KR20100114749A - Aluminium complex derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

PURPOSE: An aluminum complex derivative and organic electro luminescence device having the same are provided to ensure excellent power efficiency and light emitting efficiency. CONSTITUTION: An aluminum complex derivative is denoted by chemical formula 1. An organic electro luminescence device comprises an anode, cathode, and layer having aluminum complex derivative between anode and cathode. The organic electro luminescence device further comprises a hole injection layer between anode and cathode, hole transport layer, hole blocking layer, light emitting layer, electron transport layer, electron injection layer or electron blocking layer.

Description

Aluminum complex derivative and organic electroluminescent device using the same {ALUMINIUM COMPLEX DERIVATIVES AND ORGANOELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to an aluminum complex derivative and an organic light emitting device employing the same, and more particularly, to an aluminum complex derivative capable of manufacturing an organic light emitting device having excellent power efficiency and luminous efficiency, and an organic light emitting device employing the same. It is about.

The organic light emitting device is gradually expanding its application field to the display and lighting field of various electronic products, but the efficiency and lifespan characteristics are restricting the expansion of the application field. There is a lot of research going on.

Phosphorescent hosts commonly used include CBP (4, 4′-N, N′-dicarbazolbiphenyl), BAlq (((1,1'-biphenyl) -4-olato) bis (2-methyl-8-quinolinolato N1 , O8) aluminum), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), among which BAlq is a hole transport layer NPB (N, N'-diphenyl-N- In the case of using Nbis (1-naphthyl) -1, 1'-biphenyl) -4, 4'-diamine and Alq3 as the electron transport layer, due to the appropriate energy level characteristics and the ability of charge transfer, Together are the most commonly used host materials for phosphorescence.

U.S. Patent Publication No. US2003 / 0129452 lists aluminum complexes as phosphorescent host materials, and states that the lifetime can be improved when the difference in ionization potential energy between the host material and the hole transport layer is 0.4 to 0.8 eV. The problem is that the efficiency is poor and the service life cannot be secured for a long time.

In addition, CBP (4, 4'-N, N'-dicarbazolbipheny) and substances in which various substituents are introduced into carbazole (Japanese Patent Publication 2008-0214244, Japanese Patent Publication 2003-0133075) are known, but in terms of efficiency and life characteristics Further improvements are needed.

The first object of the present invention is to provide a novel aluminum complex derivative that can improve the characteristics such as color purity, power efficiency and luminous efficiency of the organic light emitting device.

In addition, the second technical problem to be solved by the present invention is to provide an organic light emitting device having improved properties by employing the aluminum complex derivative.

The present invention provides an aluminum complex derivative of the general formula (1) to achieve the first object.

Aluminum complex derivative represented by the following general formula (1):

                     (One)

Wherein R ₁ to R ₁₁ are the same or different and each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted carbon number 10- 40 condensed aromatic ring, substituted or unsubstituted condensed aromatic heterocycle having 10 to 40 carbon atoms, substituted or unsubstituted styryl group, substituted or unsubstituted amino group, substituted or unsubstituted carbonyl group, substituted or unsubstituted carboxyl group, substituted or unsubstituted aryl A substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 40 carbon atoms Groups, substituted or unsubstituted straight chain, crushed or cyclic alkyl groups having 1 to 40 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, substituted or unsubstituted carbon atoms 7-40 An aralkyl group, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 3 to 40 carbon atoms,

Het is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, wherein the heteroaryl group is pyridine, pyrimidine, pyrazine, triazine, aziridine azaindolidine, indolidine, aluminum complex, indole, naphthalidine, quinox Selected from the group consisting of saline, terpyridine, bipyridine, phenanthroline, phenazine quinoline, carbazole, indolocarbazole,

The substituents of R ₁ to R ₁₁ and Het are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An alkylamino group having 1-40 carbon atoms, an aryl group having 6-40 carbon atoms, an aryloxy group having 6-40 carbon atoms, an arylamino group having 6-40 carbon atoms, an arylsilyl group having 6-40 carbon atoms, a heteroaryl group having 3-40 carbon atoms At least one substituent selected from the group consisting of monovalent, divalent or fused substituted).

According to one embodiment of the present invention, the substituents of R ₁ to R ₆ , Het or R ₁ to R ₆ , Het may combine with each other to form a substituted or unsubstituted saturated or unsaturated ring, and the saturated or Substituents of an unsaturated ring may be attached or fused together in a pendant manner.

In addition, the aluminum complex derivative according to an embodiment of the present invention may be, for example, any one compound selected from the group represented by the following formula (2) to formula (45), but is not limited to these exemplary compounds:

(2) (3) (4) (5)

(2) (3) (4) (5)

(6) (7) (8) (9)

(6) (7) (8) (9)

(10) (11) (12) (13)

(10) (11) (12) (13)

(14) (15) (16) (17)

(18) (19) (20) (21)

(22) (23) (24) (25)

(26) (27) (28) (29)

(30) (31) (32) (33)

(34) (35) (36) (37)

(38) (39) (40) (41)

(42) (43) (44) (45)

The present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an aluminum complex derivative represented by the formula (1), interposed between the anode and the cathode.

According to an embodiment of the present invention, the anode and the cathode between the hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, further comprising at least one layer selected from the group consisting of electron blocking layer, electron transport layer and electron injection layer The aluminum complex derivative may be included in the light emitting layer between the anode and the cathode, and the thickness of the light emitting layer is preferably 50 to 2,000 Pa.

According to another embodiment of the present invention, the hole injection layer, the hole transport layer, the hole blocking layer, the light emitting layer, the electron blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process.

In addition, the organic light emitting display device including the aluminum complex derivative according to the present invention may be used in a display device, a display device, and a monochrome or white lighting device.

By using the aluminum complex derivative according to the present invention, it is possible to provide an organic light emitting device excellent in color purity, power efficiency and luminous efficiency.

The present invention can be effectively used in all layers of the organic field device as a derivative having a basic skeleton of the aluminum complex represented by the formula (1), especially when employed as a light emitting layer host, holes and electrons are easy to move, holes and electrons It is possible to maximize the exciton formation in the light emitting layer because it can maintain the balance.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. Halogen atom, hydroxy group, nitro group, cyano group, silyl group (in this case referred to as "alkylsilyl group"), substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R ''), R 'and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case referred to as an" alkylamino group "), a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 20 carbon atoms A halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, C6-20 heteroaryl group or C6-20 hetero It may be substituted with an aralkyl group.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the alkyl group.

The aryl group used in the compound of the present invention means an aromatic system including one or more rings, and the rings may be attached or fused together by a pendant method. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, biphenyl, terphenyl anthracenyl, phenanthryl, pyrenyl, chrysenyl and fluoranthenyl, and at least one hydrogen atom of the aryl group may be It may be substituted with the same substituent as in the case of an alkyl group (for example, "arylamino group" when substituted with an amino group, "arylsilyl group" when substituted with a silyl group, and "aryloxy group" when substituted with an oxy group. ).

Heteroaryl group which is a substituent used in the compound of the present invention, N, O, P means a ring aromatic system having 3 to 30 carbon atoms containing 1, 2 or 3 hetero atoms selected from S, and the remaining ring atoms are carbon, The rings may be attached or fused together in a pendant manner. Specific examples of the heteroaryl group include pyridine, pyrimidine, pyrazine, triazine, aziridine azaindolidine, indolidine, aluminum complex, indole, naphthalidine, quinoxaline, terpyridine, bipyridine, phenanthroline, phena Gin quinoline, carbazole, indolocarbazole and the like. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

In addition, the present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an aluminum complex derivative represented by the formula represented between the anode and the cathode.

Referring to the organic light emitting device according to the present invention in more detail, the organic light emitting device is one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a total embroidery layer and an electron injection layer between the anode and the cathode Also, the hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer serves to increase the probability of light emitting coupling in the light emitting layer by efficiently transferring holes or electrons to the light emitting layer.

The hole injection layer and the hole transport layer are laminated to facilitate the injection of holes from the anode and the transport of the injected holes. As the material for the hole transport layer, electron donor molecules having small ionization potential are used. Diamine, triamine or tetraamine derivatives based on amines are frequently used. In the present invention, as the material of the hole transport layer, as long as it is commonly used in the art, various materials can be used without limitation, for example, N, N' -bis (3-methylphenyl) -N, N ' -Diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) or N, N' -di (naphthalen-1-yl) -N, N' -diphenyl benzidine (α-NPD ) Can be used. In addition, a hole injection layer (HIL) may be further stacked below the hole transport layer, and the hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc or Starburst type amines such as TCTA, m-MTDATA, IDE406 (manufactured by Idemitsu Corp.) and the like can be used.

                 CuPc TCTA

            m-MTDATA

An organic light emitting layer is stacked on the hole transport layer, and the organic light emitting layer may be made of a single material or may be made of a host / dopant.

In general, when the compound is used as a single material, a host / dopant-based light emitting layer is preferable, because an intermolecular interaction generates a mound peak at long wavelengths, resulting in poor color purity, and low efficiency due to a light emission decay effect. The aluminum complex derivative may be used as a host material in the host / dopant light emitting layer. The dopant material in the host / dopant light emitting layer is not particularly limited as long as it is generally used in the art. The electron transport layer serves to increase the chance of recombination in the light emitting layer by smoothly transporting electrons supplied from the cathode to the light emitting layer and suppressing movement of holes that are not bonded in the light emitting layer. Such electron transport layer material is not particularly limited as long as it is a material used in the art, for example, Alq 3 (tri-8-hydroxyquinoline aluminum), PBD (2- (4-biphenylyl) -5- ( 4-t-butylphenyl) -1,3,4-oxadiazole), TNF (2,4,7-trinitro fluorenone), BMD, BND and the like can be used.

Meanwhile, an electron injection layer (EIL), which facilitates electron injection from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li ₂ O, BaO.

Furthermore, in addition to the above-described hole injection layer, hole transport layer, electron transport layer, and electron injection layer, the organic light emitting device according to the present invention may further include additional functional laminated structures such as a hole blocking layer or an electron blocking layer. . At this time, the hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level because the life and efficiency of the device is reduced when holes are introduced into the cathode through the organic light emitting layer. The material constituting the hole blocking layer is not particularly limited, but should have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, or the like may be used.

More specifically, FIGS. 1A to 1F illustrate organic light emitting diodes having various types of stacked structures. Referring to this, the organic light emitting diode of FIG. 1A includes an anode / hole injection layer / light emitting layer / cathode. The organic electroluminescent device of FIG. 1B has a structure consisting of an anode / hole injection layer / light emitting layer / electron injection layer / cathode. In addition, the organic light emitting display device of FIG. 1c has a structure of an anode / hole injection layer / hole transporting layer / light emitting layer / cathode, and the organic light emitting device shown in FIG. 1d includes an anode / hole injection layer / hole transporting layer / light emitting layer / electron injection. The organic electroluminescent device of FIG. 1E has a structure of a layer / cathode, and has an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. Finally, the organic electroluminescent device of FIG. 1F is an anode. It has a structure of / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

The organic electroluminescent device according to the present invention may include the aluminum complex derivative in various laminated structures interposed between the anode and the cathode. Preferably, the aluminum complex derivative is used as a host material in the light emitting layer between the anode and the cathode. Can be used.

In addition, the thickness of the light emitting layer including the aluminum complex derivative may be 50 to 2,000 kPa, but when the thickness is less than 50 kPa, the luminous efficiency is lowered, and when it exceeds 2,000 kPa, the driving voltage is uneconomical. .

A method of manufacturing an organic light emitting display device according to the present invention will be described with reference to FIGS. 1A to 1F.

First, an anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used. A glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, as the anode material, materials commonly used in the art, such as transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), or zinc oxide (ZnO), may be used. have. A hole injection layer is stacked on the anode, and then a hole transport layer is formed on the hole injection layer.

Next, after the light emitting layer is laminated on the hole transport layer, a hole blocking layer is selectively formed thereon. Finally, after the electron transport layer is laminated on the hole blocking layer, the electron injection layer may be selectively formed, and the organic light emitting diode according to the present invention may be manufactured by vacuum thermal depositing a metal for forming a cathode on the electron injection layer. Will be. Lamination of the organic layer is performed by one or more methods selected from the methods of vacuum thermal deposition, spin coating or inkjet printing.

On the other hand, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminium-lithium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), Magnesium-silver (Mg-Ag) or the like may be used, and a transmissive cathode using ITO or IZO may be used to obtain a front light emitting device.

1A to 1F are cross-sectional views illustrating a laminated structure of organic light emitting diodes according to an exemplary embodiment of the present invention.

Claims (10)

Aluminum complex derivative represented by the following general formula (1):

                     (One) Wherein R ₁ to R ₁₁ are the same or different and each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted carbon number 10- 40 condensed aromatic ring, substituted or unsubstituted condensed aromatic heterocycle having 10 to 40 carbon atoms, substituted or unsubstituted styryl group, substituted or unsubstituted amino group, substituted or unsubstituted carbonyl group, substituted or unsubstituted carboxyl group, substituted or unsubstituted aryl A substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 40 carbon atoms Groups, substituted or unsubstituted straight chain, crushed or cyclic alkyl groups having 1 to 40 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, substituted or unsubstituted carbon atoms 7-40 An aralkyl group, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 3 to 40 carbon atoms, Het is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, wherein the heteroaryl group is pyridine, pyrimidine, pyrazine, triazine, aziridine azaindolidine, indolidine, aluminum complex, indole, naphthalidine, quinox Selected from the group consisting of saline, terpyridine, bipyridine, phenanthroline, phenazine quinoline, carbazole, indolocarbazole, The substituents of R ₁ to R ₁₁ and Het are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An alkylamino group having 1-40 carbon atoms, an aryl group having 6-40 carbon atoms, an aryloxy group having 6-40 carbon atoms, an arylamino group having 6-40 carbon atoms, an arylsilyl group having 6-40 carbon atoms, a heteroaryl group having 3-40 carbon atoms At least one substituent selected from the group consisting of monovalent, divalent or fused substituted). The method of claim 1, The R ₁ to R ₆ , Het or the substituents of R ₁ to R ₆ , Het combine with each other to form a substituted or unsubstituted saturated or unsaturated ring aluminum complex derivative. The method of claim 2, Substituents of the saturated or unsaturated ring is an aluminum complex derivative, characterized in that attached or fused together in a pendant method. The method of claim 1, An aluminum complex derivative, which is any one compound selected from the group represented by the following formulas (2) to (41):

(2) (3) (4) (5)

(6) (7) (8) (9)

       (10) (11) (12) (13)

(14) (15) (16) (17)

(18) (19) (20) (21)

(22) (23) (24) (25)

(26) (27) (28) (29)

(30) (31) (32) (33)

(34) (35) (36) (37)

(38) (39) (40) (41)

(42) (43) (44) (45) Anode; Cathode; And an aluminum complex derivative according to any one of claims 1 to 4 interposed between the anode and the cathode. The method of claim 5, further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode. An organic electroluminescent device. The organic light emitting device of claim 6, wherein the aluminum complex derivative is included in a light emitting layer between the anode and the cathode. 8. The organic light emitting device of claim 7, wherein the light emitting layer has a thickness of 50 to 2,000 kPa. The organic light emitting device of claim 6, wherein the hole injection layer, the hole transport layer, the hole blocking layer, the light emitting layer, the electron blocking layer, the electron transport layer, and the electron injection layer are formed by a single molecule deposition method or a solution process. . The organic electroluminescent device according to claim 5, which is used for a display device, a display device, and a monochrome or white illumination device.

Images