KR102298596B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device having improved driving voltage, efficiency, and lifetime.

Description

Organic light emitting device

The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifetime.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

In the organic light emitting device as described above, the development of an organic light emitting device having improved driving voltage, efficiency, and lifespan is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifetime.

In order to solve the above problems, the present invention provides the following organic light emitting device:

anode; hole injection layer; hole transport layer; light emitting layer; and a negative electrode;

The hole injection layer includes a compound represented by the following formula (1),

The hole transport layer comprises a compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 haloalkyl; substituted or unsubstituted C _1-60 haloalkoxy substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted phenyl; Or a substituted or unsubstituted pyridinyl,

[Formula 2]

In Formula 2,

Y ₁ and Y ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or Y ₁ and Y ₂ are substituted or unsubstituted C _{6 Forming a C 2-60} heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of _{-60 aromatic ring, or substituted or unsubstituted N, O and S,}

L ₁ is a single bond; substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,

L ₂ and L ₃ are each independently, a single bond; substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,

Ar ₃ and Ar ₄ are each independently, di(C _6-60 aryl)amino; substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

The organic light emitting device described above has excellent driving voltage, efficiency, and lifetime.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole injection layer 3 , a hole transport layer 4 , a light emitting layer 5 , and a cathode 6 .
2 shows a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 7, an electron injection layer 8 and a cathode 6 An example of an organic light emitting device is shown.
3 is a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), light emitting layer (5), electron control layer (9), electron transport layer (7), electron injection layer (8) and an example of an organic light emitting device including a cathode 6 .

Hereinafter, it will be described in more detail to help the understanding of the present invention.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group 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 -Dimethylheptyl, 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 alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. 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, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, 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, phenanthroline group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description of the above-described heterocyclic group may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Hereinafter, the present invention will be described in detail for each configuration.

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may further include a hole injection layer between the anode and a hole transport layer to be described later.

The hole injection material is a layer that injects holes from the electrode, and the hole injection material has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound that prevents the exciton from moving to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

In the present invention, the compound represented by Formula 1 is included as a hole injection material.

Preferably, X ₁ , X ₂ , X ₃ and X ₄ are each independently cyano; Or it may be a substituted or unsubstituted C _{6-20 aryl,}

More preferably, X ₁ , X ₂ , X ₃ and X ₄ are each independently cyano; phenyl substituted with 1 cyano; phenyl substituted with two cyanos; phenyl substituted with 1 cyano and 1 trifluoromethyl; or phenyl substituted with 2 cyano and 1 fluoro;

Most preferably, X ₁ , X ₂ , X ₃ and X ₄ are each independently cyano or any one selected from the group consisting of:

Preferably, R ₁ and R ₂ are each independently hydrogen; halogen; cyano; amino; substituted or unsubstituted C _1-20 alkyl; substituted or unsubstituted C _1-20 haloalkyl; Or it may be a substituted or unsubstituted C _1-20 haloalkoxy,

More preferably, R ₁ and R ₂ are each independently hydrogen; cyano; fluoro; trifluoromethyl; or trifluoromethoxy.

Preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of;

More preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

Preferably, X ₁ and X ₃ may be identical to each other.

Preferably, X ₂ and X ₄ may be identical to each other.

Preferably, R ₁ and R ₂ may be identical to each other.

Preferably, Ar ₁ and Ar ₂ may be the same as each other.

More preferably, X ₁ and X ₃ may be the same, X ₂ and X ₄ may be the same, R ₁ and R ₂ may be the same, and Ar ₁ and Ar ₂ may be the same.

Representative examples of the compound represented by Formula 1 are as follows:

.

.

The compound represented by Formula 1 is, for example, when X ₁ and X ₃ are the same, X ₂ and X ₄ are the same, R ₁ and R ₂ are the same, and Ar ₁ and Ar ₂ are the same, as shown in Scheme 1 It can be prepared by a manufacturing method, and other compounds can be prepared similarly.

[Scheme 1]

In Scheme 1, X ₁ to X ₄ , R ₁ , R ₂ , Ar ₁ and Ar ₂ are as defined in Formula 1 above, and Z ₁ and Z ₂ are each independently a halogen, preferably Z ₁ and each Z ₂ is independently chloro or bromo.

In Reaction Scheme 1, the reactor, catalyst, solvent, etc. used may be suitably changed for a desired product. The manufacturing method may be more specific in Preparation Examples to be described later.

hole transport layer

The hole transport layer used in the present invention is a layer that receives holes from the hole injection layer formed on the anode or the anode and transports them to the light emitting layer. As a material with high hole mobility, it is suitable.

In the present invention, the compound represented by Formula 2 is included as a hole transport material.

Preferably, Y ₁ and Y ₂ are each independently substituted or unsubstituted C _6-20 aryl, or Y ₁ and Y ₂ are bonded to each other to form a substituted or unsubstituted C _6-20 aromatic ring, or substituted or may form _{a C 2-20} heteroaromatic ring comprising any one or more heteroatoms selected from the group consisting of unsubstituted N, O and S;

More preferably, Y ₁ and Y ₂ are each independently phenyl, or may combine with each other to form any one selected from the group consisting of:

Preferably, L ₁ is a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₁ may be a single bond, phenylene, biphenylrylene, naphthylene, or phenanthrenylene.

Preferably, L ₂ and L ₃ are each independently a single bond; substituted or unsubstituted C _6-20 arylene; Or it may be _{a C 2-20} heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L ₂ and L ₃ may each independently be a single bond, phenylene, biphenylrylene, phenylene substituted with 4 deuterium, naphthylene, or phenanthrenylene.

Preferably, Ar ₃ and Ar ₄ are each independently di(C _6-20 aryl)amino; substituted or unsubstituted C _6-20 aryl; Or it may be _{a C 2-20} heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, Ar ₃ and Ar ₄ may each independently be phenyl, biphenylyl, terphenylyl, naphthyl, triphenylenyl, dibenzofuranyl, or diphenylamino.

Representative examples of the compound represented by Formula 2 are as follows:

.

.

The compound represented by Chemical Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below, and other compounds may be prepared similarly.

[Scheme 2]

In Scheme 2, Y ₁ and Y ₂ , L ₁ to L ₃ , Ar ₃ and Ar ₄ are as defined in Formula 2 above, Z ₃ is halogen, and preferably Z ₃ is chloro or bromo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

light emitting layer

The light emitting layer used in the present invention is a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode, 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-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted derivative. It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

electronic control layer

The organic light emitting device according to the present invention may further include an electron control layer between the light emitting layer and an electron transport layer to be described later.

The electron control layer refers to a layer that controls the mobility of electrons according to the energy level of the light emitting layer in the organic light emitting device.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer between the light emitting layer and the cathode.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable.

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 to 3 . FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole injection layer 3 , a hole transport layer 4 , a light emitting layer 5 , and a cathode 6 . 2 shows a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 7, an electron injection layer 8 and a cathode 6 An example of an organic light emitting device is shown. 3 is a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), light emitting layer (5), electron control layer (9), electron transport layer (7), electron injection layer (8) and an example of an organic light emitting device including a cathode 6 .

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. 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. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

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

On the other hand, the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double-sided emission type depending on the material used.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

Preparation 1-1

2,5-dibromocyclohexa-2,5-diene-1,4-dione (15.0 g, 56.4 mmol), (4-(trifluoromethyl)phenyl)boronic acid (23.6 g, 124.1 mmol), tetrakis (tri Phenylphosphine) palladium (0) (6.53 g, 5.65 mmol) and potassium carbonate (68.6 g, 496.5 mmol) were placed in a mixed solution of tetrahydrofuran (650 ml) and water (200 ml), and at 80 ° C. was stirred for 4 hours. After completion of the reaction, using water and ethyl acetate, extraction was performed, concentration was performed, and column separation was performed using methylene chloride and n-hexane. Thereafter, a precipitate was prepared using methylene chloride and petroleum ether, followed by filtration to obtain compound 1-1-A (8.60 g, 21.7 mmol).

MS[M+H] ⁺ = 397

Compound 1-1-A (8.60 g, 21.7 mmol) and malononitrile (14.4 g, 217.0 mmol) were placed in methylene chloride (1100 ml) under a nitrogen stream, and cooled to 0 °C. Then, titanium chloride (23.8ml, 217.0mmol) and pyridine (35.0ml, 434.1mmol) were slowly added in this order, followed by stirring at 60°C for 24 hours. After completion of the reaction, extraction was performed using water and methylene chloride, followed by concentration, and column separation was performed using methylene chloride, ethyl acetate, and n-hexane. Thereafter, a precipitate was prepared using methylene chloride and petroleum ether, followed by filtration to obtain compound 1-1 (1.9 g, 3.85 mmol).

MS[M+H] ⁺ = 493

Preparation 1-2

Except for using (4-cyano-2,3,5,6-tetrafluorophenyl)boronic acid instead of (4-(trifluoromethyl)phenyl)boronic acid, the preparation method of compound 1-1A of Preparation Example 1-1 and Compound 1-2-A was prepared in the same manner.

MS[M+H] ⁺ = 455

Compound 1-2 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-2-A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 551

Preparation 1-3

Except for using (3,5-dicyanophenyl)boronic acid instead of (4-(trifluoromethyl)phenyl)boronic acid, Compound 1-3 in the same manner as in the preparation of Compound 1-1-A of Preparation Example 1-1 A was prepared.

MS[M+H] ⁺ = 361

Compound 1-3 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-3A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 457

Preparation Example 1-4

Use 2,5-dibromo-3,6-difluorocyclohexa-2,5-diene-1,4-dione instead of 2,5-dibromocyclohexa-2,5-diene-1,4-dione (4-(trifluoromethyl) Except for using (3,4-dicyanophenyl)boronic acid instead of phenyl)boronic acid, compound 1-4A was prepared in the same manner as in the preparation method of compound 1-1-A of Preparation Example 1-1.

MS[M+H] ⁺ = 397

Compound 1-4 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-4A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 493

Preparation 1-5

Except for using (3,5-dicyano-2,4,6-trifluorophenyl)boronic acid instead of (3,4-dicyanophenyl)boronic acid, the same method as for the preparation of compound 1-4A of Preparation Example 1-4 Compound 1-5-A was prepared by the method.

MS[M+H] ⁺ = 504

Compound 1-5 was prepared in the same manner as in Preparation Example 1-4, except that Compound 1-5-A was used instead of Compound 1-4-A.

MS[M+H] ⁺ = 601

Preparation 1-6

Use 2,5-dibromo-3,6-dioxocyclohexa-1,4-diene-1,4-dicarbonitrile instead of 2,5-dibromocyclohexa-2,5-diene-1,4-dione (4-(trifluoromethyl) Except that (4-(trifluoromethoxy)phenyl)boronic acid was used instead of phenyl)boronic acid, compound 1-6-A was prepared in the same manner as in the preparation method of compound 1-1-A of Preparation Example 1-1.

MS[M+H] ⁺ = 479

Compound 1-6 was prepared in the same manner as in the preparation of Compound 1-1 of Preparation Example 1-1, except that Compound 1-6-A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 575

Preparation 1-7

Except for using (4-cyano-3-(trifluoromethyl)phenyl)boronic acid instead of (3,4-dicyanophenyl)boronic acid, the compound in the same manner as in the preparation method of Compound 1-4A of Preparation Example 1-4 1-7-A was prepared.

MS[M+H] ⁺ = 483

Compound 1- in the same manner as in the preparation method of Compound 1-4 of Preparation Example 1-4, except that Compound 1-7-A was used instead of Compound 1-4A and 4-(cyanomethyl)benzonitrile was used instead of malononitrile. 7 was prepared.

MS[M+H] ⁺ = 731

Preparation 1-8

Except for using (3-cyano-4,5-difluorophenyl) boronic acid instead of (4- (trifluoromethyl) phenyl) boronic acid, the compound was prepared in the same manner as in the preparation method of Compound 1-1-A of Preparation Example 1-1. 1-8-A was prepared.

MS[M+H] ⁺ = 383

Compound 1-8 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-8-A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 479

Preparation 1-9

Except for using (6-cyanopyridin-3-yl)boronic acid instead of (4-(trifluoromethyl)phenyl)boronic acid, Compound 1- 9-A was prepared.

MS[M+H] ⁺ = 313

Compound 1-9 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-9-A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 409

Preparation Example 1-10

Except for using (4-cyano-3-fluoro-5-(trifluoromethoxy)phenyl)boronic acid instead of (3,4-dicyanophenyl)boronic acid, the method for preparing compound 1-4A of Preparation Example 1-4 and Compound 1-10-A was prepared in the same manner.

MS[M+H] ⁺ = 551

Compound 1-10 was prepared in the same manner as in the preparation method of Compound 1-4 of Preparation Example 1-4, except that Compound 1-10-A was used instead of Compound 1-4-A.

MS[M+H] ⁺ = 649

Preparation Example 1-11

Except for using (4,5-dicyano-2-fluorophenyl)boronic acid instead of (4-(trifluoromethyl)phenyl)boronic acid, the compound was prepared in the same manner as in the preparation method of Compound 1-1-A of Preparation Example 1-1. 1-11-A was prepared.

MS[M+H] ⁺ = 397

Compound 1-11 was prepared in the same manner as in the preparation method of Compound 1-1 of Preparation Example 1-1, except that Compound 1-11-A was used instead of Compound 1-1-A.

MS[M+H] ⁺ = 493

Preparation 2-1

2-Bromo-9,9-diphenyl-9H-fluorene (20 g, 50.5 mmol) and di([1,1'-biphenyl]-4-yl)amine (17.8 g, 55.5 mmol) and sodium Toluene (200 ml) was added to tert-butoxide (7.27 g, 75.8 mmol), followed by heating and stirring for 5 minutes. Bis(tri-tert-butylphosphine)palladium (0.052 g, 0.101 mmol) was slowly added dropwise to the solution, followed by heating and stirring for 1 hour. After completion of the reaction and filtration, the layers were separated with toluene and water. After removal of the solvent, it was recrystallized from ethyl acetate to obtain compound 2-1 (28.7 g, 89.2% yield).

MS[M+H] ⁺ = 637

Preparation Example 2-2

Preparation Example except that bis(4-(naphthalen-1-yl)phenyl-2,3,5,6-d4)amine was used instead of di([1,1'-biphenyl]-4-yl)amine Compound 2-2 was prepared in the same manner as in the preparation method of 2-1.

MS[M+H] ⁺ = 746

Preparation 2-3

Compound 2-3 was prepared in the same manner as in Preparation Example 2-1, except that N-phenyltriphenylen-2-amine was used instead of di([1,1'-biphenyl]-4-yl)amine. .

MS[M+H] ⁺ = 636

Preparation 2-4

Use 2-bromo-9,9'-spirobi[fluorene] instead of 2-bromo-9,9-diphenyl-9H-fluorene and di([1,1'-biphenyl]-4-yl)amine Instead of using N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine, Compound 2 in the same manner as in Preparation Example 2-1 -4 was prepared.

MS[M+H] ⁺ = 636

Preparation Example 2-5

Use 2-bromospiro[fluorene-9,8'-indolo[3,2,1-de]acridine] instead of 2-bromo-9,9-diphenyl-9H-fluorene and di([1,1' Except for using N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1'-biphenyl]-4-amine instead of -biphenyl]-4-yl)amine, Compound 2-5 was prepared in the same manner as in Preparation Example 2-1.

MS[M+H] ⁺ = 815

Preparation 2-6

N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1'-biphenyl]-4-amine instead of N4,N4,N4'-triphenyl-[1,1'-biphenyl ] Except for using -4,4'-diamine, compound 2-6 was prepared in the same manner as in Preparation Example 2-5.

MS[M+H] ⁺ = 816

Preparation 2-7

Use 2'-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] instead of 2-bromo-9,9-diphenyl-9H-fluorene and di([1,1'- Compound 2-7 was prepared in the same manner as in Preparation Example 2-1, except that N-phenylnaphthalen-2-amine was used instead of biphenyl]-4-yl)amine.

MS[M+H] ⁺ = 625

Preparation 2-8

Preparation Example 2, except that 4'-bromo-10,10-dimethyl-10H-spiro [anthracene-9,9'-fluorene] was used instead of 2-bromo-9,9-diphenyl-9H-fluorene Compound 2-8 was prepared in the same manner as in the preparation method of -1.

MS[M+H] ⁺ = 678

Example 1

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) to a thickness of 100 nm was placed in distilled water in which a dispersant was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and the distilled water was manufactured by Millipore Co. Secondary filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

Compound 1-1 prepared above was thermally vacuum deposited on the prepared ITO transparent electrode to form a hole injection layer with a thickness of 5 nm. A hole transporting layer having a thickness of 40 nm was formed by vacuum-depositing the compound 2-1 prepared above as a hole transporting material thereon. On the hole transport layer, compound H1 and compound D1 were vacuum-deposited at a weight ratio of 25:1 to form a light emitting layer with a thickness of 30 nm. Compound ET1 was vacuum-deposited on the light emitting layer to form an electron control layer with a thickness of 3 nm. On the electron control layer, compound ET2 and lithium quinolate (LiQ) were vacuum-deposited in a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 35 nm. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were sequentially deposited to a thickness of 1.2 nm and 200 nm to form a cathode, thereby manufacturing an organic light emitting diode.

In the above process, the deposition rate of organic material was maintained at 0.04 nm/sec to 0.07 nm/sec, the deposition rate of lithium fluoride was maintained at 0.03 nm/sec, and the deposition rate of aluminum was maintained at 0.2 nm/sec, The vacuum degree during deposition is 2 ⅹ10 ^-7 torr to 5 x 10 ^-6 torr was maintained.

Examples 2 to 14

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds of Table 1 were used instead of Compound 1-1 and Compound 2-1.

Comparative Examples 1 to 7

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds of Table 1 were used instead of Compound 1-1 and Compound 2-1. Compounds I-A to I-C and HT-A to HT-C of Table 1 are as follows.

Experimental example

For each of the organic light emitting devices of Examples and Comparative Examples, the driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2 , and the luminance at a current density of 20 mA/cm 2} was 98% of the initial luminance (LT98) ) was measured. The results are shown in Table 1 below.

hole injection layer hole transport layer Voltage
(V) current efficiency
(cd/A) color coordinates
(x,y) LT98
(hr) Example 1 compound 1-1 compound 2-1 3.99 5.81 (0.132, 0.110) 137 Example 2 compound 1-2 compound 2-6 3.87 5.97 (0.132, 0.110) 151 Example 3 compound 1-3 compound 2-8 3.94 5.86 (0.132, 0.110) 142 Example 4 compound 1-4 compound 2-2 3.91 6.02 (0.132, 0.110) 158 Example 5 compound 1-5 compound 2-3 3.90 5.93 (0.132, 0.110) 151 Example 6 compound 1-6 compound 2-4 3.87 5.83 (0.132, 0.110) 140 Example 7 compound 1-7 compound 2-1 3.98 5.94 (0.132, 0.110) 154 Example 8 compounds 1-8 compound 2-5 4.00 5.82 (0.132, 0.110) 138 Example 9 compounds 1-9 compound 2-6 3.97 5.81 (0.132, 0.110) 146 Example 10 compounds 1-10 compound 2-7 3.95 5.85 (0.132, 0.110) 147 Example 11 compound 1-11 compound 2-2 3.89 5.99 (0.132, 0.110) 156 Example 12 compound 1-5 compound 2-1 3.94 5.90 (0.132, 0.110) 155 Example 13 compound 1-4 compound 2-4 3.92 5.98 (0.132, 0.110) 157 Example 14 compounds 1-10 compound 2-2 3.97 5.92 (0.132, 0.110) 152 Comparative Example 1 I-A compound 2-7 4.24 5.39 (0.132, 0.112) 118 Comparative Example 2 I-B compound 2-4 4.30 5.38 (0.132, 0.110) 112 Comparative Example 3 I-C compound 2-1 4.26 5.26 (0.132, 0.111) 113 Comparative Example 4 compound 1-1 HT-A 4.34 5.42 (0.132, 0.111) 104 Comparative Example 5 compound 1-5 HT-B 4.31 5.44 (0.132, 0.110) 101 Comparative Example 6 I-A HT-C 4.41 5.17 (0.132, 0.112) 99 Comparative Example 7 I-C HT-A 4.39 5.09 (0.132, 0.111) 100

As shown in Table 1, the organic light emitting device of an embodiment using the compound represented by Formula 1 as the hole injection layer and the compound represented by Formula 2 as the hole transport layer uses only each compound or (Comparative Examples 1 to 5) ), compared to the case where neither was used (Comparative Examples 6 and 7), it was confirmed that it was excellent in terms of voltage, efficiency, particularly lifespan.

1: Substrate 2: Anode
3: hole injection layer 4: hole transport layer
5: light emitting layer 6: cathode
7: electron transport layer 8: electron injection layer
9: Electronic control layer

Claims (11)

anode; hole injection layer; hole transport layer; light emitting layer; and a negative electrode;
The hole injection layer includes a compound represented by the following formula (1),
The hole transport layer includes a compound represented by the following formula (2),
The hole injection layer and the hole transport layer are adjacent to each other,
Organic light emitting device:
[Formula 1]

In Formula 1,
X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 haloalkyl; substituted or unsubstituted C _1-60 haloalkoxy; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of

[Formula 2]

In Formula 2,
Y ₁ and Y ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or Y ₁ and Y ₂ are substituted or unsubstituted C _{6 by bonding to each other Forming a C 2-60} heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of _{-60 aromatic ring, or substituted or unsubstituted N, O and S,}
L ₁ is a single bond; substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,
L ₂ and L ₃ are each independently, a single bond; substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,
Ar ₃ and Ar ₄ are each independently, di(C _6-60 aryl)amino; substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
X ₁ , X ₂ , X ₃ and X ₄ are each independently cyano; phenyl substituted with 1 cyano; phenyl substituted with two cyanos; phenyl substituted with 1 cyano and 1 trifluoromethyl; or phenyl substituted with 2 cyano and 1 fluoro;
organic light emitting device.
According to claim 1,
R ₁ and R ₂ are each independently hydrogen; cyano; fluoro; trifluoromethyl; or trifluoromethoxy;
organic light emitting device.
delete According to claim 1,
X ₁ and X ₃ are the same, X ₂ and X ₄ are the same, R ₁ and R ₂ are the same, Ar ₁ and Ar ₂ are the same,
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
Y ₁ and Y ₂ are each independently phenyl, or combine with each other to form any one selected from the group consisting of:
Organic light emitting device:

.
According to claim 1,
L ₁ is a single bond, phenylene, biphenylrylene, naphthylene, or phenanthrenylene;
organic light emitting device.
According to claim 1,
L ₂ and L ₃ are each independently a single bond, phenylene, biphenylrylene, phenylene substituted with 4 deuterium, naphthylene, or phenanthrenylene;
organic light emitting device.
According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, triphenylenyl, dibenzofuranyl, or diphenylamino;
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

.

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