KR20190056336A - Organic light emitting device - Google Patents

Abstract

The present invention relates to an organic light-emitting device excellent in driving voltage, light-emitting efficiency, and service life. The organic light-emitting device according to an embodiment of the present invention includes: a positive electrode; a light-emitting layer; a hole blocking layer; and a negative electrode, wherein the hole blocking layer includes compounds represented by chemical formula 1, and the light-emitting layer includes compounds represented by chemical formula 2. The organic light-emitting device according to the present invention is characterized in that it is possible to control an energy level between each layer by adjusting substances included in the hole blocking layer and the light-emitting layer, and thus the driving voltage, efficiency, and service life can be improved.

Description

[0001] The present invention relates to an organic light emitting device,

The present invention relates to an organic light emitting device having excellent driving voltage, light emitting efficiency, and long life.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has 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 material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention provides an organic light emitting device having excellent driving voltage, light emitting efficiency, and long life.

In order to achieve the above object, A light emitting layer; A hole blocking layer; And a cathode, wherein the hole blocking layer comprises a compound represented by the following Formula 1, and the light emitting layer comprises a compound represented by the following Formula 2:

[Chemical Formula 1]

In Formula 1,

L ₁ and L ₂ or are bonded to each 1 and 2-position of naphthalene, or bonded to the position 2 and 11 of the naphthalene,

L ₁ is substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,

L ₂ is a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,

Ar ₃ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,

Ar ₃ does not have a pyridine, quinoline, isoquinoline, phenanthridine, benzo [f] quinoline, benzo [f] isoquinoline, benzo [h] quinoline or benzo [h] isoquinoline structure,

(2)

In Formula 2,

Ar ' ₁ and Ar' ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,

R ' ₁ and R' ₂ are each independently selected from the group consisting of hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; A substituted or unsubstituted C _2-60 alkenyl group; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing at least one hetero atom selected from the group consisting of N, O and S,

a and b each independently represent an integer of 0 to 4;

The organic light emitting device according to the present invention can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting diode by using the compound represented by the formula (1) and the compound represented by the formula (2).

Fig. 1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a light emitting layer 3, a hole blocking layer 4, and a cathode 5.
Fig. 2 is a cross-sectional view of a substrate 1, an anode 2, a hole injecting layer 6, a hole transporting layer 7, a luminescent layer 3, a hole blocking layer 4, an electron transporting layer 8, And a cathode (5).

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

는 다른 치환기에 연결되는 결합을 의미한다. In the present specification,

Quot; means a bond connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 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 one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

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 the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, an isoxazolyl group, A benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group,

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.

The present invention relates to a positive electrode; A light emitting layer; A hole blocking layer; And a cathode, wherein the hole blocking layer comprises the compound represented by Formula 1, and the emitting layer comprises the compound represented by Formula 2.

The organic light emitting device according to the present invention is characterized in that it can improve the driving voltage, efficiency and lifetime by adjusting the energy levels between the hole blocking layer and the light emitting layer to control the energy levels.

Hereinafter, the present invention will be described in detail with respect to each constitution and from an anode to a cathode.

anode

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to 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), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

Hole injection layer

The organic light emitting device according to the present invention may further include a hole injection layer on the anode. The hole injecting layer is formed of a hole injecting material. The hole injecting material has a hole injecting effect on the anode, an excellent hole injecting effect on the light emitting layer or the light emitting material due to its ability to transport holes, A compound which prevents migration to the electron injection layer or the electron injecting material and is excellent in the thin film forming ability is preferable.

It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene- Based organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

Hole transport layer

The organic light emitting device according to the present invention may further include a hole transport layer on the anode or the hole injection layer. The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable.

Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light-

The organic light emitting device according to the present invention includes a light emitting layer on the anode, the hole injecting layer, or the hole transporting layer.

The light emitting layer may include a host and a dopant. In the present invention, the compound represented by Formula 2 is used as the host.

In Formula 2, preferably, Ar ' ₁ is naphthyl, phenanthrenyl, dibenzofuranyl, or a substituent represented by the following formula:

In the above, A is a benzene ring fused with two adjacent rings.

Preferably, Ar ' ₁ is naphthyl, phenanthrenyl, dibenzofuranyl, or a substituent represented by the following:

Preferably, Ar ' ₂ is biphenyl, terphenyl, naphthylphenyl, or phenanthrenylphenyl.

Preferably, R _'1 and R' ₂ is hydrogen.

Preferably, the compound represented by Formula 2 is any one selected from the group consisting of the following compounds:

The compound represented by the formula (2) can be prepared by the following reaction scheme (2).

[Reaction Scheme 2]

In the above Reaction Scheme 2, the definitions other than X '' 'are as defined above, and X' '' denotes a substituent used in the Suzuki coupling reaction, preferably halogen, more preferably bromo, or chloro to be. The above reaction means a Suzuki coupling reaction, and the above production method can be further specified in the production example to be described later.

As the dopant, an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex or the like can be used. Particularly, in the present invention, a compound represented by the following formula (3) may be used as the dopant.

(3)

In Formula 3,

L " is substituted or unsubstituted C _6-60 arylene,

Ar " ₁ to Ar " ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl comprising at least one of substituted or unsubstituted O, N, Si and S;

Preferably, L " is any one selected from the group consisting of:

In the above,

R " are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _3-60 cycloalkyl. More preferably, R " , Or cyclopentyl.

Preferably, Ar " ₁ and Ar " ₄ are dibenzofuranyl.

Preferably, Ar " ₂ and Ar " ₃ are phenyl and the phenyl is unsubstituted or substituted with _{Ci_ 60} alkyl, tri ( _{Ci_60} ) alkylsilyl, or phenyl.

Preferably, the compound represented by Formula 3 is any one selected from the group consisting of the following compounds:

Hole blocking layer

The organic light emitting device according to the present invention includes a hole blocking layer on the light emitting layer. The hole blocking layer serves to prevent holes injected from the holes from being transferred to the electron transport layer without being recombined in the light emitting layer.

Particularly, in the present invention, the compound represented by Formula 1 is used in the hole blocking layer.

In the formula 1, L ₁ and L ₂ may be bonded at positions 1 and 2 of naphthalene, respectively, or at positions 2 and 1 of naphthalene, Can:

[Formula 1-1]

[Formula 1-2]

Preferably, L < ₁ > is phenylene. More preferably, L _< 1 > is 1,3-phenylene, or 1,4-phenylene.

Preferably, L < ₂ > is a bond or phenylene. More preferably, L ₂ is a bond, 1,3-phenylene, or 1,4-phenylene.

Preferably, Ar < ₁ > is phenyl.

Preferably, Ar ₂ is phenyl, or biphenyl.

Preferably, Ar < ₃ > is any one selected from the group consisting of:

In the above,

X is _{NR 1, CR 2 R 3,} SiR 4 R 5, S, or O,

R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; A substituted or unsubstituted C _2-60 alkenyl group; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heterocyclic group containing at least one of substituted or unsubstituted O, N, Si and S,

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

More preferably, Ar < ₃ > is any one selected from the group consisting of:

More preferably, Ar ₃ is the above (a), (b), or (c) and L ₂ is a bond; Ar ₃ is the above (d), (f), (g), or (h); L ₂ is 1,4-phenylene; Or Ar ₃ is the above (e), and L ₂ is a bond, 1,3-phenylene, or 1,4-phenylene.

The compound represented by Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by the formula (1) can be prepared by the following reaction scheme (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are as defined above, and X 'and X "denote substituents used in the Suzuki coupling reaction. The above step 1 'refers to a Suzuki coupling reaction, and the production method can be further specified in the production example to be described later.

Electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer on the hole blocking layer. The electron transporting layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer, Materials with high mobility are suitable.

Specific examples of the electron transporting material include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

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. The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable.

Specific examples of materials that can be used for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, Anthrone, and derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, 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- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

cathode

The negative electrode material is preferably 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

Organic light emitting device

The organic light emitting device according to the present invention can be manufactured by sequentially laminating the above-described structures. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, a hole blocking layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. Further, the light emitting layer can be formed by a solution coating method as well as a vacuum deposition method for the host and the dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

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

Meanwhile, the organic light emitting diode according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

[ Manufacturing example ]

Manufacturing example  1: Preparation of compound 1

(Step 1)

(20.0 g, 89.7 mmol), 2,4-diphenyl-6- (4- (4,4,5,5,5-tetramethyl-1,3,2-dioxabor Yl) phenyl) -1,3,5-triazine (50.0 g, 94.1 mmol) and potassium carbonate (24.8 g, 179.3 mmol). After refluxing, tetrakis (triphenylphosphine) palladium (0) (1.2 g, 1.0 mmol) was added and the mixture was stirred under heating for further 5 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. The residue was distilled off under reduced pressure and then washed with ethanol to obtain Compound 1-A (39 g, yield: 96%).

MS: [M + H] < ⁺ > = 452

(Step 2)

Compound 1-A (39 g, 86.4 mmol) and potassium carbonate (23.9 g, 172.7 mmol) were added to an acetonitrile solvent (300 mL) and heated to 50 占 폚. After stirring for 30 minutes, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (39.1 g, 129.6 mmol) was added, the temperature was lowered to room temperature , And the mixture was further stirred for 1 hour. After completion of the reaction, the impurities were removed by primary filtration. Compound 1-B (60 g, yield 95%) was then prepared through an ethanol slurry.

MS: [M + H] < ⁺ > = 734

(Step 3)

Borane acid (25.9 g, 71.6 mmol) and potassium carbonate (18.8 g, 136.3 mmol) were added to a solution of compound 1-B (50 g, 68.2 mmol), (9,9- Was added to 400 mL of a hydrofuran solvent, and the mixture was heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (2.4 g, 2.0 mmol) was added and the mixture was stirred for 6 hours. The reaction solution was cooled, filtered, and Compound 1 (47 g, yield 91.7%) was obtained through purification of the EtOH slurry.

MS: [M + H] < ⁺ > = 752

Manufacturing example  2: Preparation of compound 3

Yl] boronic acid was used in place of 9,9'-spiro [fluorene] -2-ylboronic acid in place of (9,9-diphenyl-9H- Compound 3 was prepared.

MS: [M + H] < ⁺ > = 750

Manufacturing example  3: Preparation of compound 5

(9,9-diphenyl-9H-fluoren-2-yl) boronic acid instead of spiro [fluorene-9,8'-indolo [3,2,1-de] acridine] Compound 5 was prepared in the same manner as Compound 1, except that the acid was used.

MS: [M + H] < ⁺ > = 839

Manufacturing example  4: Preparation of compound 7

Compound 7 was prepared in the same manner as Compound 1, except that triphenylene-2-ylboronic acid was used instead of (9,9-diphenyl-9H-fluoren-2-yl) boronic acid.

MS: [M + H] < ⁺ > = 662

Manufacturing example  5: Preparation of Compound 9

(Step 1)

Boronic acid (31.2 g, 89.7 mmol) and potassium carbonate (24.8 g, 179.3 mmol) were added to a solution of 1- bromomonaphthalene-2-ol (20.0 g, 89.7 mmol) And the mixture was heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (3.1 g, 2.6 mmol) was added and the mixture was further stirred with heating for 3 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. The residue was distilled off under reduced pressure and then washed with ethanol to obtain Compound 9-A (38 g, yield 95%).

MS: [M + H] < ⁺ > = 447

(Step 2)

Compound 9-B was prepared in the same manner as Compound 1-B except for using Compound 9-A instead of Compound 1-A.

MS: [M + H] < ⁺ > = 729

(Step 3)

Compound 9-B was used in the place of Compound 1-B and 2,4-diphenyl-6- (4- (4,4,5,5-tetrahydro-2H- , 5-tetramethyl-1,3,2-dioxaborolen-2-yl) phenyl) -1,3,5-triazine was used in place of Respectively.

MS: [M + H] < ⁺ > = 738

Manufacturing example  6: Preparation of compound 11

(Step 1)

(20.0 g, 89.7 mmol), triphenylene-2-ylboronic acid (24.4 g, 89.7 mmol) and potassium carbonate (24.8 g, 179.3 mmol) were placed and the mixture was heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (3.1 g, 2.6 mmol) was added and the mixture was further stirred with heating for 3 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure, followed by washing with ethanol to obtain Compound 11-A (30 g, yield 91%).

MS: [M + H] < ⁺ > = 371

(Step 2)

Compound 11-B was prepared in the same manner as compound 1-B, except that compound 11-A was used in place of compound 1-A.

MS: [M + H] < ⁺ > = 653

(Step 3)

Compound 11-B (50 g, 76.6 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxabororen- ) Phenyl) -1,3,5-triazine (33.4 g, 76.6 mmol), potassium carbonate (20.3 g, 153.2 mmol) and tetrakis (triphenylphosphine) palladium (0) And the mixture was heated and stirred for 4 hours. After completion of the reaction, the reaction solution was cooled and filtered, and Compound 11 (47 g, yield 93%) was obtained through purification of the EtOH slurry.

MS: [M + H] < ⁺ > = 662

Manufacturing example  7: Preparation of compound 13

(Step 1)

2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolen-2-yl) phenyl) Instead of 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolen-2-yl) phenyl) Compound 13-A was prepared in the same manner as Compound 1-A, except that azine was used.

MS: [M + H] < ⁺ > = 452

(Step 2)

Compound 13-B was prepared in the same manner as compound 1-B except that compound 13-A was used in place of compound 1-A.

MS: [M + H] < ⁺ > = 734

(Step 3)

(9,9-diphenyl-9H-fluoren-4-yl) boron instead of (9,9-diphenyl-9H- Compound 13 was prepared in the same manner as Compound 1, except that the acid was used.

MS: [M + H] < ⁺ > = 752

Manufacturing example  8: Preparation of compound 14

Ylboronic acid was used instead of 9,9'-spiro [fluorene] -2-ylboronic acid instead of (9,9-diphenyl-9H- 14.

MS: [M + H] < ⁺ > = 750

Manufacturing example  9: Preparation of compound 18

Compound 14 was prepared in the same manner as Compound 13, except that [1,1'-biphenyl] -4-ylboronic acid was used in place of (9,9-diphenyl-9H-fluoren- .

MS: [M + H] < ⁺ > = 588

Manufacturing example  10: Preparation of compound 19

Compound 19 was prepared in the same manner as Compound 7, except that Compound 13-B was used instead of Compound 1-B.

MS: [M + H] < ⁺ > = 662

Manufacturing example  11: Preparation of Compound 50

(Step 1)

2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolen-2-yl) phenyl) Instead of 2 - ([1,1'-biphenyl] -3-yl) -4-phenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolene -2-yl) phenyl) -1,3,5-triazine, the compound 50-A was prepared in the same manner as the compound 1-A.

MS: [M + H] < ⁺ > = 528

(Step 2)

Compound 50-B was prepared in the same manner as compound 1-B, except that compound 50-A was used in place of compound 1-A.

MS: [M + H] < ⁺ > = 810

(Step 3)

(9H-carbazol-9-yl) phenyl) boronic acid was used in place of (9,9-diphenyl-9H-fluoren- 50.

MS: [M + H] < ⁺ > = 753

Preparation Example 12: Preparation of Compound 66

(7-phenyl-7H-benzo [c] fluorene-2-yl) boronic acid instead of 4,4,5,5-tetramethyl- 7-yl) phenyl) -1,3,2-dioxaborolene was used in place of the compound (1).

MS: [M + H] < ⁺ > = 802

Manufacturing example  13: Preparation of compound 82

Compound 82 was synthesized in the same manner as Compound 1, except that (4- (phenanthrene-2-yl) phenyl) boronic acid was used in place of (9,9-diphenyl-9H- .

MS: [M + H] < ⁺ > = 688

Manufacturing example  14: Preparation of Compound A

(15.1 g, 60.7 mmol), (10-phenylanthracene-9-yl) boronic acid (18.1 g, 60.7 mmol) and potassium carbonate (25.1 g, 182.1 mmol) were placed and heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 3 mol%) was added and the mixture was heated and stirred for additional 6 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from ethanol to obtain Compound A (19.9 g, yield 78%).

MS: [M + H] < ⁺ > = 421

Manufacturing example  15: Preparation of compound B

(15.1 g, 60.7 mmol), (10-phenylanthracene-9-yl) boronic acid (18.1 g, 60.7 mmol) and potassium carbonate (25.1 g, 182.1 mmol) were placed and heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 3 mol%) was added and the mixture was heated and stirred for further 7 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound B (18.1 g, yield 71%) was prepared by recrystallization from ethanol.

MS: [M + H] < ⁺ > = 421

Manufacturing example  16: Preparation of compound C

(15.1 g, 50.5 mmol) and potassium carbonate (20.9 g, 151.4 mmol) were added to a solution of 2-bromonaphtho [2,3-b] benzofuran ) Were added and heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (1.7 g, 3 mol%) was added and the mixture was heated and stirred for additional 8 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was recrystallized with ethanol to obtain Compound C (16.3 g, yield 69%).

MS: [M + H] < ⁺ > = 471

Manufacturing example  17: Preparation of compound D

(15.1 g, 60.7 mmol), (10-phenylanthracene-9-yl) boronic acid (18.1 g, 60.7 mmol) and potassium carbonate (25.1 g, 182.1 mmol) were placed and heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 3 mol%) was added and the mixture was further heated and stirred for 5 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was recrystallized from ethanol to obtain Compound (D) (20.2 g, yield 79%).

MS: [M + H] < ⁺ > = 421

Manufacturing example  18: Preparation of Compound E

(10 g, 42.9 mmol), (10- (naphthalen-1-yl) anthracene-9-yl) boronic acid (14.9 g, 42.9 mmol) and potassium carbonate g, 128.7 mmol), and the mixture was heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (1.4 g, 3 mol%) was added and the mixture was further heated and stirred for 5 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was recrystallized with ethanol to obtain Compound E (16.1 g, yield 82%).

MS: [M + H] < ⁺ > = 457

Manufacturing example  19: Preparation of compound F

Boronic acid (12.3 g, 35.3 mmol) and potassium carbonate (14.6 g, 35.3 mmol) were added to a solution of 2- (4-bromophenyl) naphthalene (10 g, 35.3 mmol), 10- (naphthalen- 105.9 mmol), and the mixture was heated and stirred. After refluxing, tetrakis (triphenylphosphine) palladium (0) (1.2 g, 3 mol%) was added and the mixture was further heated and stirred for 6 hours. After completion of the reaction, the temperature was lowered to room temperature, and then the impurities were removed by primary filtration. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized with ethanol to obtain Compound F (14.3 g, yield 80%).

MS: [M + H] < ⁺ > = 507

Manufacturing example  20: Preparation of compound G

(15.9 g, 48.5 mmol) and (10- (naphthalen-2-yl) anthracene-9-yl) boronic acid (16.9 g, 48.5 (triphenylphosphine) palladium (0) (1.7 g, 3 mol%) was added, and the mixture was heated for further 6 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and then filtered to remove impurities. The filtrate was poured into water and extracted with chloroform to obtain an organic layer, which was then dried over anhydrous magnesium sulfate. The compound G (17.1 g, yield 66%) was prepared by recrystallization.

MS: [M + H] < ⁺ > = 533

[ Example ]

Example  One

A thin glass substrate coated with ITO (indium tin oxide) having a thickness of 1300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following compound HI-A was vacuum deposited on the ITO transparent electrode prepared as described above to a thickness of 600 Å to form a hole injection layer. The following compound HAT-CN (50 Å) and the following compound HT-A (600 Å) were sequentially vacuum-deposited on the hole injection layer to form a hole transport layer. Subsequently, Compound A and Compound BD, which were previously prepared to a film thickness of 200 ANGSTROM, were vacuum deposited on the hole transport layer at a weight ratio of 25: 1 to form a light emitting layer. Compound 1 prepared above was vacuum deposited on the light emitting layer to a thickness of 50 Å to form a hole blocking layer. An electron transport layer was formed on the hole blocking layer at a 2: 1 weight ratio of the following compound ET-A and LiQ (8-hydroxyquinolatolithium) in a thickness of 300 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron transporting layer to form a cathode.

The deposition rate of the organic material was maintained at 0.4 to 0.9 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. by keeping the ^-7 to 5 × 10 ^-8 torr, an organic light emitting device was produced.

Example  2 to 26

The organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound A and Compound 1, respectively.

Comparative Example  1 to 7

The organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound A and Compound 1, respectively. In Table 1 below, ET1, ET2, ET3, ET4, ET5 and ET6 compounds are as follows.

Experimental Example

The driving voltage, luminous efficiency and color coordinates were measured at a current density of 10 mA / cm < ² > at a current density of 20 mA / cm < ² & gt _; ) Were measured. The results are shown in Table 1 below.

BH HBL Voltage (V) Efficiency (cd / A) The color coordinates (x, y) T ₉₀ (hr) Example 1 Compound A Compound 1 3.68 7.32 (0.130, 0.147) 181 Example 2 Compound A Compound 3 3.69 7.53 (0.131, 0.147) 160 Example 3 Compound A Compound 5 3.81 7.25 (0.130, 0.146) 201 Example 4 Compound A Compound 7 3.88 7.35 (0.131, 0.147) 210 Example 5 Compound A Compound 9 3.92 7.16 (0.130, 0.146) 221 Example 6 Compound A Compound 11 3.88 7.35 (0.130, 0.147) 217 Example 7 Compound A Compound 13 3.68 7.44 (0.130, 0.147) 195 Example 8 Compound A Compound 14 3.77 7.52 (0.131, 0.147) 162 Example 9 Compound A Compound 18 3.72 7.48 (0.130, 0.147) 172 Example 10 Compound B Compound 19 3.92 7.45 (0.130, 0.148) 165 Example 11 Compound B Compound 50 3.96 7.64 (0.130, 0.147) 153 Example 12 Compound B Compound 66 3.86 7.78 (0.131, 0.147) 157 Example 13 Compound B Compound 82 3.83 7.65 (0.130, 0.147) 167 Example 14 Compound C Compound 1 3.25 7.77 (0.130, 0.148) 162 Example 15 Compound C Compound 7 3.19 7.95 (0.130, 0.147) 145 Example 16 Compound C Compound 11 3.20 7.68 (0.131, 0.147) 177 Example 17 Compound D Compound 50 3.54 7.13 (0.130, 0.146) 162 Example 18 Compound D Compound 66 3.65 7.01 (0.130, 0.147) 185 Example 19 Compound E Compound 82 3.69 7.88 (0.130, 0.147) 199 Example 20 Compound E Compound 18 3.88 7.68 (0.131, 0.147) 201 Example 21 Compound E Compound 19 3.91 7.53 (0.130, 0.147) 186 Example 22 Compound F Compound 1 3.52 8.24 (0.130, 0.148) 160 Example 23 Compound F Compound 3 3.57 8.16 (0.130, 0.147) 153 Example 24 Compound F Compound 5 3.61 8.36 (0.131, 0.147) 158 Example 25 Compound G Compound 19 3.88 7.46 (0.130, 0.148) 186 Example 26 Compound G Compound 50 3.73 7.56 (0.130, 0.147) 170 Comparative Example 1 Compound A ET1 4.21 6.25 (0.130, 0.147) 132 Comparative Example 2 Compound A ET2 4.38 6.12 (0.130, 0.147) 145 Comparative Example 3 Compound A ET3 3.92 6.01 (0.131, 0.147) 112 Comparative Example 4 Compound F ET1 4.12 6.72 (0.130, 0.147) 95 Comparative Example 5 Compound F ET4 4.42 6.35 (0.130, 0.148) 120 Comparative Example 6 Compound F ET5 4.51 6.29 (0.130, 0.147) 160 Comparative Example 7 Compound F ET6 4.20 6.51 (0.130, 0.147) 135

1: substrate 2: anode
3: light emitting layer 4: hole blocking layer
5: cathode 6: hole injection layer
7: hole transport layer 8: electron transport layer
9: Electron injection layer

Claims (15)

anode;
A light emitting layer;
A hole blocking layer; And
A cathode,
Wherein the hole blocking layer comprises a compound represented by the following Formula 1,
Wherein the light emitting layer comprises a compound represented by the following general formula (2)
Organic Light Emitting Device:
[Chemical Formula 1]

In Formula 1,
L ₁ and L ₂ or are bonded to each 1 and 2-position of naphthalene, or bonded to the position 2 and 11 of the naphthalene,
L ₁ is substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,
L ₂ is a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,
Ar ₃ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,
Ar ₃ does not have a pyridine, quinoline, isoquinoline, phenanthridine, benzo [f] quinoline, benzo [f] isoquinoline, benzo [h] quinoline or benzo [h] isoquinoline structure,
(2)

In Formula 2,
Ar ' ₁ and Ar' ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,
R ' ₁ and R' ₂ are each independently selected from the group consisting of hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; A substituted or unsubstituted C _2-60 alkenyl group; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing at least one hetero atom selected from the group consisting of N, O and S,
a and b each independently represent an integer of 0 to 4;
The method according to claim 1,
L < ₁ > is phenylene,
Organic light emitting device.
The method according to claim 1,
L < ₂ > is a bond,
Organic light emitting device.
The method according to claim 1,
Ar < ₁ > is phenyl,
Organic light emitting device.
The method according to claim 1,
Ar < ₂ > is phenyl, or biphenyl,
Organic light emitting device.
The method according to claim 1,
Ar < ₃ > is any one selected from the group consisting of:
Organic Light Emitting Device:

In the above,
X is _{NR 1, CR 2 R 3,} SiR 4 R 5, S, or O,
R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; A substituted or unsubstituted C _2-60 alkenyl group; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heterocyclic group containing at least one of substituted or unsubstituted O, N, Si and S,
n, m and l are each independently an integer of 0 to 4;
The method according to claim 1,
Wherein the compound represented by the formula (1) is any one selected from the group consisting of the following compounds:
Organic Light Emitting Device:

The method according to claim 1,
Ar < ₁ > is selected from the group consisting of naphthyl, phenanthrenyl, dibenzofuranyl,
Organic Light Emitting Device:

In the above, A is a benzene ring fused with two adjacent rings.
The method according to claim 1,
Ar ' ₂ is biphenyl, terphenyl, naphthylphenyl, or phenanthrenylphenyl,
Organic light emitting device.
The method according to claim 1,
R ' ₁ and R ' ₂ are hydrogen,
Organic light emitting device.
The method according to claim 1,
Wherein the compound represented by Formula 2 is any one selected from the group consisting of the following compounds:
Organic Light Emitting Device:

The method according to claim 1,
Wherein the light emitting layer further comprises a compound represented by the following general formula (3)
Organic Light Emitting Device:
(3)

In Formula 3,
L " is substituted or unsubstituted C _6-60 arylene,
Ar " ₁ to Ar " ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl comprising at least one of substituted or unsubstituted O, N, Si and S;
13. The method of claim 12,
L "is any one selected from the group consisting of:
Organic Light Emitting Device:

In the above,
R " are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _3-60 cycloalkyl.
13. The method of claim 12,
Ar " ₁ and Ar " ₄ are dibenzofuranyl,
Organic light emitting device.
13. The method of claim 12,
Wherein the compound represented by the formula (3) is any one selected from the group consisting of the following compounds:
Organic Light Emitting Device:

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