KR102665301B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic light-emitting compound represented by the following [Chemical Formula I], and when it is used in an electron blocking layer, etc., it is possible to implement an organic electroluminescent device with excellent quantum efficiency and luminous efficiency characteristics.
[Formula Ⅰ]

Description

An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to organic light-emitting compounds, and more specifically, to organic light-emitting compounds employed in the organic material layer within an organic light-emitting device, and to organic light-emitting devices with significantly improved light-emitting properties such as luminous efficiency and quantum efficiency by employing the same.

Organic electroluminescent devices not only can be formed on transparent substrates, but also can be driven at low voltages of 10 V or less compared to plasma display panels or inorganic electroluminescent (EL) displays, and consume relatively little power. It has the advantage of excellent color and can display three colors: green, blue, and red, so it has recently been the subject of much attention as a next-generation display device.

However, in order for these organic electroluminescent devices to exhibit the above characteristics, the materials that make up the organic layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, must be supported by stable and efficient materials. However, the development of stable and efficient organic material layer materials for organic electroluminescent devices has not yet been sufficiently developed. Therefore, there is a continued need for the development of new materials that can improve luminescence characteristics and the development of organic layer structures within devices.

Therefore, the present invention seeks to provide a novel organic light-emitting compound that can be employed in the electron blocking layer in an organic light-emitting device to significantly improve luminous efficiency, and an organic light-emitting device containing the same.

In order to solve the above problems, the present invention provides an organic light-emitting compound represented by the following [Chemical Formula I] and an organic electroluminescent device containing the same.

[Formula Ⅰ]

A detailed description of the structure and substituents of [Chemical Formula I] will be described later.

An organic electroluminescent device employing the organic light-emitting compound according to the present invention as an electron blocking layer can realize significantly improved luminous efficiency compared to conventional devices and can be usefully used in various display devices.

1 is a representative diagram showing the structure of an organic light-emitting compound according to the present invention.

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

The present invention is an organic light-emitting compound represented by the following [Chemical Formula I], which is characterized in that an aromatic heterocycle containing a carbazolyl group or carbazole is introduced as a substituent to the characteristic skeleton structurally represented by [Chemical Formula I]. And, when used in an organic layer such as an electron blocking layer in an organic electroluminescent device due to this framework and the introduced substituents, an organic electroluminescent device with excellent quantum efficiency and luminous efficiency can be implemented.

[Formula Ⅰ]

In the above [Chemical Formula I],

L is a single bond, or is selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms (m is an integer of 0 to 3).

X is O, S or R-C-R (wherein R is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms).

R ₁ and R ₂ are each independently selected from hydrogen, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms ( n is an integer from 1 to 4, and when n is 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other).

A is a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted aromatic heterocycle having 12 to 40 carbon atoms including carbazole.

The present invention introduces a substituent A into the characteristic skeleton structurally represented by [Chemical Formula I], and A may be any one selected from the following [Structural Formula 1].

[Structural Formula 1]

In [Structural Formula 1] above,

X _{1 and} It is selected from an aryl group of 30 and a substituted or unsubstituted heteroaryl group of 2 to 50 carbon atoms, and Rc is an alkyl group of 1 to 6 carbon atoms.

R ₃ is selected from a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

Meanwhile, in the definition of L, Ra, Rb and R ₁ to R ₃ , substituted or unsubstituted means that L, Ra, Rb and R ₁ to R ₃ are deuterium, cyano group, halogen group, hydroxy group, nitro group, and carbon number 1. Alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, heteroaryl group of 2 to 24 carbon atoms, arylamino group of 1 to 24 carbon atoms, heteroarylamino group of 1 to 24 carbon atoms, carbon number 1 It is selected from the group consisting of an alkylsilyl group having 1 to 24 carbon atoms and an arylsilyl group having 1 to 24 carbon atoms, and is substituted with 1 or 2 or more selected substituents, is substituted with a substituent in which 2 or more of the substituents are connected, or does not have any substituent. means that

For specific examples, substituted aryl group means that phenyl group, biphenyl group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, etc. are substituted with other substituents. do.

Substituted heteroaryl groups include pyridyl group, thiophenyl group, triazine group, quinoline group, phenanthroline group, imidazole group, thiazole group, oxazole group, carbazole group, and condensed heterocyclic groups thereof, such as benzquinoline group and benzyl group. It means that imidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are substituted with other substituents.

In the present invention, examples of the above substituents will be described in detail below, but are not limited thereto.

In the present invention, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited to these.

Specific examples of silyl groups used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, and dimethylfurylsilyl. etc. can be mentioned.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of monocyclic aryl groups include phenyl group, biphenyl group, terphenyl group, and stilbene group, and examples of polycyclic aryl groups include naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, and tetracenyl group. , chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited to these examples.

In addition, the aryl group may also be further substituted with one or more substituents. More specifically, one or more hydrogen atoms in the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, or an amino group (-NH ₂ , -NH(R), -N(R')(R"), R' and R" are independently alkyl groups having 1 to 10 carbon atoms, in which case they are referred to as "alkylamino groups"), amidino groups, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms, alkynyl group of 1 to 24 carbon atoms, hetero group of 1 to 24 carbon atoms It may be substituted with an alkyl group, an aryl group with 6 to 24 carbon atoms, an arylalkyl group with 6 to 24 carbon atoms, a heteroaryl group with 2 to 24 carbon atoms, a heteroarylalkyl group with 2 to 24 carbon atoms, etc.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms. Examples include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, and acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, iso Examples include oxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, and phenothiazinyl group, but are not limited to these.

In the present invention, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example etc.

In the present invention, the fluorenyl group includes the structure of an open fluorenyl group, where the open fluorenyl group is a structure in which one ring compound is disconnected in a structure where two ring organic compounds are connected through one atom. , for example etc.

Additionally, various specific examples of substituents according to the present invention can be clearly identified through the specific compounds described below.

The organic light-emitting compound according to the present invention represented by [Formula I] can be used as an organic material layer of an organic electroluminescent device due to its structural specificity, such as a characteristic skeleton and substituents introduced into the skeleton, and more specifically, the substituents introduced into the structure. Depending on its properties, it can be used as an electron blocking layer for the organic material layer.

Preferred specific examples of the compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited to these.

As described above, by introducing a substituent A having a characteristic structure into a characteristic skeletal structure, an organic light-emitting compound having the unique properties of the introduced substituent can be synthesized. For example, by introducing substituents used in the hole injection layer material, hole transport layer material, light emitting layer material, electron transport layer material, and electron blocking layer material used in the manufacture of organic electroluminescent devices into the above structure, the conditions required for each organic material layer can be met. The material can be manufactured, and in particular, when the compound of [Chemical Formula I] according to the present invention is employed in the electron blocking layer, the luminous efficiency and quantum efficiency characteristics of the device can be further improved.

The organic light-emitting compound according to the present invention can be applied to organic electroluminescent devices according to conventional manufacturing methods.

An organic electroluminescent device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic material layer disposed between them, and the organic light emitting compound according to the present invention is used in the organic material layer of the device. Except that it can be manufactured using conventional device manufacturing methods and materials.

The organic material layer of the organic electroluminescent device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, etc. However, it is not limited to this and may include fewer or more organic layers.

Therefore, in the organic electroluminescent device according to the present invention, the organic material layer may include one or more of an electron injection layer, an electron transport layer, a layer that simultaneously performs electron injection and electron transport, an electron blocking layer, and a light emitting layer, and among the layers, One or more layers may include the organic light-emitting compound represented by [Chemical Formula I].

In addition, the organic electroluminescent device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to deposit a metal or conductive metal oxide or thereof on a substrate. It can be manufactured by depositing an alloy to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. .

In addition to this method, an organic electroluminescent device can also be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer, but is not limited to this and may have a single layer structure. In addition, the organic material layer uses a variety of polymer materials to form a smaller number of layers by a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than deposition. It can be manufactured in layers.

As an anode material, a material with a large work function is generally preferred to ensure smooth hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , conductive polymers such as polypyrrole and polyaniline, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof, multilayers such as LiF/Al or LiO ₂ /Al. Structural materials, etc., but are not limited to these.

The hole injection material is a material that can easily inject holes from the anode at a low voltage. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Examples include anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport material is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The light-emitting material is a material that can emit light in the visible range by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material with good quantum efficiency for fluorescence or phosphorescence is preferred. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole, and Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited to these.

The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic electroluminescent device according to the present invention may be a front-emitting type, a rear-emitting type, or a double-sided emitting type depending on the material used.

In addition, the organic light-emitting compound according to the present invention can function in organic electronic devices, including organic solar cells, organic photoreceptors, and organic transistors, on a principle similar to that applied to organic electroluminescent devices.

Hereinafter, synthesis examples of preferred compounds and device examples are presented to aid understanding of the present invention. However, the following examples are for illustrating the present invention and are not intended to limit the scope of the present invention.

Synthesis example 1: Synthesis of Compound 1

(One) Manufacturing example 1: Synthesis of intermediate 1-1

3-Bromodibenzofuran (10 g, 0.041 mol, TCI), methyl 2-aminobenzoate (7.34 g, 0.047 mol, Sigma Aldrich), cesium carbonate (19.78 g, 0.061 mol, Sigma Aldrich), catalyst Pd(OAc) ₂ (0.18 g , 0.0008 mol, sigma aldrich), and xantphos (0.94 g, 0.0016 mol, sigma aldrich) were mixed with 150 mL of toluene and stirred at 100°C for 6 hours to react. After completion of the reaction, extraction was performed with ethyl acetate and column purification was performed to obtain 9.7 g of <Intermediate 1-1> (yield 75.5%).

(2) Manufacturing example 2: Synthesis of intermediate 1-2

Intermediate 1-1 (10 g, 0.032 mol) and 150 mL of diisopropylether were added, stirred, and then 40 mL of methyl magnesium bromide was slowly added dropwise, followed by reaction by stirring at 50°C for 12 hours. After completion of the reaction, extraction was performed with ethyl acetate and column purification was performed to obtain 6.5 g of <Intermediate 1-2> (yield 65%).

(3) Production example 3 : Synthesis of intermediate 1-3

Intermediate 1-2 (10 g, 0.032 mol) and 40 mL of phosphoric acid were added and stirred for 6 hours to react. After completion of the reaction, an excess amount of distilled water was added, filtered, and column purified to obtain 7 g of <Intermediate 1-3> (yield 74.2%).

(4) Manufacturing example 4: Synthesis of intermediates 1-4

1-bromo-2-nitrobenzene (50 g, 0.247 mol, sigma aldrich), 2-bromophenylboronic acid (59.6 g, 0.297 mol, sigma aldrich), potassium carbonate (90.4 g, 0.94 mol, sigma aldrich), catalyst Pd(PPh) ₃ ) 400 mL of THF and 80 mL of water were added to ₄ (17.16 g, 0.015 mol, Sigma Aldrich) and stirred at 60°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 66.7 g of <Intermediate 1-4> (yield 96%).

(5) Manufacturing example 5: Synthesis of intermediates 1-5

Intermediate 1-4 (28 g, 0.1 mol), triphenylphosphine (79.2 g, 0.302 mol, Sigma Aldrich), and 200 mL of 1,2-dichlorobenzene were added and stirred at 180°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification (N-HEXANE) was performed to obtain 20 g of <Intermediate 1-5> (yield 80%).

(6) Manufacturing example 6: Synthesis of intermediates 1-6

Intermediate 1-5 (20 g, 0.081 mol), iodobenzene (41.4 g, 0.203 mol, Sigma Aldrich), potassium carbonate (33.69 g, 0.244 mol, Sigma Aldrich), Cu (10.33 g, 0.162 mol, Sigma Aldrich), dibenzo -18-crown-6 (2.93 g, 0.008 mol, sigma Aldrich) and 150 mL of dimethylformamide were added and stirred at 150°C for 12 hours to react. After completion of the reaction, the layers were separated in H ₂ O: MC and purified by column (N-HEXANE) to obtain 24 g of <Intermediate 1-6> (yield 93%).

(7) Manufacturing example 7: Synthesis of intermediates 1-7

Intermediate 1-7 (20 g, 0.062 mol), Bis(pinacolato)dibron (20.49 g, 0.081 mol, sigma aldrich), potassium acetate (12.18 g, 0.124 mol, sigma aldrich), PdCl ₂ (dppf) (1.36 g, 0.0019 mol, Sigma aldrich) and 400 mL of 1,4-Dioxane were added and stirred at 95°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 14 g of <Intermediate 1-7> (yield 61%).

(8) Manufacturing example 8: Synthesis of intermediate 1-8

Intermediate 1-7 (17 g, 0.046 mol), 1-boromo-4-iodobenzene (15.68 g, 0.055 mol, Sigma Aldrich), sodium hydroxide (5.54 g, 0.138 mol, Sigma Aldrich), Pd(PPh ₃ ) ₄ ( 3.26 g, 0.0028 mol, Sigma aldrich), 200 mL of THF, and 60 mL of water were added and stirred at 60°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 16.9 g of <Intermediate 1-8> (yield 92%).

(9) Manufacturing example 9: Synthesis of Compound 1

Intermediate 1-8 (10 g, 0.025 mol), Intermediate 1-3 (7.52 g, 0.025 mol), Sodium tert-butoxide (3.62 g, 0.038 mol, Sigma Aldrich), Catalyst Pd(dba) ₂ (0.72 g, 0.0013) 150 mL of toluene was added to tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) and stirred at 100°C for 6 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 12 g of Compound 1 (yield 77.5%).

H-NMR (200MHz, CDCl3):δppm, 1H(8.55/d, 7.94/d, 7.89/d, 7.79/d, 7.66/d, 7.59/d, 7.45/m, 7.43/m, 7.38/m, 7.35 /s, 7.33/d, 7.32/m, 7.25/m, 7.11/s, 7.05/d, 7.02/m, 6.73/m, 6.55/d) 2H (7.58/m, 7.54/d, 7.50/d, 6.69 /d) 6H (1.72/s)

LC/MS: m/z=616[(M+1) ⁺ ]

Synthesis example 2: Synthesis of Compound 27

(One) Manufacturing example 1: Synthesis of intermediate 27-1

3-Bromodibenzofuran (10 g, 0.034 mol, TCI), methyl 2-amino-5-bromobenzoate (9.39 g, 0.041 mol, Sigma Aldrich), cesium carbonate (16.62 g, 0.051 mol, Sigma Aldrich), catalyst Pd(OAc) 150 mL of toluene was added to ₂ (0.15 g, 0.0007 mol, sigma aldrich) and xantphos (0.79 g, 0.0014 mol, sigma aldrich) and stirred at 100°C for 6 hours to react. After completion of the reaction, extraction was performed with ethyl acetate and column purification was performed to obtain 9.6 g of <Intermediate 27-1> (yield 7%).

(2) Manufacturing example 2: Synthesis of intermediate 27-2

Intermediate 27-1 (10 g, 0.027 mol) and 150 mL of diisopropylether were added, stirred, and then 40 mL of methyl magnesium bromide was slowly added dropwise, followed by stirring at 50°C for 12 hours to react. After completion of the reaction, extraction was performed with ethyl acetate and column purification to obtain 7.4 g of <Intermediate 27-2> (yield 68.9%).

(3) Manufacturing example 3: Synthesis of intermediate 27-3

Intermediate 27-2 (10 g, 0.025 mol) and 40 mL of phosphoric acid were added and stirred for 6 hours to react. After completion of the reaction, an excess amount of distilled water was added, filtered, and column purified to obtain 7.2 g of <Intermediate 27-3> (yield 75.4%).

(4) Manufacturing example 4: Synthesis of intermediate 27-4

Intermediate 27-3 (10 g, 0.026 mol), phenylboronic acid (3.87 g, 0.032 mol, Sigma Aldrich), potassium carbonate (10.96 g, 0.08 mol, Sigma Aldrich), Pd(PPh ₃ ) ₄ (1.53 g, 0.0013 mol) , Sigma aldrich), 200 mL of THF, and 40 mL of H ₂ O were added and stirred under reflux for 5 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 7.8 g of <Intermediate 27-4> (yield 78.6%).

(5) Manufacturing example 5: Synthesis of intermediate 27-5

4-iododibenzofuran (10 g, 0.034 mol, Sigma Aldrich), 2-bromoaniline (11.70 g, 0.068 mol, Sigma Aldrich), Sodium tert-butoxide (4.90 g, 0.051 mol, Sigma Aldrich), catalyst Pd(dba) ₂ ( 150 mL of toluene was added to 0.98 g, 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.69 g, 0.0034 mol, sigma aldrich) and stirred at 100°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.4 g of <Intermediate 27-5> (yield 73%).

(6) Manufacturing example 6: Synthesis of intermediate 27-6

Add 150 mL of dimethylformamide to intermediate 27-5 (10 g, 0.030 mol, sigma aldrich), potassium acetate (4.35 g, 0.044 mol, sigma aldrich), and Pd(PPh ₃ ) ₄ (1.03 g, 0.0009 mol, sigma aldrich). The reaction was stirred at 100°C for 12 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 4 g of <Intermediate 27-6> (yield 52.6%).

(7) Manufacturing example 7: Synthesis of intermediate 27-7

Intermediate 27-6 (10 g, 0.039 mol), bromobenzene (7.9 g, 0.051 mol, Sigma Aldrich), potassium carbonate (13.43 g, 0.097 mol, Sigma Aldrich), Cu (4.94 g, 0.078 mol, Sigma Aldrich), dibenzo -18-crown-6 (1.40 g, 0.004 mol, Sigma Aldrich) and 150 mL of Dimethylformamide were added and stirred at 150°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 9.2 g of <Intermediate 27-7> (yield 71%).

(8) Manufacturing example 8: Synthesis of intermediate 27-8

Intermediate 27-7 (10 g, 0.03 mol), N-Bromosuccinimide (5.9 g, 0.033 mol, Sigma aldrich), and 150 mL of dimethylformamide were added and stirred at room temperature for 2 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 10 g of <Intermediate 27-8> (yield 80.9%).

(9) Manufacturing example 9: Synthesis of intermediate 27-9

Intermediate 27-8 (10 g, 0.024 mol), Bis(pinacolato)dibron (8.01 g, 0.032 mol, sigma aldrich), potassium acetate (4.76 g, 0.049 mol, sigma aldrich), PdCl ₂ (dppf) (0.53 g, 0.0007 mol, Sigma aldrich), 400 mL of 1,4-Dioxane was added and stirred at 95°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8 g of <Intermediate 27-9> (yield 71.9%).

(10) Manufacturing example 10: Synthesis of intermediate 27-10

Intermediate 27-9 (10 g, 0.022 mol), 1-boromo-4-iodobenzene (6.77 g, 0.024 mol, Sigma Aldrich), sodium hydroxide (9.03 g, 0.065 mol, Sigma Aldrich), Pd(PPh ₃ ) ₄ ( 1.26 g, 0.0011 mol, Sigma aldrich), 150 mL of THF, and 50 mL of water were added and stirred under reflux for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.4 g of <Intermediate 27-10> (yield 79%).

(11) Manufacturing example 11: Synthesis of compound 27

Intermediate 27-10 (10 g, 0.021 mol), Intermediate 27-4 (8.46 g, 0.023 mol), Sodium tert-butoxide (3.94 g, 0.041 mol, Sigma Aldrich), Catalyst Pd(dba) ₂ (0.59 g, 0.001 150 mL of toluene was added to tri-tert-Bu-phosphine (0.41 g, 0.002 mol, sigma aldrich) and stirred at 100°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 12 g of compound 27 (yield 74.9%).

H-NMR (200MHz, CDCl3):δppm, 1H(8.18/d, 8.00/d, 7.77/s, 7.61/s, 7.53/d, 7.45/m, 7.41/m, 7.36/d, 7.35/s, 7.11 /s, 6.61/s) 2H (7.66/d, 7.58/m, 7.54/d, 7.52/d, 7.51/m, 7.50/d, 7.38/m, 7.32/m, 6.69/d) 3H (7.89/d) ) 6H(1.72/s)

LC/MS: m/z=782[(M+1) ⁺ ]

Synthesis example 3: Synthesis of Compound 64

(One) Manufacturing example 1: Synthesis of intermediate 64-1

Intermediate 30-3 (10 g, 0.026 mol), naphthalene-1-boronic acid (5.46 g, 0.032 mol), potassium carbonate (10.96 g, 0.079 mol, Sigma Aldrich), Pd(PPh ₃ ) ₄ (1.53 g, 0.0013) mol, sigma aldrich), 200 mL of THF, and 40 mL of H ₂ O were added and stirred under reflux for 6 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.3 g of <Intermediate 64-1> (yield 73.8%).

(2) Manufacturing example 2: Synthesis of Compound 64

Intermediate 64-1 (10 g, 0.031 mol), 9-(4-bromophenyl)-9H-carbazole (14.53 g, 0.034 mol, Mascot.), Sodium tert-butoxide (5.97 g, 0.062 mol, Sigma Aldrich), catalyst Toluene 150 mL was added to Pd(dba) ₂ (0.89 g, 0.0016 mol, Sigma Aldrich) and tri-tert-Bu-phosphine (0.63 g, 0.0031 mol, Sigma Aldrich) and stirred at 100°C for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 15.3 g of compound 64 (yield 74%).

H-NMR (200MHz, CDCl3):δppm, 1H(8.42/d, 8.12/d, 8.08/d, 8.04/d, 7.94/d, 7.89/d, 7.66/d, 7.63/d, 7.50/m, 7.38 /m, 7.36/d, 7.35/s, 7.33/m, 7.32/m, 7.29/m, 7.25/m, 7.11/s, 6.61/m) 2H (8.55/d, 7.61/d, 7.55/m, 7.37 /d, 6.63/d) 6H (1.72/s)

LC/MS: m/z=666[(M+1) ⁺ ]

Device Example (EBL)

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

Device Examples 1 to 9

Using the compound represented by [Chemical Formula I] according to the present invention as the compound of the electron blocking layer, a blue light-emitting organic electroluminescent device having the following device structure was manufactured, and the luminescence properties including luminescence efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (α-NPB 100 nm) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

To form a hole injection layer on the ITO transparent electrode, it was formed to a thickness of 5 nm using HAT_CN using vacuum thermal evaporation, and then a hole transport layer was formed to a thickness of 100 nm using α-NPB. The electron blocking layer was formed to a thickness of 10 nm using the chemical formulas 1, 12, 21, 27, 37, 49, 64, 76, and 92 implemented in the present invention. In addition, the light emitting layer was formed using [BH1] as a host compound and [BD1] as a dopant compound to a thickness of about 20 nm, and additionally an electron transport layer (50% doped with [201] compound Liq below). An organic electroluminescent device was manufactured by depositing 30 nm of LiF, 1 nm of LiF, and 100 nm of aluminum by deposition.

Device Comparative Example 1

The organic electroluminescent device for Device Comparative Example 1 was manufactured in the same manner as the device structure of Example 1 except that TCTA was used instead of Chemical Formula 1.

Experimental Example 1: Light emission characteristics of device examples 1 to 9

The voltage, current, and luminous efficiency of the organic electroluminescent device manufactured according to the above example were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the current density was 10 mA/cm2. The voltage was defined as “driving voltage” and compared. The results are shown in [Table 1] below.

Example electronic low layer V cd/A QE(%) CIEx CIey One Formula 1 4.04 7.66 6.50 0.144 0.153 2 Formula 12 4.15 7.46 6.27 0.145 0.154 3 Formula 21 4.09 7.59 6.40 0.144 0.155 4 Formula 27 4.18 7.42 6.24 0.145 0.156 5 Formula 37 4.22 7.10 6.01 0.145 0.154 6 Chemical formula 49 4.08 7.58 6.39 0.145 0.155 7 Formula 64 4.13 7.43 6.26 0.145 0.155 8 Chemical formula 76 4.20 7.25 6.14 0.144 0.154 9 Formula 92 4.24 7.14 6.01 0.145 0.154 Comparative Example 1 TCTA 4.20 6.40 5.30 0.145 0.156

Looking at the results shown in [Table 1], first, when the electron blocking layer according to the present invention is applied to a compound device, it can be confirmed that the luminous properties such as luminous efficiency and quantum efficiency are significantly superior to those of the conventional device (comparative example). .

[HAT_CN] [α-NPB] [BH1] [BD1] [201] [TCTA]

Device Example (HTL)

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

Device Examples 10 to 18

Using the compound represented by [Chemical Formula I] according to the present invention as a hole transport layer compound, a blue light-emitting organic electroluminescent device having the following device structure was manufactured, and luminescence properties including luminescence efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (100 nm) / emission layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, HAT_CN is used to form a 5 nm thick vacuum thermal evaporation method, and then a hole transport layer is formed using the formulas 1, 12, 21, 27, 37, 49, and 64 implemented by the present invention. , 76, and 92 were used to form a film with a thickness of 100 nm, respectively. In addition, the light-emitting layer was formed using [BH1] as a host compound and [BD1] as a dopant compound to a thickness of about 20 nm, and additionally an electron transport layer (50% doped with [201] compound Liq below). An organic electroluminescent device was manufactured by depositing 1 nm of LiF and 100 nm of aluminum by deposition.

Device Comparative Example 2

The organic electroluminescent device for Comparative Device Example 2 was manufactured in the same manner as the device structure of Example 10, except that α-NPB was used instead of Chemical Formula 1.

Experimental Example 2: Light emission characteristics of device examples 1 to 9

The voltage, current, and luminous efficiency of the organic electroluminescent device manufactured according to the above example were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the current density was 10 mA/cm2. The voltage was defined as “driving voltage” and compared. The results are shown in [Table 2] below.

Example hole transport layer V cd/A QE(%) CIEx CIey 10 Formula 1 3.97 6.87 5.91 0.144 0.154 11 Formula 12 4.10 6.64 5.65 0.145 0.154 12 Formula 21 4.04 6.71 5.80 0.144 0.155 13 Formula 27 4.12 6.59 5.50 0.145 0.156 14 Formula 37 4.15 6.54 5.53 0.145 0.154 15 Formula 49 4.02 6.80 5.84 0.145 0.155 16 Formula 64 4.09 6.61 5.59 0.145 0.155 17 Chemical formula 76 4.14 6.63 5.64 0.144 0.154 18 Formula 92 4.16 6.56 5.60 0.145 0.154 Comparative Example 2 α-NPB 4.14 5.4 4.6 0.145 0.156

Looking at the results shown in [Table 2], first, it can be seen that when the hole transport layer according to the present invention is applied to a compound device, the luminous properties such as luminous efficiency and quantum efficiency are significantly superior to those of a conventional device (comparative example).

[HAT_CN] [α-NPB] [BH1] [BD1] [201]

Claims (7)

Organic luminescent compound represented by the following [Chemical Formula I]:
[Formula Ⅰ]

In the above [Chemical Formula I],
L is a single bond or an unsubstituted arylene group having 6 to 20 carbon atoms (m is an integer of 0 to 3),
X is O, S or RCR (where R is an unsubstituted alkyl group having 1 to 6 carbon atoms or an unsubstituted aryl group having 6 to 20 carbon atoms),
R ₁ and R ₂ are each independently selected from hydrogen, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms ( n is an integer from 1 to 4, and when n is 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other),
A is any one selected from the following [Structural Formula 1],
[Structural Formula 1]

In [Structural Formula 1] above,
X ₁ and X ₂ are the same as or different from each other and are each independently O, S, N-Ra or Rb-C-Rc,
Ra is any one selected from a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and Rb and Rc are Each is an unsubstituted alkyl group having 1 to 6 carbon atoms,
R ₃ is any one selected from a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms. delete According to paragraph 1,
In the definition of Ra and R ₁ to R ₃ , substituted or unsubstituted means that Ra and R ₁ to R ₃ are deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group with 1 to 24 carbon atoms, or 1 to 24 carbon atoms. Halogenated alkyl group, aryl group with 6 to 24 carbon atoms, heteroaryl group with 2 to 24 carbon atoms, arylamino group with 6 to 24 carbon atoms, heteroarylamino group with 1 to 24 carbon atoms, alkylsilyl group with 1 to 24 carbon atoms and 6 to 6 carbon atoms. An organic light-emitting compound selected from the group consisting of 24 arylsilyl groups, and substituted with 1 or 2 or more selected substituents, substituted with a substituent in which 2 or more of the substituents are linked, or having no substituent. According to paragraph 1,
[Formula I] is an organic light-emitting compound selected from the following [Compound 1] to [Compound 96]:







An organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode,
An organic electroluminescent device, wherein at least one of the organic layers includes at least one organic light-emitting compound represented by [Chemical Formula I] according to claim 1. According to clause 5,
The organic layer includes one or more of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,
An organic electroluminescent device, characterized in that at least one of the layers includes an organic light-emitting compound represented by [Chemical Formula I]. According to clause 6,
An organic electroluminescent device, wherein the electron blocking layer includes an organic light-emitting compound represented by [Chemical Formula I].