KR20180127909A - Novel hetero ring compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The compound can be used as a material of an organic material layer of the organic light emitting device and can improve efficiency, low driving voltage and/or lifetime characteristics in the organic light emitting device.

Description

[0001] The present invention relates to a novel heterocyclic compound and an organic light emitting device using the same,

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

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 relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

The present invention provides a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

R < ₁ > and R < ₂ > are hydrogen,

X ₁ to X ₃ are each independently N or CH, with the proviso that at least one of X ₁ to X ₃ is N,

Ar ₁ and Ar ₂ are each independently a 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,

Ar ₃ is substituted or unsubstituted C _6-60 aryl; Carbazolyl; 9-phenylcarbazolyl; Dibenzofuranyl; Dibenzothiophenyl; Or a substituent represented by the following formula (2): < EMI ID =

(2)

In Formula 2,

Y ₁ and Y ₂ are each independently N or CH, provided that at least one of Y ₁ and Y ₂ is N,

Z is O, or S,

Ar ₄ is 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,

R is hydrogen; 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,

n is an integer of 1 to 4;

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.

The compound represented by the general formula (1) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device. In particular, the compound represented by Formula 1 can be used as a hole injecting, hole transporting, hole injecting and transporting, light emitting, electron transporting, or electron injecting material.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

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

The present invention provides a compound represented by the above formula (1).

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.

In Formula 1, Formula 1 may be represented by Formula 1-1 to Formula 1-4, depending on the bonding position.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Formulas 1-1 to 1-4,

X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ and Ar ₃ are as defined above.

Preferably, Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, Dibenzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl. More preferably, Ar ₁ and Ar ₂ are each independently phenyl or biphenylyl.

Preferably, Ar ₃ is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, anthracenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, - phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl.

Preferably, in Formula 2, Ar ₄ is phenyl, biphenyl, naphthyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9- It is sleepy. Also preferably, in Formula 2, R is hydrogen.

Representative examples of the compound represented by the above formula (1) are as follows:

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, R ₁ , R ₂ , X ₁ to X ₃ , Ar ₁ , Ar ₂ , and Ar ₃ are as defined above, and X is halogen. Preferably, X is chloro.

The reaction scheme 1 is a Suzuki coupling reaction in which a compound represented by the formula 1-a and a compound represented by the formula 1-b are reacted with a palladium catalyst in the presence of a base to produce a compound represented by the formula 1 to be. The above production method can be more specific in the production example to be described later.

Also, the present invention provides an organic light emitting device including the compound represented by Formula 1. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, And a compound to be displayed.

In addition, the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by the general formula (1).

The organic material layer may include an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound represented by the above formula (1).

Further, the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound represented by the above formula (1).

The organic material layer may include a light emitting layer and an electron transporting layer, and the electron transporting layer may include a compound represented by the general formula (1).

In addition, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the compound represented by Formula 1 may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula (1). In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. 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 and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. 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.

In addition, the compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. 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.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

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.

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.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also 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, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

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 emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer 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. Do. Specific examples 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 with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the 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 thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, 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- 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.

The organic light emitting device 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.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

The preparation of the compound represented by Formula 1 and the organic light emitting device comprising the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  One

Compound A (7.68 g, 11.23 mmol) and compound a1 (3.67 g, 10.70 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (240 mL) to give Preparation Example 1 (7.69 g, 83%).

MS [M + H] < ⁺ > = 865

Manufacturing example  2

To a 500 mL round bottom flask under nitrogen was added a solution of compound B (12.30 g, 16.20 mmol) and compound a2 (4.12 g, 15.43 mmol) in 220 mL of tetrahydrofuran, followed by the addition of 2M aqueous potassium carbonate solution (110 mL) , And tetrakis- (triphenylphosphine) palladium (0.53 g, 0.46 mmol) were added thereto, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (320 mL) to give Preparation Example 2 (10.08 g, 76%).

MS [M + H] < ⁺ > = 865

Manufacturing example  3

Compound C (10.57 g, 13.96 mmol) and compound a2 (3.55 g, 13.30 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (100 mL) , And tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) were 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 from 180 mL of tetrahydrofuran to give Preparation Example 3 (9.95 g, 87%).

MS [M + H] < ⁺ > = 863

Manufacturing example  4

Compound D (10.47 g, 15.02 mmol) and compound a2 (3.82 g, 14.31 mmol) were completely dissolved in 260 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (130 mL) , And tetrakis- (triphenylphosphine) palladium (0.50 g, 0.43 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (280 mL) to give Preparation Example 4 (8.44 g, 73%).

MS [M + H] < ⁺ > = 803

Manufacturing example  5

Compound E (12.23 g, 17.15 mmol) and compound a2 (4.36 g, 16.33 mmol) were dissolved in 280 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (140 mL) , And tetrakis- (triphenylphosphine) palladium (0.57 g, 0.49 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (250 mL) to give Preparation Example 5 (10.27 g, 77%).

MS [M + H] < ⁺ > = 819

Manufacturing example  6

Compound A (7.05 g, 10.32 mmol) and compound a3 (3.37 g, 9.83 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (100 mL) , And tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (240 mL) to give Preparation Example 6 (6.49 g, 81%).

MS [M + H] < ⁺ > = 865

Manufacturing example  7

Compound A (7.05 g, 10.32 mmol) and compound a4 (3.37 g, 9.83 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (100 mL) , And tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (240 mL) to give Preparation Example 7 (6.49 g, 81%).

MS [M + H] < ⁺ > = 787

Manufacturing example  8

Compound A (9.00 g, 13.17 mmol) and Compound a5 (4.29 g, 12.54 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.43 g, 0.38 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (240 mL) to give Preparation Example 8 (7.77 g, 72%).

MS [M + H] < ⁺ > = 864

Manufacturing example  9

Compound F (11.26 g, 15.53 mmol) and compound a2 (3.95 g, 14.79 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.51 g, 0.44 mmol) were 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 from ethyl acetate (280 mL) to give Preparation Example 9 (8.11 g, 66%).

MS [M + H] < ⁺ > = 831

Manufacturing example  10

Compound G (13.97 g, 18.36 mmol) and compound a6 (4.65 g, 17.48 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (110 mL) , And tetrakis- (triphenylphosphine) palladium (0.61 g, 0.52 mmol) were added thereto, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (250 mL) to prepare Preparative Example 10 (10.9 g, 72%).

MS [M + H] < ⁺ > = 866

Manufacturing example  11

Compound H (10.57 g, 13.96 mmol) and compound a2 (3.55 g, 13.30 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (100 mL) , And tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) were 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 from 180 mL of tetrahydrofuran to give Preparation Example 11 (8.96 g, 87%).

MS [M + H] < ⁺ > = 865

Manufacturing example  12

Compound I (10.47 g, 15.02 mmol) and compound a2 (3.82 g, 14.31 mmol) were completely dissolved in 260 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (130 mL) , And tetrakis- (triphenylphosphine) palladium (0.50 g, 0.43 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (280 mL) to give Preparation Example 12 (7.60 g, 65%).

MS [M + H] < ⁺ > = 821

Manufacturing example  13

Compound J (12.23 g, 17.15 mmol) and compound a2 (4.36 g, 16.33 mmol) were dissolved in 280 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (140 mL) , And tetrakis- (triphenylphosphine) palladium (0.57 g, 0.49 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (250 mL) to give Preparation Example 13 (9.25 g, 69%).

MS [M + H] < ⁺ > = 805

Manufacturing example  14

Compound F (9.37 g, 12.92 mmol) and compound a3 (4.22 g, 12.30 mmol) were dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.43 g, 0.37 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from tetrahydrofuran (220 mL) to give Preparation Example 14 (9.15 g, 86%).

MS [M + H] < ⁺ > = 907

Manufacturing example  15

Compound K (11.07 g, 15.20 mmol) and compound a2 (4.51 g, 16.89 mmol) were completely dissolved in 280 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (140 mL) And tetrakis- (triphenylphosphine) palladium (0.59 g, 0.51 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (250 mL) to give Preparation Example 15 (8.17 g, 55%).

MS [M + H] < ⁺ > = 882

Manufacturing example  16

To a 500 mL round bottom flask under nitrogen was added a solution of compound L (11.74 g, 15.78 mmol) and compound a2 (4.68 g, 17.53 mmol) in 280 mL of tetrahydrofuran, followed by the addition of 2M aqueous potassium carbonate (140 mL) , And tetrakis- (triphenylphosphine) palladium (0.61 g, 0.53 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (250 mL) to give Preparation 16 (9.12 g, 58%).

MS [M + H] < ⁺ > = 899

Example  1-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 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, which was secondly filtered with 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.

On the ITO transparent electrode thus prepared, a compound represented by the following chemical formula HAT was thermally vacuum deposited to a thickness of 150 Å to form a hole injection layer. A hole transport layer was formed on the hole injection layer by vacuum evaporation of a compound (1150 ANGSTROM) represented by the following formula (HT1), which is a hole transport material. Subsequently, a compound represented by the following formula (EB1) was vacuum deposited on the hole transport layer to a thickness of 100 ANGSTROM to form an electron blocking layer. Subsequently, a compound represented by the following formula (BH) and a compound represented by the following formula (BD) were vacuum deposited on the electron blocking layer to a thickness of 200 angstroms at a weight ratio of 25: 1 to form a light emitting layer. A hole blocking layer was formed on the light emitting layer by vacuum evaporation of a compound represented by the following formula (HB1) to a film thickness of 50 angstroms. Subsequently, the compound prepared in Preparation Example 1 and the compound represented by LiQ shown below were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 310 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of the lithium fluoride of the cathode was 0.3 Å / sec and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 < ^-6 > torr to manufacture an organic light emitting device.

Example  1-2 to 1-12

Except that the compounds described in Table 1 were used instead of the compound prepared in Preparation Example 1 to prepare an organic light emitting device.

Comparative Example  1-1 to 1-4

Except that the compounds described in Table 1 were used instead of the compound prepared in Preparation Example 1 to prepare an organic light emitting device. ET1, ET2, ET3, and ET4 used in Table 1 are as follows.

Experimental Example  One

The voltage, efficiency, color coordinates and lifetime of the organic light-emitting device manufactured in Examples and Comparative Examples were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (1600 nits) to 95%.

compound
(Electron transport layer) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) T95
(hr) Example 1-1 Production Example 1 4.23 5.91 (0.140, 0.049) 290 Examples 1-2 Production Example 4 4.34 5.86 (0.141, 0.046) 285 Example 1-3 Production Example 5 4.66 5.52 (0.141, 0.047) 255 Examples 1-4 Production Example 6 4.37 5.82 (0.142, 0.042) 280 Examples 1-5 Production Example 7 4.58 5.66 (0.141, 0.045) 250 Examples 1-6 Production Example 8 4.39 5.89 (0.140, 0.045) 285 Examples 1-7 Production Example 9 4.21 5.95 (0.142, 0.043) 280 Examples 1-8 Production Example 12 4.35 5.83 (0.141, 0.050) 290 Examples 1-9 Production Example 13 4.32 5.81 (0.141, 0.043) 295 Example 1-10 Production Example 14 4.51 5.61 (0.141, 0.044) 275 Example 1-11 Production Example 15 4.63 5.58 (0.141, 0.044) 310 Examples 1-12 Production Example 16 4.62 5.59 (0.141, 0.044) 305 Comparative Example 1-1 ET 1 5.28 5.34 (0.141, 0.045) 220 Comparative Example 1-2 ET 2 4.85 5.12 (0.140, 0.043) 235 Comparative Example 1-3 ET 3 4.92 5.23 (0.141, 0.044) 225 Comparative Example 1-4 ET 4 4.73 5.04 (0.141, 0.046) 245

As shown in Table 1, it was confirmed that the organic light emitting device manufactured using the compound of the present invention as an electron transport layer exhibited excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device. fluorene-9,8-indoloacridine The asymmetric compounds of the present invention wherein an aryl group is connected to the 3-position and an electron-withdrawing substituent is connected to the 5-position are prepared by reacting the compound of Comparative Examples 1-1 to 1-4, The organic light emitting device of the present invention exhibits low voltage and high efficiency characteristics. As shown in Table 1, it was confirmed that the compounds according to the present invention are excellent in electron transporting ability and applicable to organic light emitting devices.

Comparative Example  2-1

Except that BH and BD were used instead of BH and BD as the light emitting layer, a compound represented by the formula GH1 and a compound represented by the following formula GD were respectively vacuum-deposited at a weight ratio of 20: Thereby forming an organic light emitting device.

Comparative Example  2-2

Was prepared in the same manner as in the above Comparative Example 2-1 except that the compound represented by the formula GH2 was used instead of the compound represented by the formula GH1 to prepare an organic light emitting device.

Example  2-1 to 2-13

Except that the compound shown in the following Table 2 was used instead of the compound represented by the formula GH1 to prepare an organic light emitting device.

Experimental Example  2

The voltage, efficiency, color coordinates and lifetime of the organic light-emitting device manufactured in Examples and Comparative Examples were measured, and the results are shown in Table 2 below. T95 means the time required for the luminance to decrease from the initial luminance (6000 nits) to 95%.

compound
(Green luminescent layer
Host) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) T95 (hr) Example 2-1 Production Example 1 3.75 126.01 (0.255, 0.718) 360 Example 2-2 Production Example 2 3.87 121.71 (0.254, 0.718) 355 Example 2-3 Production Example 4 3.86 121.63 (0.253, 0.717) 345 Examples 2-4 Production Example 6 3.88 122.77 (0.256, 0.718) 340 Example 2-5 Production Example 7 3.84 123.55 (0.252, 0.717) 345 Examples 2-6 Production Example 8 3.85 121.42 (0.255, 0.719) 335 Examples 2-7 Production Example 9 3.84 121.91 (0.255, 0.708) 340 Examples 2-8 Production Example 10 3.96 119.65 (0.256, 0.707) 330 Examples 2-9 Production Example 11 3.98 119.81 (0.254, 0.706) 345 Examples 2-10 Production Example 12 3.97 117.75 (0.255, 0.708) 325 Examples 2-11 Production Example 13 3.91 116.55 (0.257, 0.695) 325 Examples 2-12 Production Example 14 3.95 118.46 (0.255, 0.699) 315 Examples 2-13 Production Example 15 4.95 118.68 (0.255, 0.697) 325 Comparative Example 2-1 GH1 4.12 106.46 (0.251, 0.715) 290 Comparative Example 2-2 GH2 4.28 98.45 (0.254, 0.702) 210

As shown in Table 2, the organic light emitting device manufactured using the compound of the present invention as a green light emitting layer exhibits excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device. fluorene-9,8-indoloacridine The asymmetric compounds of the present invention in which the aryl group is connected to the 3-position and the electron-withdrawing substituent is connected to the 5-position are used as the host of the green light- Lower voltage, and higher efficiency. As shown in the results of Table 2, it was confirmed that the compounds of the present invention are excellent in light emitting ability and applicable to organic light emitting devices.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (9)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R < ₁ > and R < ₂ > are hydrogen,
X ₁ to X ₃ are each independently N or CH, with the proviso that at least one of X ₁ to X ₃ is N,
Ar ₁ and Ar ₂ are each independently a 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,
Ar ₃ is substituted or unsubstituted C _6-60 aryl; Carbazolyl; 9-phenylcarbazolyl; Dibenzofuranyl; Dibenzothiophenyl; Or a substituent represented by the following formula (2): < EMI ID =
(2)

In Formula 2,
Y ₁ and Y ₂ are each independently N or CH, provided that at least one of Y ₁ and Y ₂ is N,
Z is O, or S,
Ar ₄ is 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,
R is hydrogen; 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,
n is an integer of 1 to 4;
The method according to claim 1,
Wherein said formula (1) is represented by any one of the following formulas (1-1) to (1-4)
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Formulas 1-1 to 1-4,
X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ and Ar ₃ are as defined in claim 1.
The method according to claim 1,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, Benzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl,
compound.
The method according to claim 1,
Ar < _{1 >} and Ar < ₂ > are each independently phenyl,
compound.
The method according to claim 1,
Ar ₃ is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, anthracenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, , Dibenzofuranyl, or dibenzothiophenyl,
compound.
The method according to claim 1,
Ar ₄ is phenyl, biphenyl, naphthyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-
compound.
The method according to claim 1,
R is hydrogen,
compound.
The method according to claim 1,
The compound represented by the formula (1) is any one selected from the group consisting of
compound:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes a compound according to any one of claims 1 to 8 The organic light-emitting device.

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