KR102230994B1 - Amine derivative and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to an amine derivative of Formula 1 and an organic light emitting device including the same.

Description

An amine derivative and an organic light-emitting device comprising the same TECHNICAL FIELD

The present specification relates to an amine derivative and an organic light emitting device including the amine derivative.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

Development of a new material for the organic light emitting device as described above is continuously required.

US Patent Application Publication No. 2004-0251816

The present specification provides an amine derivative and an organic light emitting device including the same.

The present specification provides an amine derivative represented by the following formula (1).

[Formula 1]

In Formula 1 above

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents are bonded to each other to be substituted or unsubstituted Forming an aliphatic ring, a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring,

L is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

R, R', R1 to R4 are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group , Or a substituted or unsubstituted heteroaryl group,

a, b, and d are each an integer of 0 to 3,

c is an integer from 0 to 4,

When a to d are each plural, the substituents in parentheses are the same as or different from each other.

In addition, the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the amine derivative.

The amine derivative according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the amine derivative, it is possible to improve efficiency, low driving voltage, and/or life characteristics in the organic light emitting device.

1 illustrates an organic light-emitting device according to an exemplary embodiment of the present specification.

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

According to an exemplary embodiment of the present specification, an amine derivative represented by the following Chemical Formula 1 is provided.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be positioned "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Examples of the substituent in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, the "substituent to which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

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 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto. It is not.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but are limited thereto. no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

Can be, etc. However, it is not limited thereto.

In the present specification, examples of the cycloalkyl group or the aryl group may be applied to the aliphatic ring.

In the present specification, the aryloxy group is a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group , 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-an And a triloxy group, a 2-anthryloxy group, a 9-anthryloxy group, a 1-phenanthryloxy group, a 3-phenanthryloxy group, and a 9-phenanthryloxy group.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and one or more heteroatoms, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, p Nanthrolinyl group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, examples of the cycloalkyl group or the aryl group may be applied to the heterocycle.

In the present specification, the arylene group is the same as the definition of the aryl group, except that it is divalent.

In the present specification, the heteroarylene group is the same as the definition of the heteroaryl group, except that it is divalent.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, the definitions of R, R', R1 to R4, Ar1, Ar2, L, and a to d are as defined in Formula 1.

According to an exemplary embodiment of the present specification, R, R', and R1 to R4 are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, R and R'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R and R'are the same as or different from each other, and each independently a linear substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R and R'are the same as or different from each other, and each independently a branched or unsubstituted alkyl group having 3 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R and R'are the same as or different from each other, and each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a terbutyl group, an isobutyl group, a pentyl group, iso They are a pentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group.

According to an exemplary embodiment of the present specification, R and R'are methyl groups.

According to an exemplary embodiment of the present specification, R1 to R4 are hydrogen.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted, N, O, or S It is a C3-C20 heteroaryl group contained.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted polycyclic group having 10 to 20 carbon atoms. An aryl group, a substituted or unsubstituted monocyclic heteroaryl group having 3 to 20 carbon atoms containing N, O, or S, or a polycyclic group having 3 to 20 carbon atoms containing substituted or unsubstituted N, O, or S It is a heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a naphthyl group, a phenanthrene group, a dibenzofuran group, or a dibenzothiophene group; Biphenyl group; A phenyl group substituted or unsubstituted naphthyl group; Terphenyl group; A fluorene group unsubstituted or substituted with a methyl group; Phenanthrene group; Triphenylene group; A carbazole group unsubstituted or substituted with a phenyl group; Dibenzofuran group; Or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are bonded to each other to form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are bonded to each other to form a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 combine with each other to form a heterocycle substituted or unsubstituted with an aryl group.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are bonded to each other to form a heterocycle substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a naphthyl group, a phenanthrene group, a dibenzofuran group, or a dibenzothiophene group; Biphenyl group; A phenyl group substituted or unsubstituted naphthyl group; Terphenyl group; A fluorene group unsubstituted or substituted with a methyl group or a phenyl group; Phenanthrene group; Triphenylene group; A carbazole group unsubstituted or substituted with a phenyl group or a naphthyl group; Dibenzofuran group; Dibenzothiophene group; Benzonaphthofuran group; Or a benzonaphthothiophene group, or combine with each other to form a substituted or unsubstituted heterocycle with an aryl group having 6 to 20 carbon atoms.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and may be independently represented by the following substituents, but are not limited thereto.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted arylene group.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a monocyclic substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a polycyclic substituted or unsubstituted arylene group having 10 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a phenylene group, a divalent biphenyl group, a divalent terphenyl group, a divalent naphthyl group, a divalent dimethylfluorene group, or a divalent phenanthrene group.

According to an exemplary embodiment of the present specification, L is a phenylene group.

According to the exemplary embodiment of the present specification, L may be represented by the following substituents.

According to another exemplary embodiment of the present specification, the amine derivative of Formula 1 may be represented by the following structural formulas.

According to an exemplary embodiment of the present specification, the amine derivative of Formula 1 may be prepared according to the following reaction formula, but is not limited thereto. In the following reaction scheme, various types of intermediates can be synthesized according to the type and number of substituents appropriately selecting a known starting material by a person skilled in the art. As for the reaction type and reaction conditions, those known in the art may be used.

In the above reaction scheme, the definitions of L, Ar1, and Ar2 are as described above.

When the preparation formula described in the examples of the present specification and the intermediates are appropriately combined based on common technical knowledge, all of the amine derivatives of Formula 1 described in the present specification can be prepared.

The organic light-emitting device according to the present invention includes a first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the amine derivative of Formula 1 above.

The organic light-emitting device according to the present invention includes a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes in the organic material layer; The hole injection layer, the hole transport layer, or the layer that simultaneously injects and transports holes is characterized in that it contains an amine derivative represented by Formula 1 above.

The organic light-emitting device according to the present invention includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons in the organic material layer; The electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons is characterized in that it contains an amine derivative represented by Formula 1 above.

The organic light-emitting device according to the present invention is characterized in that the organic material layer includes an electron-suppression layer, and the electron-suppression layer includes an amine derivative represented by Formula 1 above.

The organic light-emitting device according to the present invention includes a hole blocking layer in the organic material layer, and the hole blocking layer includes an amine derivative represented by Formula 1 above.

The organic light-emitting device according to the present invention is characterized in that the organic material layer includes an emission layer, and the emission layer includes an amine derivative represented by Formula 1 above.

The organic light-emitting device of the present invention may be manufactured by a conventional method and material of an organic light-emitting device, except that one or more organic material layers are formed using the above-described compound.

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 injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers. In addition, the organic material layer may include at least one of an electron transport layer, an electron injection layer, and a layer that simultaneously transports electrons and injects electrons, and at least one of the layers may include the compound.

For example, the structure of the organic light-emitting device of the present invention may have a structure as shown in FIG. 1, but is not limited thereto.

1 shows a structure of an organic light-emitting device in which a first electrode 2, an organic material layer 3 including an amine derivative of Formula 1, a light emitting layer 4, and a second electrode 5 are sequentially stacked on a substrate 1 Is illustrated.

1 illustrates an organic light emitting device and is not limited thereto.

For example, the organic light-emitting device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, and uses a metal or conductive metal oxide or alloy thereof on a substrate. After depositing an anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, and an organic material layer including the amine derivative of Formula 1 thereon, a material that can be used as a cathode is formed thereon. It can be prepared by vapor deposition. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention 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); A combination of metal and oxide such as ZnO:Al or SnO _{2 :Sb;} Poly(3-methyl compounds), poly[3,4-(ethylene-1,2-dioxy) compounds] (PEDT), conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and 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 substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Of organic matter, anthraquinone, and conductive polymers of a series of polyaniline and polycompounds, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer and having high mobility for holes is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in a visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include amine derivatives, dibenzofuran derivatives, ladder furan Compounds, pyrimidine derivatives, and the like, but are not limited thereto.

When the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light-emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one of the organic material layers is formed using the amine derivative.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be produced by depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The present specification also provides a method of manufacturing an organic light emitting device formed using the amine derivative.

Specifically, in the exemplary embodiment of the present specification, preparing a substrate; Forming a cathode or an anode on the substrate; Forming one or more organic material layers on the cathode or anode; And forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the amine derivative.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include 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 transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

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

The hole blocking layer is a layer that prevents holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but are not limited thereto.

The organic light-emitting device according to the present specification may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

The manufacturing method of the amine derivative of Formula 1 and the manufacturing of an organic light emitting device using the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing Example 1

Compound A (5.50 g, 12.67 mmol) and compound a1 (6.15 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 240 mL of ethyl acetate to prepare compound 1 (8.13 g, 85%).

MS[M+H] ⁺ = 751

Manufacturing Example 2

Compound A (5.50 g, 12.67 mmol) and compound a2 (6.71 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 240 mL of ethyl acetate to prepare compound 2 (6.25 g, 62%).

MS[M+H] ⁺ = 791

Manufacturing Example 3

Compound A (5.50 g, 12.67 mmol) and compound a3 (4.44 g, 18.12 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 240 mL of ethyl acetate to prepare compound 3 (7.77 g, 73%).

MS[M+H] ⁺ = 841

Manufacturing Example 4

Compound A (5.50 g, 12.67 mmol) and compound a4 (7.63 g, 13.94 mmol) were completely dissolved in 180 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 250 mL of ethyl acetate to prepare compound 4 (5.95 g, 55%).

MS[M+H] ⁺ = 858

Manufacturing Example 5

Compound A (5.50 g, 12.67 mmol) and compound a5 (6.15 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 240 mL of ethyl acetate to prepare compound 5 (7.28 g, 76%).

MS[M+H] ⁺ = 751

Manufacturing Example 6

Compound A (5.50 g, 12.67 mmol) and compound a6 (6.48 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 240 mL of ethyl acetate to prepare compound 6 (4.76 g, 48%).

MS[M+H] ⁺ = 775

Manufacturing Example 7

Compound A (5.50 g, 12.67 mmol) and compound a7 (6.15 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 mL of ethyl acetate to prepare compound 7 (5.67 g, 58%).

MS[M+H] ⁺ = 752

Manufacturing Example 8

Compound A (5.50 g, 12.67 mmol) and compound a8 (6.71 g, 13.94 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.43 g, 0.37 mmol) was added, 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 with 150 mL of ethyl acetate to prepare compound 8 (6.67 g, 66%).

MS[M+H] ⁺ = 792

Manufacturing Example 9

Compound A (5.50 g, 12.67 mmol) and compound a9 (5.09 g, 13.94 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol) was added, 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 with 290 mL of ethyl acetate to prepare compound 9 (6.03 g, 70%).

MS[M+H] ⁺ = 676

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

A hole injection layer was formed by thermally vacuum deposition of a compound of the following compound HI1 and the following compound HI2 to a 98:2 molar ratio of 100 Å on the prepared anode ITO transparent electrode. A hole transport layer was formed by vacuum depositing a compound (1150Å) represented by the following formula HT1 on the hole injection layer. Subsequently, the compound 1 was vacuum-deposited on the hole transport layer with a film thickness of 50 Å to form an electron suppressing layer. Subsequently, a light emitting layer was formed by vacuum depositing a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200 Å on the electron suppressing layer at a weight ratio of 25:1. A hole blocking layer was formed by vacuum depositing a compound represented by the following Chemical Formula HB1 with a film thickness of 50 Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of organic material was maintained at 0.4 to 0.7 Å/sec, lithium fluoride at the cathode was maintained at 0.3 Å/sec, and the deposition rate for aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 to An organic light emitting device was manufactured by maintaining ^{5x10 -6 torr.}

Examples 1-2 to 1-9

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1.

Comparative example 1-1 and 1-2

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1. The compounds of EB1, EB2, and used in Table 1 are as follows.

Experimental Example 1

When a current was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(Electronic suppression layer) Voltage
(V@20mA
/cm ² ) efficiency
(cd/A@20mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Compound 1 3.51 6.31 (0.140, 0.047) 275 Example 1-2 Compound 2 3.53 6.26 (0.141, 0.047) 280 Example 1-3 Compound 3 3.56 6.37 (0.143, 0.047) 285 Example 1-4 Compound 4 3.52 6.28 (0.139, 0.046) 280 Example 1-5 Compound 5 3.60 6.39 (0.140, 0.047) 285 Example 1-6 Compound 6 3.63 6.14 (0.141, 0.045) 275 Example 1-7 Compound 7 3.64 6.25 (0.140, 0.045) 280 Example 1-8 Compound 8 3.78 6.43 (0.139, 0.046) 290 Example 1-9 Compound 9 3.73 6.42 (0.140, 0.045) 295 Comparative Example 1-1 EB1 4.17 5.72 (0.139, 0.045) 160 Comparative Example 1-2 EB2 3.95 6.03 (0.142, 0.042) 230

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron suppressing layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device. Comparative Examples 1-1 and 1-2 In, the organic light-emitting device manufactured by using the compound of EB1 and EB2, which has a central core similar to the core of the present invention, and the amine group is directly bonded without a linking group at the second position, as an electron suppressing layer, has a longer life than the device of the present invention. I got a falling result.

As in the compounds of the present invention, a material in which an amine group is substituted with a linking group including phenyl is structurally more stable, and the Tg is increased by 30 to 50° C. or higher than when there is no linking group, thereby increasing thermal stability, thereby greatly increasing the lifespan.

As shown in the results of Table 1, it was confirmed that the compound according to the present invention has excellent electron blocking ability and thus can be applied to an organic light-emitting device.

Although the preferred embodiment (electron suppression layer) of the present invention has been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention. It belongs to the scope of the invention.

1: substrate
2: first electrode
3: organic material layer
4: light-emitting layer
5: second electrode

Claims (8)

An amine derivative represented by the following formula (1):
[Formula 1]

In Formula 1 above
Ar1 and Ar2 are the same as or different from each other, and each independently contains one or more heteroatoms selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or N, O and S having 3 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a heteroaryl group; Or a heteroaryl group containing at least one heteroatom selected from the group consisting of N, O and S having 3 to 20 carbon atoms substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms,
L is a phenylene group, a divalent biphenyl group, a divalent terphenyl group, a divalent naphthyl group, a divalent dimethylfluorene group, or a divalent phenanthrene group,
R and R'are the same as or different from each other, and each independently is an alkyl group having 1 to 10 carbon atoms,
R1 to R4 are hydrogen,
a, b, and d are integers of 3,
c is an integer of 4. The amine derivative of claim 1, wherein Formula 1 is represented by the following Formula 2:
[Formula 2]

In Formula 2, the definitions of R, R', R1 to R4, Ar1, Ar2, L, and a to d are as defined in Formula 1. delete delete The amine derivative of claim 1, wherein Formula 1 is any one selected from the following compounds:

A first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the amine derivative of any one of claims 1, 2 and 5. The organic light emitting device. The organic light-emitting device of claim 6, wherein the organic material layer includes an emission layer, and the emission layer includes the amine derivative. The organic light-emitting device of claim 6, wherein the organic material layer includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, a hole transport layer, or an electron blocking layer includes the amine derivative.

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