KR20190121283A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device with improved driving voltage, efficiency, and lifespan. The organic light emitting device comprises: a positive electrode; a negative electrode; a light emitting layer between the positive electrode and the negative electrode; an electron suppression layer between the positive electrode and the light emitting layer; and a hole transport layer between the electron suppression layer and the positive electrode.

Description

Organic light emitting device

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

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, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

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 made 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, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, 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 and the electrons meet each other. When it 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.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

anode,

cathode,

A light emitting layer between the anode and the cathode, and

An electron suppression layer between the anode and the light emitting layer,

The emission layer includes a compound represented by the following formula (1),

The electron suppression layer comprises a compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₄ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, or two adjacent groups combine to form a benzene ring,

Ar ₁ is substituted or unsubstituted C _6-60 aryl,

, 또는

이고,Ar ₂ is

, or

ego,

Ar ₃ is substituted or unsubstituted C _6-60 aryl,

R ₅ to R ₈ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, or two adjacent groups combine to form a benzene ring,

[Formula 2]

L is a bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₄ to Ar ₆ are each independently C _6-60 aryl.

The organic light emitting element described above is excellent in driving voltage, efficiency and lifetime.

FIG. 1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, an electron suppression layer 3, a light emitting layer 4, and a cathode 5.
2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 6, an electron suppression layer 3, a light emitting layer 4, an electron transport layer 7, and a cathode 5. It is shown.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" 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; Alkylaryl 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 including one or more of N, O and S atoms, or two or more substituents of the above-described substituents connected or substituted. . 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 phenyl 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 this specification, although carbon number of an imide group is not specifically 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, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

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

In the present specification, the alkyl group may be linear or branched 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 -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the 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, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to 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, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but 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. According to an 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.

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

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 O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group (phenanthroline), thiazolyl group, Isooxazolyl group, oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. 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, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group 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.

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

Anode and cathode

An anode and a cathode used in the present invention mean an electrode used in an 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, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, 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 LiO ₂ / Al, and the like, but are not limited thereto.

Light emitting layer

The light emitting layer used in the present invention means a layer capable of emitting light in the visible light region by combining holes and electrons received from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and the present invention includes a compound represented by Chemical Formula 1 as a host.

In Formula 1, preferably, R ₁ to R ₄ are all hydrogen, or two adjacent groups are bonded to each other to form a benzene ring, and the rest are hydrogen. More preferably, Chemical Formula 1 is represented by the following Chemical Formulas 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, Ar ₁ , Ar ₃ , R ₅ to R ₈ are as defined above.

Preferably, Ar ₁ is phenyl, biphenylyl, naphthyl, or dimethylfluorenyl.

Preferably, Ar ₂ is any one selected from the group consisting of:

Preferably, Ar ₃ is phenyl, biphenylyl, or naphthyl.

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

The compound represented by Chemical Formula 1 may be prepared by the same method as in Scheme 1 below.

Scheme 1

In Scheme 1, R ₁ to R ₄ , Ar ₁ , Ar ₂ , Ar _3, and R ₅ to R ₈ are as defined above, and X is each independently halogen. The manufacturing method may be more specific in the production examples to be described later.

The dopant material is not particularly limited as long as it is a material used for an organic light emitting device. For example, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, etc. are mentioned. 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 a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

Electron suppression layer

The organic light emitting device according to the present invention includes an electron suppression layer between the anode and the light emitting layer. Preferably, the electron suppression layer is included in contact with the anode side of the light emitting layer.

The electron suppression layer serves to improve efficiency of the organic light emitting device by inhibiting electrons injected from the cathode from being transferred toward the anode without recombination in the emission layer. In the present invention, a compound represented by Chemical Formula 2 is used as a material constituting the electron suppression layer.

Preferably, Formula 2 is represented by the following Formula 2-1, or 2-2:

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, Ar ₄ , Ar ₅ , and Ar ₆ are as defined above.

Preferably, Ar ₄ is phenyl.

Preferably, Ar ₅ and Ar ₆ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenanthrenyl, phenanthrenylphenyl, or Triphenylenyl.

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

The compound represented by Formula 2 may be prepared by the same method as in Scheme 2 below.

Scheme 2

In Scheme 2, L, Ar ₄ , Ar ₅ and Ar ₆ are as defined above, X is halogen. The manufacturing method may be more specific in the production examples to be described later.

Hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer between the electron suppression layer and the anode.

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 of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a nonconjugated portion together.

Hole injection layer

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

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, and has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and is produced in the light emitting layer 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 also desirable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

Electron transport layer

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

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode to transport electrons to the light emitting layer, and also suppresses the transfer of holes from the light emitting layer. As a material which can receive and transfer to a light emitting layer, a material having high mobility to electrons is suitable.

Specific examples of the electron transporting material 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 according to 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 cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

Electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode as necessary.

The electron injection layer is a layer for injecting electrons from an electrode, has an ability 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 It is preferable to use a compound which prevents the movement to a layer and is excellent in thin film formation ability.

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

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

Organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1. FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, an electron suppression layer 3, a light emitting layer 4, and a cathode 5. In addition, the structure of the organic light emitting element in the case of including the hole transport layer 6 and the electron transport layer 7 is illustrated in FIG.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configuration. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. And, after forming the above-described respective layers, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate to an anode material in the reverse order of the above-described configuration (WO 2003/012890). In addition, the light emitting layer may be formed of a host and a dopant not only by vacuum deposition but also by solution coating. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

Hereinafter, preferred examples are provided 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]

Preparation Example 1-1 Preparation of Compound 1-1

Step 1) Preparation of Compound 1-a

2-chloro-4- (naphthalen-2-yl) quinazolin (12.00 g, 41.38 mmol), 2-chloro-5H-benzo [b] carbazole (11.42 g, 45.52 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere ) Was completely dissolved in DMAC (50 ml) / Xylene (200 ml) solution, and then K ₃ PO ₄ (20.05 g, 62.07 mmol) was added thereto, followed by heating and stirring for 3 hours. The mixture was cooled to room temperature, filtered, washed twice with water (500 ml), washed with ethyl acetate (300 ml) and dried at room temperature for 24 hours to prepare compound 1-a (11.07 g, yield: 53%). It was.

MS: [M + H] ⁺ = 637

Step 2) Preparation of Compound 1-1

Compound 1-a (11.07 g, 21.92 mmol) and 9H-carbazole (4.03 g, 24.11 mmol) were completely dissolved in Xylene (220 ml) in a 500 ml round bottom flask in nitrogen atmosphere, followed by sodium tert-butoxide (2.74 g). , 28.50 mmol) was added, Pd (t-Bu ₃ P) ₂ (0.22 g, 0.44 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, concentrated under reduced pressure, and recrystallized twice with ethyl acetate (300 ml) to give compound 1-1 (7.86 g, yield: 57%).

MS: [M + H] ⁺ = 637

Preparation Example 1-2 Preparation of Compound 1-2

Step 1) Preparation of Compound 1-b

2-chloro-4-phenylquinazolin and 3-chloro-5H-benzo [b] instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively Except for using carbazole, Compound 1-b was prepared by the same method as the method for preparing Compound 1-a.

Step 2) Preparation of Compound 1-2

Compound 1-2 was prepared by the same method as the method for preparing compound 1-1, except that compound 1-b was used instead of compound 1-a.

MS: [M + H] ⁺ = 587

Preparation Example 1-3: Preparation of Compound 1-3

Step 1) Preparation of Compound 1-c

2-chloro-4-phenylquinazolin and 9-bromo-11H-benzo [a instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively ] Compound 1-c was prepared by the same method as the method for preparing compound 1-a, except that carbazole was used.

Step 2) Preparation of Compound 1-3

In a 500 ml round bottom flask in nitrogen atmosphere, compound 1-c (12.34 g, 24.68 mmol) and (9-phenyl-9H-carbazol-2-yl) boronic acid (8.15 g, 28.38 mmol) were added to tetrahydrofuran (240 After completely dissolved in ml), 2M aqueous potassium carbonate solution (120 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.86 g, 0.74 mmol) was added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with tetrahydrofuran (240 ml) to prepare compound 1-3 (11.36 g, yield: 69%).

MS: [M + H] ⁺ = 663

Preparation Example 1-4: Preparation of Compound 1-4

Step 1) Preparation of Compound 1-d

2-chloro-4-phenylquinazolin and 10-chloro-7H-benzo [c] instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively Except for using carbazole, Compound 1-d was prepared by the same method as the method for preparing Compound 1-a.

Step 2) Preparation of Compound 1-4

Compound 1-4 was prepared by the same method as the method for preparing compound 1-1, except that compound 1-d was used instead of compound 1-a.

MS: [M + H] ⁺ = 587

Preparation Example 1-5: Preparation of Compound 1-5

Step 1) Preparation of Compound 1-e

4- (biphenyl-4-yl) -2-chloroquinazolin and 9-bro, instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively Compound 1-e was prepared by the same method as the method for preparing compound 1-a, except that mother-7H-benzo [c] carbazole was used.

Step 2) Preparation of Compound 1-5

Compound 1-5 was prepared by the same method as the method for preparing compound 1-1, except that compound 1-e was used instead of compound 1-a.

MS: [M + H] ⁺ = 663

Preparation Example 1-6 Preparation of Compound 1-6

Step 1) Preparation of Compound 1-f

2-chloro-4-phenylquinazolin and 10-bromo-7H-benzo [c instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively ] Compound 1-f was prepared by the same method as the preparation method of compound 1-a, except that carbazole was used.

Step 2) Preparation of Compound 1-6

Compound 1-6 was prepared by the same method as the method for preparing compound 1-3, except that compound 1-f was used instead of compound 1-c.

MS: [M + H] ⁺ = 663

Preparation Example 1-7 Preparation of Compound 1-7

Step 1) Preparation of Compound 1-g

2-chloro-4-phenylquinazolin and 8-bromo-11H-benzo [a instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole, respectively ] Compound 1-g was prepared by the same method as the preparation method of compound 1-a, except that carbazole was used.

Step 2) Preparation of Compound 1-7

Of compounds 1-3, except that compound 1-g and 9-phenyl-9H-carbazol-3-ylboronic acid are used instead of compound 1-c and 9-phenyl-9H-carbazol-2-ylboronic acid In the same manner as in the preparation method, compound 1-7 was prepared.

MS: [M + H] ⁺ = 663

Preparation Example 1-8: Preparation of Compound 1-8

Of compounds 1-3, except that compounds 1-b and 9-phenyl-9H-carbazol-3-ylboronic acid are used instead of compounds 1-c and 9-phenyl-9H-carbazol-2-ylboronic acid In the same manner as in the preparation method, compound 1-8 was prepared.

MS: [M + H] ⁺ = 663

Preparation Example 1-9: Preparation of Compound 1-9

Step 1) Preparation of Compound 1-h

2-chloro-4- (9,9-dimethyl-9H-fluorene-2- instead of 2-chloro-4- (naphthalen-2-yl) quinazolin and 2-chloro-5H-benzo [b] carbazole Compound 1-h was prepared by the same method as the method for preparing compound 1-a, except for using one) quinazolin and 3-chloro-5H-benzo [b] carbazole.

Step 2) Preparation of Compound 1-9

Compound 1-9 was prepared by the same method as the method for preparing compound 1-3, except that compound 1-h was used instead of compound 1-c.

MS: [M + H] ⁺ = 779

Preparation Example 1-10: Preparation of Compound 1-10

Of compounds 1-3, except that compound 1-f and 9-phenyl-9H-carbazol-3-ylboronic acid are used instead of compound 1-c and 9-phenyl-9H-carbazol-2-ylboronic acid In the same manner as the preparation method, compound 1-10 was prepared.

MS: [M + H] ⁺ = 663

Preparation Example 1-11: Preparation of Compound 1-11

Of compounds 1-3, except that compounds 1-e and 9-phenyl-9H-carbazol-3-ylboronic acid are used instead of compounds 1-c and 9-phenyl-9H-carbazol-2-ylboronic acid In the same manner as in the preparation method, compound 1-11 was prepared.

MS: [M + H] ⁺ = 663

Preparation Example 1-12 Preparation of Compound 1-12

Compound 1-12 was prepared by the same method as the method for preparing compound 1-3, except that compound 1-e was used instead of compound 1-c.

MS: [M + H] ⁺ = 663

Preparation Example 2-1 Preparation of Compound 2-1

Compound 5-phenyl-5,12-dihydroindolo [3,2-a] carbazole (6.47 g, 19.49 mmol), N-([1,1'-biphenyl) in a 500 ml round bottom flask in nitrogen atmosphere ] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl] -4-amine (10.18 g, 21.44 mmol) completely dissolved in Xylene (230 ml) and then sodium tert- Butoxide (2.43 g, 25.33 mmol) was added, Pd (t-Bu ₃ P) ₂ (0.20 g, 0.39 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, concentrated under reduced pressure, and recrystallized twice with ethyl acetate (250 ml) to give compound 2-1 (10.67 g, yield: 76%).

MS: [M + H] ⁺ = 723

Preparation Example 2-2: Preparation of Compound 2-2

N, N-di (biphenyl-4-yl) -4'-bromobiphenyl-4- instead of N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine A compound 2-2 was prepared in the same manner as the method for preparing compound 2-1, except that amine was used.

MS: [M + H] ⁺ = 804

Preparation Example 2-3: Preparation of Compound 2-3

N- (biphenyl-4-yl) -N- (4-bromophenyl) -9, instead of N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine, Compound 2-3 was prepared in the same manner as in the preparation of compound 2-1, except that 9-dimethyl-9H-fluorene-2-amine was used.

MS: [M + H] ⁺ = 768

Preparation Example 2-4: Preparation of Compound 2-4

N- (biphenyl-4-yl) -N- (4-bromophenyl) -9, instead of N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine, Compound 2-4 was prepared by the same method as the method for preparing compound 2-1, except that 9-dimethyl-9H-fluorene-2-amine was used.

MS: [M + H] ⁺ = 844

Preparation Example 2-5: Preparation of Compound 2-5

Except for using N- (4-bromophenyl) -N-phenylbiphenyl-4-amine instead of N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine And the compound 2-5 was manufactured by the method similar to the manufacturing method of compound 2-1.

MS: [M + H] ⁺ = 652

Preparation Example 2-6 Preparation of Compound 2-6

Except for using N- (4-bromophenyl) -N-phenylterphenyl-4-amine instead of N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine And the compound 2-6 was manufactured by the method similar to the manufacturing method of compound 2-1.

MS: [M + H] ⁺ = 723

EXAMPLE

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as the detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as the distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and 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.

On the ITO transparent electrode prepared as described above, a compound represented by the following HAT was thermally vacuum deposited to a thickness of 150 kPa to form a thin film. Subsequently, the compound represented by the following HT-1 is deposited to a thickness of 1150 kPa on the thin film to form a hole transport layer, and the compound represented by Formula 2-1 prepared above is deposited to a thickness of 100 kPa on the thin film to form an electron blocking layer. Formed. Subsequently, 10 wt% of the compound represented by the following RD-1 was doped into the compound represented by Formula 1-2 of the preparation example to form a light emitting layer having a thickness of 300 Pa. The hole blocking layer was formed by evaporating to a thickness of 50 kV of the compound represented by the following HB-1, and then the compound represented by the following ET-1 was deposited to a thickness of 310 kV to form an electron transporting layer. 12 전자 of lithium fluoride (LiF) and 1,000 Å of aluminum were sequentially deposited on the electron transport layer to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- The} organic light emitting device was manufactured by maintaining ⁷ to 5 × 10 ⁻⁶ torr.

Examples 2 to 24

In Example 1, except that the compound represented by Formula 1, instead of the compound represented by Formula 1-2 and / or the compound represented by Formula 2-1, the compound prepared in Preparation Example shown in Table 1 below An organic light emitting device was manufactured in the same manner.

Comparative Examples 1 to 18

An organic light emitting device according to the same method as Example 1 except for using the compound represented by Table 2 instead of the compound represented by Formula 1-2 and / or the compound represented by Formula 2-1 in Example 1 Was prepared. RH-1 and EB-1 compounds described in Table 2 below are as follows.

Experimental Example

When a current was applied to the organic light emitting diodes manufactured in Examples and Comparative Examples, the driving voltage, the luminous efficiency, the emission peak, and the lifetime were measured, and the results are shown in Table 1 below. T97 means the time it takes for the brightness to decrease from 3000 nit to 97%.

Host Electron suppression layer Voltage
(V) efficiency
(Cd / A) CIEx
(cd / m ² ) CIEy
(cd / m ² ) T97
(hr) Example 1 1-2 2-1 3.98 23.4 0.653 0.331 405 Example 2 1-5 2-1 3.91 24.5 0.655 0.333 385 Example 3 1-8 2-1 3.96 23.2 0.654 0.334 380 Example 4 1-12 2-1 3.97 23.4 0.651 0.335 375 Example 5 1-2 2-2 3.94 23.5 0.652 0.334 415 Example 6 1-5 2-2 3.91 23.2 0.652 0.335 370 Example 7 1-8 2-2 3.93 23.4 0.651 0.335 375 Example 8 1-12 2-2 3.95 24.5 0.652 0.334 375 Example 9 1-2 2-3 3.95 25.2 0.651 0.331 400 Example 10 1-5 2-3 3.96 25.4 0.654 0.332 375 Example 11 1-8 2-3 3.95 25.5 0.652 0.333 380 Example 12 1-12 2-3 3.91 25.2 0.653 0.334 375 Example 13 1-2 2-4 3.96 23.4 0.652 0.336 405 Example 14 1-5 2-4 3.91 24.5 0.653 0.334 385 Example 15 1-8 2-4 3.96 23.2 0.654 0.335 375 Example 16 1-12 2-4 3.91 23.4 0.652 0.335 395 Example 17 1-2 2-5 3.92 23.5 0.655 0.334 415 Example 18 1-5 2-5 3.97 24.5 0.651 0.334 380 Example 19 1-8 2-5 3.93 23.2 0.652 0.334 385 Example 20 1-12 2-5 3.91 23.4 0.653 0.333 375 Example 21 1-2 2-6 3.92 23.5 0.655 0.334 420 Example 22 1-5 2-6 3.97 23.2 0.651 0.334 380 Example 23 1-8 2-6 3.93 23.4 0.652 0.334 385 Example 24 1-12 2-6 3.91 23.5 0.653 0.333 385

Host Electron suppression layer Voltage
(V) efficiency
(Cd / A) CIEx
(cd / m ² ) CIEy
(cd / m ² ) T97
(hr) Comparative Example 1 RH-1 EB-1 4.71 19.5 0.651 0.332 285 Comparative Example 2 RH-1 2-1 4.19 24.2 0.651 0.332 315 Comparative Example 3 RH-1 2-2 4.23 23.5 0.653 0.334 320 Comparative Example 4 RH-1 2-3 4.15 24.6 0.654 0.336 325 Comparative Example 5 RH-1 2-4 4.28 23.7 0.655 0.331 320 Comparative Example 6 RH-1 2-5 4.22 24.8 0.651 0.333 310 Comparative Example 7 RH-1 2-6 4.20 23.9 0.655 0.330 325 Comparative Example 8 1-1 EB1 4.32 22.1 0.654 0.335 335 Comparative Example 9 1-2 EB1 4.32 21.5 0.653 0.336 340 Comparative Example 10 1-3 EB1 4.34 22.5 0.652 0.334 355 Comparative Example 11 1-4 EB1 4.45 22.4 0.651 0.335 365 Comparative Example 12 1-5 EB1 4.23 21.5 0.652 0.334 360 Comparative Example 13 1-6 EB1 4.36 21.1 0.653 0.332 355 Comparative Example 14 1-7 EB1 4.44 22.0 0.654 0.333 355 Comparative Example 15 1-8 EB1 4.39 22.3 0.652 0.331 350 Comparative Example 16 1-9 EB1 4.31 22.4 0.653 0.335 345 Comparative Example 17 1-10 EB1 4.41 22.5 0.651 0.336 355 Comparative Example 18 1-11 EB1 4.32 22.9 0.653 0.334 360 Comparative Example 19 1-12 EB1 4.43 22.4 0.652 0.335 355

As shown in Table 1 and 2, the embodiment using the compound represented by the formula (1) according to the present invention as a host, the compound represented by the formula (2) according to the present invention as an electron suppressing layer, the driving voltage compared to the comparative example It was confirmed that the lower the efficiency and the longer the life.

In particular, in Examples 9 to 12, when the compound represented by the formula (1) according to the present invention was used as a host of the light emitting layer, and the compound represented by the formula 2-3 is used as the electron suppression layer, the luminous efficiency was the highest. In addition, in Examples 5, 9, 13, 17, and 21, the longest life was obtained when the chemical formula 1-2 was used as the host of the light emitting layer.

Through this, when the compound represented by the formula (1) of the present invention as a host of the light emitting layer, and the compound represented by the formula (2) of the present invention as an electron blocking layer material, it was confirmed that the driving voltage, luminous efficiency and life characteristics are simultaneously improved .

1: substrate 2: anode
3: electron suppression layer 4: light emitting layer
5: cathode 6: hole transport layer
7: electron transport layer

Claims (10)

anode,
cathode,
A light emitting layer between the anode and the cathode,
An electron suppression layer between the anode and the light emitting layer, and
In the organic light-emitting device comprising a hole transport layer between the electron suppression layer and the anode,
The emission layer includes a compound represented by the following formula (1),
The electron suppression layer comprises a compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₄ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, or two adjacent groups combine to form a benzene ring,
Ar ₁ is substituted or unsubstituted C _6-60 aryl,
Ar ₂ is

, or

ego,
Ar ₃ is substituted or unsubstituted C _6-60 aryl,
R ₅ to R ₈ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, or two adjacent groups combine to form a benzene ring,
[Formula 2]

L is a bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₄ to Ar ₆ are each independently C _6-60 aryl.
The method of claim 1,
Formula 1 is represented by the following formula 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6,
Organic light emitting device:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

The method of claim 1,
Ar ₁ is phenyl, biphenylyl, naphthyl, or dimethylfluorenyl,
Organic light emitting device.
The method of claim 1,
Ar ₂ is any one selected from the group consisting of
Organic light emitting device:

The method of claim 1,
Ar ₃ is phenyl, biphenylyl, or naphthyl,
Organic light emitting device.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

The method of claim 1,
Formula 2 is represented by the following formula 2-1, or 2-2,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

The method of claim 1,
Ar ₄ is phenyl,
Organic light emitting device.
The method of claim 1,
Ar ₅ and Ar ₆ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, phenanthrenyl, phenanthrenylphenyl, or triphenylenyl ,
Organic light emitting device.
The method of claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

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