithium and the lithium substituted aromatic compound through a condensation reaction of a ketone compound (first step). Subsequently, when the hydroxy group of the tertiary alcohol is substituted with L ₁ of the arylamine substituent in the presence of an acid catalyst (second step), and the remaining bromine group of the aromatic group is condensed with the diaryl amine compound with a Pd-based catalyst, the compound of formula 1 (Step 3). BINAP in the scheme represents 2,2'-bis (diphenylphosphino) -1,1'-binafthyl.

Scheme 2

Step 1:

Step 2:

Scheme 2 can be used primarily when the compound of formula (2) comprises a substituted or unsubstituted arylamine group of C18 to C60 as substituent A and an aromatic group of C10 to C60 that does not contain a nitrogen atom as substituent E.

First, a tertiary alcohol is prepared through a lithium substitution reaction of an aromatic group using basic n-butyl lithium as a starting material and a condensation reaction of the ketone compound with the lithium substituted aromatic compound (first step). When the hydroxy group of the tertiary alcohol is substituted with L ₁ of the arylamine substituent by an acid catalyst, a compound of Chemical Formula 2 may be obtained (second step).

Scheme 3

Step 1:

Step 2:

Third step:

.

.

Scheme 3 can be used primarily when the compound of formula (2) comprises a substituted or unsubstituted arylamine group of C18 to C60 as substituent A and an aromatic group of C10 to C60 that does not contain a nitrogen atom as substituent E.

First, a dibromo aromatic compound as a starting material is converted into a tertiary alcohol through a lithium substitution reaction of an aromatic group using n-butyl lithium and the lithium substituted aromatic compound through a condensation reaction of a ketone compound (first step). Subsequently, when the hydroxy group of the tertiary alcohol is substituted with an aromatic substituent containing no nitrogen atom in the presence of an acid catalyst (second step), and the remaining bromine group of the aromatic group is condensed with a diaryl amine compound with a Pd-based catalyst, The compound of can be obtained (third step).

Hereinafter, an organic electroluminescent device using the organic light emitting compound according to the present invention will be described.

The organic electroluminescent device according to the present invention can be realized in various structures. Referring to FIG. 1, an organic electroluminescent device 100 according to an embodiment of the present invention includes an anode 2 formed on a transparent substrate 1, a cathode 10, and a light emitting layer 6 inserted therebetween. Include. If necessary, one or more layers of the hole injection layer 3, the hole transport layer 4, or the electron blocking layer 5 may be inserted between the anode 2 and the light emitting layer 6. One or more layers of the hole blocking layer 7, the electron transport layer 8, or the electron injection layer 9 may be inserted between the cathode 10 and the light emitting layer 6. However, the structure of the organic EL device according to the present invention is not limited thereto. For example, one layer may be formed of the light emitting layer and the electron transporting layer by doping a small amount of fluorescent or phosphorescent dye into the electron transporting layer without forming a separate light emitting layer. The organic layers between the two electrodes 2 and 10 may be formed by vacuum deposition.

The anode 2 of the organic electroluminescent device of the present invention may be formed using a metal, an alloy, an electroconductive compound or a mixture thereof having a work function of about 4 eV or more. Specifically, transparent conductive materials such as Au or CuI, ITO (indium tin oxide), SnO ₂ and ZnO which are metals are mentioned. The thickness of the anode layer may be about 10 to 200 nm.

The cathode 10 of the organic electroluminescent device of the present invention may be formed using a metal, alloy, electroconductive compound or mixtures thereof having a work function of less than about 4 eV. Specific examples include aluminum, Na, Na-K alloys, calcium, magnesium, lithium, lithium alloys, indium, aluminum, magnesium alloys, and aluminum alloys. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may be used. Among these, aluminum (Al) which is excellent in stability especially can be used as a cathode. The thickness of the cathode layer may be about 10 to 200 nm.

In order to increase the luminous efficiency of the organic electroluminescent device, at least one electrode should preferably have a light transmittance of 10% or more. The sheet resistance of the electrode should preferably be several hundreds of mm 3 / mm or less. The thickness of the electrode is 10 nm to 1 탆, preferably 10 to 400 nm. Such an electrode may be manufactured by forming the above electrode material into a thin film through vapor deposition or sputtering such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like.

The hole injection layer 3 and the hole transport layer 4 may be formed using the compound of the formula (1) and / or 2 according to the present invention. In addition, within the content ranges that do not impair the effects of the present invention, materials commonly used as hole transport materials among photoconductive materials and known materials used for forming the hole transport layer or the hole injection layer of the organic electroluminescent device are further included. May be included. For example, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (hereinafter referred to as TPD), N, N'-bis (1- Naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (hereinafter referred to as NPD), N, N'-diphenyl-N, N'-dinaphthyl -4,4'-diaminobiphenyl, N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N, N'N'-tetraphenyl-4, 4'-diaminobiphenyl; Porphyrin compound derivatives such as Copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; Polymers having aromatic tertiary amines in the main or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (p-tolyl) amine, 4 ', 4' Triarylamine derivatives such as 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as metal phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamine stilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilanes.

The electron blocking layer 5 is at least one selected from fac-tris (1-phenylpyrazolato, N, C2 ') iridium (III) (Irppz) and the hole injection layer 3 or the hole transport layer 4 described above. It can be formed using a species.

The light emitting layer 6 may be formed by including the compound of Formula 1 and / or 2 according to the present invention, within a content range that does not impair the effects of the present invention, in the phosphorescent host, fluorescent host or dopant in the visible region It may further include one or more. It is also possible to form using a known light emitting material, for example, a phosphorescent fluorescent material, a fluorescent brightener, a laser dye, an organic scintillator and a fluorescence reagent. Specific examples include polyaromatic compounds such as AlQ ₃ , anthracene, phenanthrene, pyrene, Kirisen, perylene, coronene rubrene, and quinakiridone; Oligophenylene compounds such as quiterphenyl; 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1 , 4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-t-butyl-2-oxazolyl) benzene, 1,4-diphenyl 1,3-butadiene, 1,6 Scintillators for liquid scintillation such as -diphenyl-1,3,5-hexatriene, -1,1,4,4-tetraphenyl-1,3-butadiene; Metal complexes of auxin derivatives; Coumarin pigments; Dicyano methylene pyran pigment; Dicyano methylenethiopyran pigments; Polymethine pigments; Oxo benzanthracene pigments; Xanthene pigments; Carbostyryl pigments; Perylene pigments; Oxazine compounds; Cytylbene derivatives; Spiro compounds; Oxadiazole compounds and the like, and these may be used in combination with the compounds of the formulas (1) and / or (2) according to the present invention within a content range which does not impair the effects of the present invention.

The hole blocking layer 7 includes 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,4'-bis (9-carbazolyl) -biphenyl (CBP), At least one selected from BAlq and allyl phosphine compounds described in Applicant's patent application 2004-0054699.

The electron transport layer 8 is preferably a material having a high electron mobility capable of receiving electrons from the electron injection layer 9 and transferring the electrons to the light emitting layer 6 well. The electron transport layer 8 and the electron injection layer 9 can be arbitrarily selected from materials commonly used as electron transport materials among photoconductive materials and known materials used in the electron transport layer or electron injection layer of organic EL devices. . Specific examples of such electron transfer compounds include imidazole derivatives, oxadiazole compounds, triazole derivatives, phenylenediamine derivatives, stilbene derivatives, styryl anthracene derivatives, fluorene derivatives, hydrazone derivatives, diphenylquinone derivatives, Perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, metal complexes of oxine derivatives, polymers of quinoxaline derivatives, phenanthroline derivatives and the like. Specifically, in one embodiment of the present invention, the electron transport layer 8 includes 8-hydroxyquinoline aluminum complex (AlQ ₃ ); AlQ ₃ Organic compounds including structures; Hydroxyflavone-metal complexes; Silacyclopentadiene (silole) compounds; It may be formed of an allyl phosphine compound. The electron injection layer 9 may be formed of an aryl phosphine compound described in the applicant's patent application No. 2007-32969, a metal complex such as lithium quinolate, an inorganic substance such as LiF, or the like.

The organic layers are supported by the transparent substrate 1. The material of the transparent substrate 1 is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For example, glass, a transparent plastic film, etc. can be used.

Each organic layer or inorganic layer constituting the organic electroluminescent device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or laser thermal transfer. There is no particular limitation on the film thickness of each layer, and may be appropriately selected depending on the properties of the material, but may be determined in the range of 2 to 5,000 nm, preferably 10 to 2500 nm.

The anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode described above for the method of manufacturing an organic electroluminescent device using the arylamine-based compound represented by Formula 1 or Formula 2 as the hole transport material An organic electroluminescent device having a structure will be described as an example.

First, a hole injection layer is formed using a hole injection material on an ITO transparent substrate having a thickness of 1 μm or less, preferably 10 to 200 nm. A hole transport layer is formed using the compound of Formula 1 and / or Formula 2 according to the present invention. Subsequently, the light emitting layer is formed so as to cover the hole transport layer by vacuum depositing a fluorescent or phosphorescent dopant with the host. Subsequently, an electron transport layer is formed on the emission layer by using the electron transport material. Subsequently, an electron injection layer is formed on the electron transport layer by using an electron injection material. Finally, the electron injection layer is coated with a thin film containing a cathode material with a thickness of 1 μm or less to form a cathode to obtain an organic electroluminescent device. When the DC voltage is applied to the organic electroluminescent device obtained by using the anode as the positive electrode and the cathode as the negative electrode, light emission can be observed through the transparent or opaque electrode (either the anode or the cathode, or both electrodes). .

Hereinafter, an organic light emitting compound according to the present invention and a method of manufacturing an organic electroluminescent device having a hole transport layer or a light emitting layer formed using the same will be described in more detail with reference to Examples. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, this is for illustrative purposes and the scope of the present invention is not limited by the present embodiment.

,

,

,

,

(Intermediate 1) (Intermediate 2) (Intermediate 3)

,

,

,

,

(Intermediate 4) (Intermediate 5) (Intermediate 6)

,

,

,

,

(Intermediate 7) (Intermediate 8) (Intermediate 9)

,

,

      (Intermediate 10) (Intermediate 11)

,

,

,

,

     (Intermediate 12) (Intermediate 13) (Intermediate 14).

Synthetic example  1: Synthesis of Compound 1

(Synthesis of Intermediate 1)

65.5 g of 4,4'-dibromobiphenyl was dissolved in 1,500 ml of purified THF under nitrogen atmosphere, and then cooled to -78 deg. In this solution, 84 ml of n-butyllithium (2.5 M hexane solution) was slowly added for 1 hour. After further stirring the reaction solution at the same temperature for 2 hours, 36 g of fluorenone was added thereto, the cooling vessel was removed, further stirred at room temperature for 4 hours, and excess water was added to the reaction solution. The organic layer was then extracted using methylene chloride (MC), water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Crystallization with hexane afforded about 75.3 g (yield: 91.1%) of intermediate 1 as a white solid.

(Synthesis of Intermediate 11)

After dissolving 14.6 g of 9-phenylcarbazole in 400 ml MC under nitrogen atmosphere, 12.4 g of Intermediate 1 was added to the solution and cooled to 0 ° C. In this solution, a solution of 4.8 g of methane sulfonic acid diluted in 100 ml MC was slowly added. After further stirring for 1 hour at room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 13.4 g (yield: 80.4%) of intermediate 11 as a white solid.

(Synthesis of Compound 1)

28.7 g of intermediate 11 and 8.5 g of diphenylamine were dissolved in 500 ml of toluene under a nitrogen atmosphere. 0.84g of BINAP, 0.4g of Pd (OAc) ₂ and 21g of t-BuONa were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After refluxing for 4 hours, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 23.5 g (yield: 72%) of compound 1 as a pale yellow solid. Spectroscopic data of the compound 1 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 6.99-7.02 (m, 2H), 7.08-7.11 (m, 6H), 7.22-7.29 (m, 9H), 7.32-7.37 (m, 6H), 7.40-7.43 (m, 5H), 7.50-7.56 (m, 6H), 7.79-7.80 (d, 2H), 7.94-7.95 (m, 2H).

Mass spectrum: m / e = 706.3 (M ⁺ ).

Differential Scanning Calorimetry (DSC) thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 151.3 ° C.

Synthetic example  2: Synthesis of Compound 2

About 27.2 g (yield: 77.7%) of Compound 2 was obtained as a light yellow solid in the same manner as in Synthesis Example 1, except that 11 g of naphthylphenylamine was used instead of 8.5 g of diphenyl amine in Synthesis Example 1. The spectroscopic data of this compound 2 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 6.90-7.00 (m, 1H), 7.01-7.02 (d, 2H), 7.04-7.06 (d, 2H), 7.16-7.20 (m, 3H), 7.25-7.30 (m, 7H), 7.33-7.45 (m, 12H), 7.48-7.52 (m, 6H), 7.73-7.75 (d, 1H), 7.77-7.79 (d, 2H), 7.84-7.86 (d , 1H), 7.92-7.94 (m, 3H).

Mass spectrum: m / e = 776.3 (M ⁺ ).

DSC Thermal Analysis (N ₂ Atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 158.1 ° C.

Synthetic example  3: Synthesis of Compound 3

(Synthesis of Intermediate 9)

16.3 g of 4-bromobiphenyl and 33 g of aniline were dissolved in 400 ml of toluene under a nitrogen atmosphere. 1.3 g of BINAP, 0.63 g of Pd (OAC) ₂ , and 40 g of t-BuONa were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After reflux for 4 hours, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 13.5 g (yield: 78.5%) of intermediate 9 as a pale yellow solid.

(Synthesis of Compound 3)

About 27 g (yield: 74.8%) of Compound 3 was obtained as a pale yellow solid in the same manner as in Synthesis Example 1, except that 12.3 g of Intermediate 9 was used instead of 8.5 g of diphenylamine in Synthesis Example 1. The spectroscopic data of this compound 3 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 7.01, 7.03, 7.04 (t, 1H), 7.13-7.16 (m, 6H), 7.25-7.29 (m, 7H), 7.34-7.48 (m, 16H ), 7.51-7.56 (m, 8H), 7.79-7.81 (d, 2H), 7.94-7.96 (d, 2H).

Mass spectrum: m / e = 802.4 (M ⁺ ).

DSC Thermal Analysis (N ₂ Atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 158.3 ° C.

Synthetic example  4: Synthesis of Compound 6

(Synthesis of Intermediate 4)

12.2 g of 9-phenyl carbazole was completely dissolved in 500 ml of glacial acetic acid, and 8.9 g of N-bromosuccinimide (NBS) was added thereto, followed by stirring for 1 hour. After adding excess water to this solution, the organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed to obtain Intermediate 4. Purification by column chromatography gave about 15 g (yield: 93%) of intermediate 4 as a white solid.

(Synthesis of Intermediate 6)

23 g of intermediate 4 and 33 g of aniline were dissolved in 400 ml of toluene under a nitrogen atmosphere. 1.3g of BINAP, 0.63g of Pd (OAc) ₂ and 40g of t-BuONa were added thereto, stirred at room temperature for 30 minutes, and heated to reflux. After reflux for 4 hours, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 18 g (yield: 75.6%) of intermediate 6 as a pale yellow solid.

(Synthesis of Compound 6)

About 29.3 g (yield: 73%) of Compound 6 was obtained as a pale yellow solid in the same manner as in Synthesis Example 1, except that 16.7 g of Intermediate 6 was used instead of 8.5 g of diphenylamine in Synthesis Example 1. The spectroscopic data of this compound 6 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 7.14-7.20 (m, 5H), 7.24-7.38 (m, 18H), 7.42-7.46 (m, 6H), 7.51-7.59 (m, 11H), 7.79-7.81 (d, 2 H), 7.95-7.99 (m, 3 H).

Mass spectrum: m / e = 891.3 (M ⁺ )

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 180.7 ° C.

Synthetic example  5: Synthesis of Compound 18

(Synthesis of intermediate 2)

23.6 g of 1,4-dibromobenzene was dissolved in 500 ml of purified THF under nitrogen atmosphere, and then cooled to -78 ° C. 40 ml of n-butyllithium (2.5 M hexane solution) was slowly added to this solution for 1 hour. After further stirring the reaction solution at the same temperature for 2 hours, 18 g of 9-floorenone was added thereto, the cooling vessel was removed, further stirred at room temperature for 4 hours, and excess water was added to the reaction solution. The organic layer was then extracted using methylene chloride, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Crystallization by column chromatography gave about 28 g of intermediate 2 (yield: 83%).

(Synthesis of Intermediate 12)

After dissolving 14.7 g of triphenylamine in 400 ml MC under nitrogen atmosphere, 10.1 g of Intermediate 2 was added to the solution and cooled to 0 ° C. In this solution, a solution of 4.8 g of methanesulfonic acid diluted in 100 ml MC was slowly added. After further stirring for 1 hour at room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 13.8 g (yield: 81.7%) of intermediate 12 as a white solid.

(Synthesis of Compound 18)

Under a nitrogen atmosphere, 25.4 g of Intermediate 12 and 16.7 g of Intermediate 6 were dissolved in 400 ml of toluene. 0.84 g of BINAP, 0.4 g of Pd (OAC) ₂ and 21 g of t-BuONa were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After 4 hours reflux, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 24 g (yield: 65.2%) of compound 18 as a pale yellow solid. The spectroscopic data of this compound 18 was as follows.

¹ H NMR (CDCl 3, 500 MHz): δ (ppm) 6.88-6.90 (d, 3H), 6.94-6.97 (m, 2H), 7.02-7.06 (m, 10H), 7.17-7.21 (m, 8H), 7.27 -7.29 (m, 4H), 7.32-7.34 (m, 3H), 7.35-7.37 (m, 2H), 7.43-7.45 (d, 3H), 7.55-7.58 (m, 4H), 7.73-7.75 (d, 2H), 7.97-7.98 (d, 1H).

Mass spectrum: m / e = 817.4 (M ⁺ ).

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 155.2 ° C.

Synthetic example  6: Synthesis of Compound 33

(Synthesis of Intermediate 13)

In a nitrogen atmosphere, 21 g of 1-bromopyrene and 17.5 g of N-phenyl-1-naphthylamine were dissolved in 500 ml of toluene. BINAP 2.1 g, Pd (OAc) ₂ 0.6 g, and t-BuONa 40 g were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After 4 hours reflux, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 20 g (yield: 64%) of intermediate 13 as a yellow solid.

(Synthesis of Intermediate 14)

After dissolving 14.7 g intermediate 13 in 400 ml MC under nitrogen atmosphere, 5.9 g of intermediate 2 was added to the solution and cooled to 0 ° C. In this solution, a solution of 4.8 g of methanesulfonic acid diluted in 100 ml MC was slowly added. After stirring for 1 hour at room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 8.3 g (yield: 64.3%) of intermediate 14 as a yellow solid.

(Synthesis of Compound 33)

19 g of intermediate 14 and 5.1 g of diphenylamine were dissolved in 700 ml of toluene under a nitrogen atmosphere. BINAP 2.1 g, Pd (OAc) ₂ 0.6 g and t-BuONa 40 g were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After 4 hours reflux, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 15 g (yield: 70.4%) of compound 33 as a yellow solid. The spectroscopic data of this compound 33 was as follows.

Mass spectrum: m / e = 826 (M ⁺ ).

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 205 ° C.

Synthetic example  7: Synthesis of Compound 29

(Synthesis of Intermediate 3)

23.3 g of 4-bromobiphenyl was dissolved in 700 ml of purified THF under nitrogen atmosphere, and then cooled to -78 ° C. 40 ml of n-butyllithium (2.5 M hexane solution) was slowly added to this solution for 1 hour. After further stirring the reaction solution at the same temperature for 2 hours, 18 g of 9-floorenone was added thereto, the cooling vessel was removed, further stirred at room temperature for 4 hours, and excess water was added to the reaction solution. Then, the organic layer was extracted using MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Crystallization with hexane gave about 28 g (yield: 83.8%) of intermediate 3 as a white) color solid.

(Synthesis of Intermediate 8)

33.8 g of intermediate 4 and 4.6 g of aniline were dissolved in 500 ml of toluene under a nitrogen atmosphere. 1.86 g of BINAP, 0.9 g of Pd (OAc) ₂ and 60 g of t-BuONa were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After 4 hours reflux, excess water in this solution was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 23 g (yield: 79.8%) of intermediate 8 as a yellow solid.

(Synthesis of Compound 29)

8.4 g of intermediate 8 and 2.4 g of intermediate 3 were dissolved in 500 ml MC under nitrogen atmosphere and then cooled to 0 ° C. in this solution. The solution which diluted 0.96 g of methanesulfonic acid in 10 ml MC in this solution was added gradually. After stirring for 1 hour at room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave Compound 4.2 (yield: 65.6%) as a pale yellow solid. The spectroscopic data of this compound 29 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 7.19-7.20 (m, 2H), 7.28-7.31 (m, 8H), 7.34-7.39 (m, 10H), 7.42-7.44 (m, 5H), 7.46-7.48 (d, 3H), 7.51-7.53 (m, 3H), 7.48-7.52 (m, 6H), 7.73-7.75 (d, 1H), 7.77-7.79 (d, 2H), 7.84-7.86 (d , 1H), 7.92-7.94 (m, 3H).

Mass spectrum; m / e = 891.4 (M ⁺ ).

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 181.2 ° C.

Synthetic example  8: Synthesis of Compound 30

(Synthesis of Intermediate 5)

After 7.3 g of 9-phenylcarbazole was completely dissolved in 300 ml of glacial acetic acid, 10.7 g of NBS was added thereto, and the mixture was stirred for 1 hour. After adding excess water to this solution, the precipitated solid was filtered, washed several times with water and again with a small amount of methanol. About 11.8 g of intermediate 5 (yield: 98.1%) was obtained as a white solid.

(Synthesis of Intermediate 10)

11.8 g of intermediate 5 and 15 g of intermediate 9 were dissolved in 300 ml of toluene under a nitrogen atmosphere. 11 g of BINAP, 0.54 g of Pd (OAc) ₂ and 40 g of t-BuONa were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux. After 4 hours reflux, excess water was added to this solution. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 16.8 g (yield: 79.4%) of intermediate 10 as a pale yellow solid.

(Synthesis of Compound 30)

10.5 g of intermediate 10 and 2.4 g of intermediate 3 were dissolved in 500 ml MC under nitrogen atmosphere and then cooled to 0 ° C. in this solution. The solution which diluted 0.96 g of methanesulfonic acid in 10 ml MC in this solution was added gradually. After stirring for 1 hour at room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave about 4.8 g (yield: 64%) of compound 30 as a pale yellow solid. The spectroscopic data of this compound 30 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 6.88-6.93 (m, 2H), 7.00-7.06 (m, 7H), 7.18-7.26 (m, 11H), 7.30-7.42 (m, 21H), 7.47-7.54 (m, 10H), 7.72-7.74 (d, 4H).

Mass spectrum: m / e = 1045.4 (M ⁺ ).

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 182.8 ° C.

Synthetic example  9: Synthesis of Compound 5

Under nitrogen atmosphere, 12.78 g of intermediate 11 and 2.58 g of carbazole were dissolved in 200 ml of DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone). 0.29 g of CuI, 21.28 g of K ₂ CO ₃ and 0.08 g of 18-Crown-6 were added to the solution, stirred at room temperature for 30 minutes, and heated to reflux at 170 ° C. After refluxing for 8 hours, after cooling to room temperature, excess water was added. The organic layer was extracted with MC, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography yielded about 5.3 g of compound 5 (yield: 47.7%) as a white solid. The spectroscopic data of this compound 5 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 7.19-7.22 (m, 1H), 7.25-7.32 (m, 6H), 7.36-7.45 (m, 11H), 7.52-7.58 (m, 10H), 7.74-7.75 (d, 2H), 7.81-7.83 (d, 2H), 7.96-7.99 (m, 2H), 8.12-8.14 (d, 2H).

Mass spectrum: m / e = 724.4 (M ⁺ ).

Thermal analysis using DSC (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 176.8 ° C.

Synthetic example  10: Synthesis of Compound 10

(Synthesis of Intermediate 15)

About 18 g (yield: 72.3%) of intermediate 15 was obtained as a green solid by the same method as the synthesis of intermediate 6, except that 38 g of p-toluidine was used instead of 33 g of aniline in the synthesis of intermediate 6 of Synthesis Example 4.

(Synthesis of Compound 10)

About 32.2 g of compound 10 as a pale yellow solid (yield: 71.1%) in the same manner as in the synthesis of compound 1, except that 17.5 g of Intermediate 15 was used instead of 8.5 g of diphenylamine in the synthesis of Compound 1 in Synthesis Example 1. Got. The spectroscopic data of this compound 10 was as follows.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 2.75 (s, 3H), 7.06-7.08 (m, 5H), 7.16-7.22 (m, 4H), 7.27-7.42 (m, 20H), 7.51- 7.57 (m, 10 H), 7.78-7.80 (d, 2 H), 7.92-7.97 (m, 4H).

Mass spectrum: m / e = 905.4 (M ⁺ ).

DSC Thermal Analysis (N ₂ Atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 180.7 ° C.

Synthetic example  11: Synthesis of Compound 13

(Synthesis of Intermediate 16)

About 20 g (yield: 73%) of Intermediate 16 was obtained as a pale green solid in the same manner as the synthesis of Intermediate 6, except that 50.7 g of 1-naphthylamine was used instead of 33 g of aniline in the synthesis of Intermediate 6 of Synthesis Example 4.

(Synthesis of Compound 13)

About 29 g (yield: 61.6%) of Compound 13 was obtained as a pale yellow solid in the same manner as Compound 1, except that 19.2 g of Intermediate 16 was used instead of 8.5 g of diphenylamine in the synthesis of Compound 1 in Synthesis Example 1. The spectroscopic data of the compound 13 was as follows.

¹ H NMR (CDCl 3, 500 MHz): δ (ppm) 6.92-6.93 (d, 1H), 7.16-7.20 (m, 2H), 7.27-7.37 (m, 8H), 7.35-7.41 (m, 16H), 7.44 7.57 (m, 11H), 7.78-7.80 (d, 2H), 7.87-7.89 (d, 1H), 7.94-7.96 (m, 4H), 8.07-8.09 (d, 1H).

Mass spectrum; m / e = 941.4 (M ⁺ ).

DSC thermal analysis (N ₂ atmosphere, 400 ° C. at room temperature, disposable Al pan): Tg = 195.8 ° C.

Example  1: Organic with Compound 18 Electroluminescence  Fabrication of the device

This example is intended to explain the fabrication of an organic electroluminescent device using compound 18 obtained in Synthesis Example 5 as the hole transport material of the hole transport layer.

First, an ITO substrate having a surface resistance of 10 Ω / □ and having a thickness of about 150 nm was subjected to ultrasonic cleaning using a mixed solution of isopropyl alcohol and pure water 1: 1, pure water, and isopropyl alcohol solution in that order, and then an inert gas. Dried. TPTE of the following formula was vacuum deposited on the washed ITO at a rate of 0.2 to 2.0 mW / sec under a vacuum of 2 × 10 ⁻⁶ torr to form a hole injection layer having a thickness of about 50 nm.

Compound 18 was vacuum deposited on the hole injection layer under a vacuum of 2 × 10 ⁻⁶ torr at a rate of 0.2˜2.0 μs / sec to form a hole transport layer having a thickness of about 50 nm. Subsequently, a light emitting material was vacuum-deposited on the hole transport layer at a rate of 0.1 mW / sec to form a blue light emitting layer having a thickness of about 30 nm. Dinaphthylanthracene was used as the host material of the light emitting layer, and 3% of the styrylamine compound was doped with the blue light emitting dopant. Compound 40 was vacuum deposited on the light emitting layer to form an electron transport layer having a thickness of about 30 nm.

TPTE

Subsequently, LiF was vacuum deposited on the electron transport layer to form an electron injection layer having a thickness of 1.0 nm, and then Al was vacuum deposited on the electron transport layer to form a cathode layer having a thickness of about 100 nm, thereby completing an organic electroluminescent device. The completed organic electroluminescent device showed a luminous efficiency of 2.50 lm / W at a current density of 10 mA / cm ² . In this case, the luminance was 752 cd / m ² and the color coordinates were (0.127, 0.94).

Example  2: organic with compound 6 Electroluminescence  Fabrication of the device

This example is intended to explain the fabrication of an organic electroluminescent device using the compound 6 obtained in Synthesis Example 4 as a hole transport material of the hole transport layer.

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 6 was used instead of Compound 18 as the hole transport material. The completed organic electroluminescent device showed a luminous efficiency of 3.22 lm / W at a current density of 10 mA / cm ² . In this case, the luminance was 977 cd / m ² and the color coordinates were (0.130, 0.194).

Example  3: organic with compound 3 Electroluminescence  Fabrication of the device

This example is for explaining the fabrication of an organic electroluminescent device using the compound 3 obtained in Synthesis Example 3 as the hole transport material of the hole transport layer.

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 3 was used instead of Compound 18 as the hole transport material. The completed organic electroluminescent device showed a luminous efficiency of 2.46 lm / W at a current density of 10 mA / cm ² . The luminance was 758 cd / m 2 and the color coordinates were (0.131, 0.190).

Comparative example  1: organic Electroluminescence  Fabrication of the device

With hole transport material  N, N instead of compound 18, N ' , N ' - Tetrabiphenylbenzidine (TBPB)  Except that Example  Organic in the same way as 1 Electroluminescence  The device was produced. Finished organic Electroluminescence  Device is 10 mA Of cm ² 2.15 at current density of lm It showed luminous efficiency of / W. At this time, the luminance is 578 CD / m ² Was Color coordinates  (0.131, 0.204).

Example  4: organic using compound 33 Electroluminescence  Fabrication of the device

This example is for explaining the fabrication of an organic electroluminescent device using the compound 33 obtained in Synthesis Example 6 as a blue light emitting material of the light emitting layer.

First, an ITO substrate having a surface resistance of 10 Ω / □ and having a thickness of about 150 nm was subjected to ultrasonic cleaning using a mixed solution of isopropyl alcohol and pure water 1: 1, pure water, and isopropyl alcohol solution in that order, and then an inert gas. Dried. TPTE was vacuum deposited on the washed ITO under a vacuum of 2 × 10 ⁻⁶ torr at a rate of 0.2˜2.0 μs / sec to form a hole injection layer having a thickness of about 50 nm. A-NPD was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of about 50 nm. Subsequently, a light emitting material was vacuum deposited on the hole transport layer to form a blue light emitting layer having a thickness of about 30 nm. Dinaphthylanthracene was used as a host material of this light emitting layer, and about 33% of compound 33 was doped with a blue light emitting dopant.

The following aryl phosphine oxide compound 40 was vacuum-deposited on the emission layer to form an electron injection transport layer having a thickness of about 30 nm. Subsequently, Al was vacuum-deposited thereon to form a cathode layer having a thickness of about 100 nm, thereby completing an organic electroluminescent device. The completed organic electroluminescent device showed a current efficiency of 3.02 cd / A at a current density of 10 mA / cm ² . At this time, the color coordinates were (0.145, 0.118).

, (화합물 40)

, (Compound 40)

Meanwhile, compound 40 may be synthesized through the method disclosed in Korean Patent Registration No. 0852987 and International Patent Application WO 2008/120957.

Table 1 puts together the evaluation result of the organic electroluminescent element produced in Example 1-2 and the comparative example 1.

Hole transport material Luminance
@ 10mA / cm2 Luminous Efficiency (lm / W)
@ 10mA / cm2 Color coordinates x y Example 1 Compound 18 752 2.50 0.127 0.194 Example 2 Compound 6 977 3.22 0.130 0.194 Example 3 Compound 3 758 2.46 0.131 0.190 Comparative Example 1 TBPB 578 2.15 0.131 0.204

Referring to Table 1, it was confirmed that the organic electroluminescent device manufactured using the organic light emitting compound of the present invention as the hole transport material has a higher luminous efficiency than the organic electroluminescent device manufactured using the conventional hole transport material TBPB. Can be. In addition, the organic light emitting compound of the present invention has a high Tg value, as can be seen in the synthesis example, it is possible to implement high thermal stability during device fabrication. For reference, the Tg values of the conventional hole injection material and the hole transport material TPTE, TBPB and α-NPD are 130 ° C., 139 ° C. and 95 ° C., respectively.

In addition, as can be seen in Example 4, it can also be confirmed that the organic light emitting compound of the present invention exhibits excellent efficiency and color coordinates even as a light emitting material.

EIL: electron injection layer
ETL: Electron Transport Layer
HBL: hole blocking layer
EML: light emitting layer
EBL: Electronic Blocks
HTL: hole transport layer
HIL: Hole Injection Layer

Claims (7)

delete An organic light emitting compound represented by the formula (2b):
(2b)

Wherein Ar ₁ , Ar ₆ and Ar ₇ are a phenyl group, naphthyl group, biphenyl group or terphenyl group substituted or unsubstituted with an alkyl group;
L ₁ and L ₂ are an unsubstituted or substituted phenylene group, naphthylene group, biphenylene group or terphenylene group;
E ₂ is an alkyl group substituted or unsubstituted biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, fluorenyl group, perrylenyl group or triphenylenyl group; And
Any two of L ₂ , Ar ₆ and Ar ₇ may be connected to each other to form a condensed ring. delete delete Anode; Cathode; An organic electroluminescent device comprising; and an organic layer interposed between the anode and the cathode.
The organic electroluminescent device according to claim 2, wherein the organic layer comprises the organic light emitting compound according to claim 2. The organic electroluminescent device according to claim 5, wherein the organic layer is a hole injection layer, a hole transport layer, or a light emitting layer. An organic electroluminescent display comprising the organic electroluminescent device of claim 5.

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