KR102111149B1 - Organic light emitting device - Google Patents

Abstract

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

Description

Organic light emitting device {Organic light emitting device}

The present invention relates to an organic light emitting device with improved driving voltage, efficiency, and life.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy 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, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The 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. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, 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. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows.

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

Conventionally, a red organic light-emitting device used in an organic light-emitting device has been known to use a derivative of an n-type and amphoteric substance having a carbazole-quinazoline bond structure as a light emitting layer. However, in this case, there was a serious problem in efficiency and lifetime deviation.

Alternatively, in a single device or a stacked device using two red-green light emitting layers, red light is emitted together with green light having a relatively low efficiency, thereby inducing color coordinate shift to increase proper yellow-green or white device efficiency. Is known. In addition, by depositing p-type derivatives that are the same as or different from the hole transport layer in the red emission layer, hole injection into the emission layer and movement of holes in the emission layer are facilitated, and hole injection into the green emission layer is facilitated. Accordingly, there is a need to develop a material having a certain molecular weight or more that forms a stable interface between the two light-emitting layers and has a high charge transport capability.

Accordingly, the present invention provides a combination of compounds represented by the derivatives set forth in the claims as a constituent material combination of the organic light emitting device. Another object is to provide an organic electroluminescent device having a low driving voltage and a long life.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device with improved driving voltage, efficiency, and life.

The present invention provides the following organic light emitting device:

anode;

Hole transport layer;

A red light emitting layer;

Green light emitting layer;

Electron transport layer; And

A cathode,

The hole transport material included in the hole transport layer and the first host included in the red light emitting layer are represented by the following Chemical Formula 1 or Chemical Formula 2,

The second host included in the red light emitting layer is represented by the following Chemical Formula 3 or Chemical Formula 4,

Single or stacked organic light emitting devices:

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

L ₁ , L ₂ and L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or C _5-60 heteroarylene containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,

G ₁ , G ₂ , G ₃ and G ₄ are each independently, substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S, or a substituted or unsubstituted monocyclic or polycyclic ring in combination with an adjacent group. To form,

Ar ₃ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 arylalkenyl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁₀₁ to R ₁₀₅ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,

r ₁₀₁ is an integer from 1 to 4,

r ₁₀₂ is an integer from 1 to 3,

r ₁₀₃ is an integer from 1 to 3,

r ₁₀₄ is an integer from 1 to 4,

r ₁₀₅ is an integer from 1 to 4,

When r ₁₀₁ to r ₁₀₅ are each 2 or more, structures in parentheses of 2 or more are the same or different from each other,

a, b and z are integers from 0 to 4,

When a, b, and z are each 2 or more, structures in 2 or more parentheses are the same or different from each other,

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

Ar ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; A substituted or unsubstituted C _6-60 arylalkyl group; Substituted or unsubstituted C _6-60 arylalkenyl,

R ₁₀₁ to R ₁₀₄ and R ₁₀₆ to R ₁₀₈ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S; Or two of R ₁₀₆ to R ₁₀₈ are bonded to each other to include a substituted or unsubstituted C _6-60 aromatic ring, or any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S Form a C _5-60 heteroaromatic ring,

R ₁₀₉ is hydrogen, substituted or unsubstituted C _6-60 aryl, or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,

L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene;

r ₁₀₁ is an integer from 1 to 4,

r ₁₀₂ is an integer from 1 to 3,

r ₁₀₃ is an integer from 1 to 3,

r ₁₀₄ is an integer from 1 to 4,

r ₁₀₆ is an integer from 1 to 2,

r ₁₀₇ is an integer from 1 to 4,

r ₁₀₈ is an integer from 1 to 4,

When r ₁₀₁ to r ₁₀₄ and r ₁₀₆ to r ₁₀₉ are each 2 or more, structures in two or more parentheses are the same or different from each other.

As described above, in the organic light emitting device according to the present invention, the combination of the hole transport layer, the red first host, and the second host has advantages of voltage drop, efficiency increase, and life increase regardless of various structures and shapes of the hole injection layer. It has a greater effect especially when the hole transport layer and the first host are used in the same structure.

In addition, as will be described later, as a result of comparing the examples through the combination according to the present invention and the comparative example, the red-green single light emitting device and the stacked white light emitting device have advantages in synthesizing the material and driving the device. I could confirm.

The organic light-emitting device described above is excellent in driving voltage, efficiency, and life.

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6.
2 is a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, a first light emitting layer 4-1, a second light emitting layer 4-2, an electron transport layer 5, An example of an organic light emitting device comprising an electron injection layer 8 and a cathode 6 is shown.

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

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

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

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

In the present specification, the silyl group 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 boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. 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 are 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 is not limited thereto.

In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. 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, styrenyl 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 cycloalkyl group has 3 to 20 carbon atoms. 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one 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, a terphenyl group, a quarterphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, 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 combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group. In the present specification, heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In this specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

The present invention provides the following organic light emitting device:

anode; Hole transport layer; A red light emitting layer; Green light emitting layer; Electron transport layer; And a cathode, wherein the hole transport material included in the hole transport layer and the first host included in the red light emitting layer are represented by Formula 1 or Formula 2, respectively, and the second host included in the red light emitting layer has the formula A single or stacked organic light-emitting device represented by 3 or Chemical Formula 4.

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

Cathode and anode

The positive electrode and the negative electrode used in the present invention mean electrodes used in organic light emitting devices.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Metal and oxide combinations 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 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 is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred.

It is preferred that the high 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 layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. , Organic anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

Hole transport layer  And Emitting layer

The organic light emitting device according to the present invention, by adjusting the material contained in the hole transport layer and the red light emitting layer, improves the driving voltage, efficiency and life of the organic light emitting device.

The hole transport layer is a layer that transports holes from the anode or the hole injection layer to the light emitting layer by receiving holes from the anode or the hole injection layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer as a hole transport material. Large materials are suitable.

In particular, the hole transport material and the first host included in the red light emitting layer are the same or different from each other, and are represented by the compound represented by Chemical Formula 1 or 2. When the hole transport material and the first host are the same compound, the interface resistance and the hole injection barrier between the hole transport layer and the red emission layer are reduced, so that holes are more easily introduced into the red emission layer. In addition, when the hole transport material and the first host are different from each other, there is an effect that holes easily enter the red light emitting layer based on the hole injection barrier of the compounds represented by Chemical Formulas 1 and 2 and the excellent hole transport ability of the two compounds. .

In the above formulas 1 and 2, preferably, G ₁ , G ₂ , G ₃ and G ₄ are each independently methyl or phenyl.

Preferably, L ₁ , L ₂ and L ₃ are each independently any one selected from the group consisting of:

In the above,

R ₁ is each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, L ₁ , L ₂ and L ₃ are each independently a single bond, phenylene, biphenylylene, or dimethylfluorenylene.

Preferably, Ar ₃ is any one selected from the group consisting of:

In the above,

R ₈ is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of N, O and S.

More preferably, Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenylene, dibenzofuranyl, carbazolyl, or dibenzothiophenyl to be.

Preferably, R ₁₀₁ to R ₁₀₅ are each independently hydrogen, phenyl, biphenyl, or naphthyl.

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

The compound represented by Chemical Formula 1 may be prepared by reacting a compound represented by Chemical Formula 1 'with a compound represented by Chemical Formula 1 ", as shown in Reaction Scheme 1 below.

[Scheme 1]

In the above scheme, definitions other than X 'are as described above, and X' is halogen, more preferably bromo. The manufacturing method may be more specific in the manufacturing examples to be described later.

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

The compound represented by Chemical Formula 2 may be prepared by reacting a compound represented by Chemical Formula 2 'with a compound represented by Chemical Formula 2 ", as shown in Reaction Scheme 2 below.

[Scheme 2]

In the above scheme, definitions other than X 'are as described above, and X' is halogen, more preferably bromo. The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, a single host has a high HOMO, a large barrier to holes, and a smooth movement of electrons in the compound, resulting in an imbalance in the emission region. Accordingly, in the present invention, the driving voltage, efficiency, and life of the organic light emitting device can be improved by using the hole transport type second host together.

Specifically, the red light emitting layer further includes a host represented by Chemical Formula 3 or 4 as a second host:

In Chemical Formula 3, preferably, Ar ₄ is each independently phenyl substituted with phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, or naphthyl Or naphthyl substituted with phenyl.

Representative examples of the compound represented by Formula 3 are as follows:

The compound represented by Chemical Formula 3 may be prepared by reacting a compound represented by Chemical Formula 3 'with a compound represented by Chemical Formula 3 ", as shown in Reaction Scheme 3 below.

[Scheme 3]

In the above scheme, the definitions other than Y 'and Y "are as described above, one of Y' and Y" is halogen (more preferably bromo), and the other is B (OH) ₂ . The manufacturing method may be more specific in the manufacturing examples to be described later.

In the above formula (4), preferably, L ₄ is a single bond, or phenylene.

Preferably, R ₁₀₉ is hydrogen, phenyl, biphenyline, naphthyl, dimethylfluorenyl, or pyridine.

Preferably, r ₁₀₆ + r ₁₀₇ + r ₁₀₈ (sum of r ₁₀₆ , r ₁₀₇ and r ₁₀₈ ) is 1.

Preferably, R ₁₀₆ to R ₁₀₉ are each independently represented by -L ₅ -Ar ₅ , L ₅ is a single bond, or a substituted or unsubstituted C _6-60 arylene; Ar ₅ is substituted or unsubstituted C _6-60 aryl, or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S. More preferably, L ₅ is a single bond, or phenylene; Ar ₅ is carbazolyl, benzocarbazolyl, dibenzothiophenyl, or dibenzofuranyl unsubstituted or substituted with phenyl, biphenylline, or terphenylline.

Representative examples of the compound represented by Formula 4 are as follows:

The compound represented by Chemical Formula 4 may be prepared by reacting a compound represented by Chemical Formula 4 'with a compound represented by Chemical Formula 4 ", as shown in Reaction Scheme 4 below. In the example can be more specific.

[Reaction Scheme 4]

In the above scheme, the definitions other than Z 'and Z "are as described above, one of Z' and Z" is halogen (more preferably bromo), and the other is B (OH) ₂ . The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, the weight ratio of the first host and the second host is preferably 99: 1 to 1:99.

In addition, the red light emitting layer may include a dopant material in addition to the host compound. The dopant material is not particularly limited as long as it is used in an organic light emitting device, and examples thereof include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.

Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, such as pyrene, anthracene, chrysene, periplanene, etc. having arylamino groups, and substituted or unsubstituted styrylamine compounds. As a compound in which at least one arylvinyl group is substituted in the substituted arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto. Preferably, a red dopant is used as the dopant.

Preferably, the red light emitting layer further includes a compound represented by Formula 5 below:

[Formula 5]

In Chemical Formula 5,

n1 is 1 or 2,

R ' ₁ to R' ₄ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,

X-Y is an auxiliary ligand.

이다. Preferably, XY is

to be.

In addition, the red light emitting layer is provided in contact with the green light emitting layer. The green light emitting layer includes a green dopant, and is not particularly limited as long as it is used in an organic light emitting device.

Electron transport layer

The electron transport layer is a layer that receives electrons from the electron injection layer or the cathode and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode well and transferring them to the light emitting layer, which has high mobility for electrons The material is suitable.

Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including 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 or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

In addition, the organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode, if necessary. The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

Organic light emitting diode

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except for using the compounds of Formulas 1 to 4 in the hole transport layer and the red light emitting layer.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, a positive electrode is formed by depositing metal or conductive metal oxides or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and / or an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the first host compound and the second host compound may be formed as a light emitting layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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

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

Further, the organic light emitting device according to the present invention can be used as a single type or stacked organic light emitting device. Specifically, in the case of a stacked organic light emitting device, the following organic light emitting device is provided:

anode; Hole transport layer; A red light emitting layer; Green light emitting layer; Electron transport layer; N-charge generation layer; P-charge generation layer; Hole transport layer; Hole control layer; Blue light emitting layer; Electron transport layer; The first host included in the red light emitting layer and the hole transport material included in the hole transport layer and the negative electrode are represented by Formula 1 or Formula 2, respectively, and the second host included in the red emitting layer is Formula 3 Or represented by the formula (4), an organic light emitting device.

In addition, the structure of the organic light emitting device according to the present invention is schematically illustrated in FIGS. 1 and 2. FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6. In addition, FIG. 2 shows an example of an organic light emitting device further including a hole injection layer, a second light emitting layer, and an electron injection layer in the organic light emitting device of FIG. 1.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

Manufacturing example  One: HTM1 ~ HTM6  Produce

One) HTM1  Produce

9,9-dimethyl-9H-fluoren-2-amine (10 g, 47.8 mmol) and 2-bromo-9,9-diphenyl-9H-fluorene (19.36 g, 48.7 mmol), sodium-t- Butoxide (6.43 g, 66.9 mmol) was added to toluene, the mixture was heated and stirred, and refluxed and [bis (tri-t-butylphosphine)] palladium (487 mg, 0.20 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare HTM1 (32.2 g, yield 80%).

MS [M + H] ⁺ = 843.10

2) HTM2  Produce

2-Bromo-9,9-diphenyl-9H-fluorene (5 g, 40.3 mmol) and N-([1,1'-diphenyl] -4-yl) -9,9-dimethyl-9H -Fluoren-2-amine (14.85 g, 41.1 mmol), sodium-t-butoxide (5.42 g, 56.4 mmol) was added to toluene, followed by heating, stirring, and refluxing. [Bis (tri-t-butylphosphine)] Palladium (41.1 mg, 0.20 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, recrystallization was performed using tetrahydrofuran and ethyl acetate to prepare HTM2 (19.1 g, yield 70%).

MS [M + H] ⁺ = 678.89

3) HTM3  Produce

<Production of Intermediate A1>

9,9-dimethyl-9H-fluoren-2-amine (150 g, 716.7 mmol) was added and dissolved in DMF (400 mL), and then NBS (177.98 g, 716.7 mmol) was slowly added dropwise at 0 ° C. at room temperature. Stir for 3 hours. After extraction with water and chloroform at room temperature, the white solid was recrystallized from hexane to prepare A-1 (165 g, yield 80%).

MS [M + H] ⁺ = 288.03

<Production of Intermediate B1>

The above prepared intermediate A1 (46.1 g, 159.9 mmol) and phenylboronic acid (20.1 g, 164.7 mmol) were added to dioxane (300 mL), followed by addition of a 2M potassium carbonate aqueous solution (100 mL), and tetrakistry After adding phenyl-phosphino palladium (462 mg, 3.99 mmol), the mixture was heated and stirred for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate aqueous solution was removed to separate the layers. After removing the solvent, the white solid was recrystallized from hexane to prepare B1 (38.8 g, yield 85%).

MS [M + H] ⁺ = 286.15

<Preparation of HTM3>

The prepared intermediate B1 (10 g, 35.0 mmol) and 2-bromo-9,9-diphenyl-9H-fluorene (28.12 g, 70.8 mmol), sodium-t-butoxide (9.42 g, 98 mmol) Was added to xylene, stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (357 mg, 0.2 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, recrystallization was performed using tetrahydrofuran and ethyl acetate to prepare HTM3 (24 g, yield 75%).

MS [M + H] ⁺ = 919.20

4) HTM4  Produce

2-Bromotriphenylene (10 g, 32.5 mmol) and N-([1,1'-diphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (10 g, 32.5 mmol), sodium-t-butoxide (12 g, 33.2 mmol) in toluene, heated and stirred to reflux [bis (tri-t-butylphosphine)] palladium (331 mg, 0.20 mmol%) I put it. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare HTM4 (13.7 g, yield 72%).

MS [M + H] ⁺ = 588.77

5) HTM5  Produce

<Production of Intermediate C1>

B1 (11.5 g, 40.3 mmol) prepared previously, 2-bromotriphenylene (12.6 g, 41.1 mmol), and sodium-t-butoxide (5.4 g, 56.4 mmol) were added to toluene, heated and stirred to reflux. And [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (58.9 mg, 2 mol%) was added. After lowering the temperature to room temperature and terminating the reaction, C1 (20.7 g, yield 70%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] ⁺ = 512.23

<Production of HTM5>

The prepared C1 (10 g, 19.5 mmol), 4-bromobiphenyl (2.2 g, 19.89 mmol), and sodium-t-butoxide (2.62 g, 27.3 mmol) were added to toluene, stirred and heated to reflux [ Bis (tri-t-butylphosphine)] palladium (149 mg, 0.29 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare HTM5 (5.7 g, yield 50%).

MS [M + H] ⁺ = 6464.29

6) HTM6  Produce

<Production of Intermediate D1>

9,9-dimethyl-9H-fluoren-2-amine (15 g, 52.5 mmol), 2-bromotriphenylene (16.46 g, 53.6 mmol), sodium-t-butoxide (7.06 g, 73.5 mmol) ) Was put in toluene, stirred under heating, refluxed, and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (767 mg, 2 mol%) was added. After lowering the temperature to room temperature and terminating the reaction, recrystallization was performed using tetrahydrofuran and ethyl acetate to prepare D1 (20.4 g, yield 76%).

MS [M + H] ⁺ = 456.57

<Production of HTM6>

D1 (10 g, 19.54 mmol) prepared above, 2-bromo-9,9-diphenyl-9H-fluorene (4.64 g, 19.9 mmol), sodium-t-butoxide (2.61 g, 27.3 mmol) Was added to xylene, stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (199 mg, 0.2 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare HTM6 (9.57 g, yield 74%).

MS [M + H] + = 752.97

Manufacturing example  2: Preparation of RM1 to RM3

<Preparation of intermediates E1 and E2>

Beta-tetrarone (β-Tetralone, CAS # 530-93-8, 18 g, 123 mmol) and 4-bromophenylhydrazine hydrochloride (CA # 622-88-8, 29 g, 129 mmol) Was added to EtOH (300 mL), and a little hydrochloric acid was added, followed by heating to reflux under nitrogen flow for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, and the product was filtered and dried in a vacuum oven for one day to obtain 25 g of E1 (10-bromo-6,7-dihydro-5H-benzo [c] carbazole) (yield 68.8%).

[M + H] = 298

25 g of E1 prepared above was added to CH ₃ CN (400 mL), and tetrachloro-1,4-benzoquinone, chloranil, DDQ (hereinafter) in a solid state in a cold bath condition at 0 ° C, CAS # 118-75-2, 21 g, 84.7 mmol) was added dropwise at the same equivalent as E1. After completion of the reaction, NaOH (10%) and water were added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with hexane to prepare 21 g of E2 (10-bromo-7H-benzo [c] carbazole) (yield 84.7%).

[M + H] = 296

<Production of intermediates F1 to F3>

1-naphthylboronic acid (CAS # 13922-41-3, 17 g, 100 mmol) and 1-chloro-2-nitrobenzene (CAS # 88-73- 3, 16 g, 100 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol, and then potassium carbonate (CAS # 584-08-7, 41 g, 300 mmol) was dissolved in water and added to the reaction solution and heated for 30 minutes. It was stirred. After 30 minutes, tetrakistriphenylphosphine palladium (0) (tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with ethyl acetate (Ethyl acetate, EA (hereinafter)) to obtain an organic layer, followed by column purification to obtain F1 (18 g, yield 75.5%).

[M + H] = 249

20 g (80 mmol) of F1 prepared above was added to 200 mL of dichloromethane (CH ₂ Cl ₂ (hereinafter)), and bromine (bromine, Br ₂ , CAS # 7726-95-6, 4.3 ml, 84) in an ice bath at 0 ° C mmol) was slowly added dropwise over 20 minutes. After the addition was completed, the reaction solution was stirred at room temperature for about a day. After the reaction was completed, the reaction solution was removed with water and an aqueous solution of sodium thiosulfate (sodium thiosulfate, Na ₂ S ₂ O ₃ (hereinafter), CAS # 10102-17-7), and extracted with dichloromethane. After extraction, the solvent was concentrated with a rotary concentrator to obtain F2 (22.8 g, yield 86.4%) through column purification.

[M + H] = 328

20 g of the prepared F3 was added to triethylphosphite (P (OEt) ₃ (hereinafter), CAS # 122-52-1, 42 mL) and heated and stirred at 180 ° C. for 8 hours. After completion of the reaction, the residual P (OEt) ₃ was removed through vacuum distillation and extracted using EA. The extracted EA was added with anhydrous magnesium sulfate (MgSO ₄ , CAS # 7487-88-9) to remove moisture and column purified to obtain 11.6 g of F3 (5-bromo-7H-benzo [c] carbazole) (yield 64.3%). .

[M + H] = 296

<Production of intermediates G1 to G3>

In the same manner as described in U.S. Patent Publication No. 2009-0076076, trichloroaluminum (Aluminium chloride, AlCl ₃ (hereinafter), CAS # 7446-70-0, 31.9 g, 239 mmol) under a stream of nitrogen is CH ₂ Cl ₂ After putting in 30 mL and stirring at 0 ° C for 10 minutes, beta-tetrarone (β-Tetralone, 17.5 g, 120 mmol) was added. Stir for 20 minutes and Br ₂ (6.74 mL, 131 mmol) was added slowly at the same temperature. After the bromine addition was completed, the reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into an ice bath and extracted with EA. The extracted organic material was dried over MgSO ₄ and concentrated using a rotary concentrator, and then the concentrated solution was purified by column to obtain 19 g of G1 (7-bromo-3,4-dihydronaphthalen-2 (1H) -one) (yield 71.1%).

[M + H] = 225

G1 (20 g, 89 mmol) and phenylhydrazine hydrochloride (CAS # 59-88-1, 12.9 g, 89 mmol) prepared above were added to 300 mL of EtOH, added with a little hydrochloric acid, and then nitrogen for 1 hour. It was heated to reflux under air flow. After completion of the reaction, the mixture was cooled to room temperature, and the product was filtered, and dried in a vacuum oven for one day to obtain 23 g of G2 (2-bromo-6,7-dihydro-5H-benzo [c] carbazole) (yield 88.7%).

[M + H] = 299

Put the prepared G2 (20 g, 67 mmol) into 400 mL of CH ₃ CN and solid tetrachloro-1,4-benzoquinone (tetrachloro-1,4-benzoquinone, chloranil, DDQ ( Hereinafter), CAS # 118-75-2, 21 g, 84.7 mmol) was slowly added dropwise at the same equivalent as G2. After completion of the reaction, NaOH (10%) and water were added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with hexane to obtain 13 g of G3 (2-bromo-7H-benzo [c] carbazole) (yield 64.7%).

[M + H] = 296

<Production of intermediates H1 to H3>

<Production of H1>

2,4-dichloroquinazoline (2,4-dichloroqinazoline, CAS # 607-68-1, 10 g, 50 mmol) and phenylboronic acid (Phenylboronic acid, PBA, CAS # 98-80-6, 6.10 g, 50 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol, then potassium carbonate (CAS # 584-08-7, 41 g, 300 mmol) was dissolved in water, added to the reaction solution, and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0) (tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with EA to obtain an organic layer, followed by column purification to obtain H1 (8.3 g, yield 68.7%).

[M + H] = 240

<Production of H2>

2,4-dichloroquinazoline (2,4-dichloroqinazoline, CAS # 607-68-1, 20 g, 100 mmol) and 4-biphenylboronic acid (PBA, CAS # 5122-94-1) , 20 g, 100 mmol) to obtain H2 (23.3 g, yield 73.2%) in the same manner as in the preparation of H1.

[M + H] = 317

<Production of H3>

2,4-dichloroquinazoline (2,4-dichloroqinazoline, CAS # 607-68-1, 20 g, 100 mmol) and 2-naphthyl boronic acid, CAS # 32316-92-0 , 18.1 g, 100 mmol) to obtain H3 (26.7 g, yield 91.3%) in the same manner as in the preparation of H1.

[M + H] = 290

<Synthesis of intermediates E2-1, F3-1, and G3-1>

<Production of E2-1>

E2 (10 g, 33.7 mmol) prepared previously is anhydrous dimethylacetamide (DMF (hereinafter), CAS # 68-12-2) under nitrogen flow, sodium hydride, NaH (hereafter), CAS # 7646 -69-7, 5 g, 35.9 mmol) was added slowly. After stirring at room temperature for 1 hour, H2 (10.9 g, 34.4 mmol) prepared above was added and stirred at room temperature for 1 day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain compound E2-1 (15.1 g, yield 78%).

[M + H] = 577.5

<Production of F3-1>

Sodium hydride, NaH (hereinafter), CAS # 7646 with F3 (10 g, 33.7 mmol) prepared previously in anhydrous dimethylacetamide, DMF (hereinafter, CAS # 68-12-2) under nitrogen flow -69-7, 5 g, 35.9 mmol) was added slowly. After stirring at room temperature for 1 hour, H3 (9.95 g, 34.1 mmol) prepared above was added and stirred at room temperature for 1 day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain compound F3-1 (14.1 g, yield 76.3%).

[M + H] = 551.46

<Production of G3-1>

G3 (10 g, 33.7 mmol) prepared previously is sodium hydride, NaH (hereinafter), CAS # 7646 in anhydrous dimethylacetamide (DMF (hereinafter), CAS # 68-12-2) under nitrogen stream -69-7, 5g, 35.9mmol) was slowly added. After stirring at room temperature for 1 hour, H1 (8.27 g, 34.4 mmol) prepared above was added and stirred at room temperature for 1 day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain compound G3-1 (12.98 g, yield 77%).

[M + H] = 501.40

1) Preparation of RM1

Intermediate E2-1 (10 g, 17.3 mmol) and N-phenyl-9H-carbazole-3-yl boronic acid, CAS # 854952-58-2, 5.12 g, 17.5 mmol ) Was dissolved in 200 mL of toluene and 100 mL of ethanol, and potassium carbonate (CAS # 584-08-7, 7.12 g, 51.9 mmol) was dissolved in water, added to the reaction solution, and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0) (tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with EA to obtain an organic layer, and then recrystallized with tetrahydrofuran and ethyl acetate to obtain RM1 (10.35 g, yield 82%).

[M + H] = 739.89

2) Preparation of RM2

Intermediate F3-1 (10 g, 18.2 mmol) and 9H-carbazole (9H-carbazole, CAS # 86-74-8, 3.12 g, 19.3 mmol), sodium-t-butoxide (2.45 g, 25.5 mmol) It was put in toluene, stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (185 mg, 0.20 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare RM2 (8.36 g, yield 71%).

MS [M + H] + = 637.76

3) Preparation of RM3

Intermediate G3-1 (10 g, 19.98 mmol) and 4-dibenzofuranylboronic acid (5.2 g, 20.35 mmol) were dissolved in 200 mL of toluene and 100 mL of ethanol, and then potassium carbonate (CAS). # 584-08-7, 7.12 g, 51.9 mmol) was dissolved in water, added to the reaction solution, and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0) (tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with EA to obtain an organic layer, and then recrystallized with tetrahydrofuran and ethyl acetate to obtain RM3 (9.15 g, yield 78%).

[M + H] = 578.68

Manufacturing example  3: Preparation of RM4 to RM6

<Production of Intermediate J1>

3-bromo-9H-carbazole (15 g, 60.9 mmol), 4-iodobiphenyl (17.9 g, 63.9 mmol), copper in xylene solvent (Cu, CAS # 7440-50-8, 4.15 g, 64 mmol) and potassium phosphate (Potassium phosphate, K ₃ PO ₄ (hereinafter), 20.4 g, 96 mmol) were added together (hereinafter referred to as Ullmann conditions) and heated and stirred for one day. After the reaction was completed, the reaction solution was cooled to room temperature, and then excess EtOH was added to precipitate the compound, extracted with CHCl ₃ , and then recrystallized using water removal and EA to obtain J1 (18.9 g, yield 78%).

MS [M + H] ⁺ = 399.3

<Production of Intermediate J2>

J2 was prepared by the same method as the preparation of the intermediate J1, except that 4-iodoterphenyl was used instead of 4-iodobiphenyl.

MS [M + H] ⁺ = 475.4

<Production of Intermediate J3>

J3 was prepared by the same method as the preparation of the intermediate J1, except that 3-iodobiphenyl was used instead of 4-iodobiphenyl.

MS [M + H] ⁺ = 399.3

<Production of Intermediate K1>

Intermediate J3 (10 g, 25.1 mmol) was dissolved in THF (250 mL), the temperature was lowered to -78 ° C, and then 2.5M n-BuLi (14 mL) was added dropwise, and after 30 minutes, triisobutylborane (25 mL, 35.1 mmol) was added, the mixture was raised to room temperature, and stirred for 1 hour. After adding 1N HCl (300 mL) and stirring for 30 minutes, the layer was separated and the solvent was removed and washed with ethyl acetate to prepare K1 (7.74 g, 85%).

MS [M + H] ⁺ = 364.22

4) Synthesis of RM4

Intermediate J1 (10 g, 25.1 mmol) and (4- (9H-carbazole-9-yl) phenyl) boronic acid (7.4 g, 25.8 mmol) were dissolved in 200 mL of toluene and 100 mL of ethanol, followed by potassium carbonate. , CAS # 584-08-7, 5 g, 30.2 mmol) was dissolved in water, added to the reaction solution, and stirred for 30 minutes. After 30 minutes, tetrakistriphenylphosphine palladium (0) (tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 2 g, 1.5 mmol) was added and further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with EA to obtain an organic layer, and then recrystallized with tetrahydrofuran and ethyl acetate to obtain RM3 (10.97 g, yield 78%).

MS [M + H] ⁺ = 561.7

5) Preparation of RM5

RM5 was prepared in the same manner as in the preparation of RM4, except that intermediate J2 was used instead of intermediate J1.

MS [M + H] ⁺ = 637.8

6) Preparation of RM6

RM6 was prepared in the same manner as in the preparation of RM4, except that intermediate J3 was used instead of intermediate J1 and intermediate K1 was used instead of (4- (9H-carbazol-9-yl) phenyl) boronic acid.

MS [M + H] ⁺ = 637.8

In addition to the compounds prepared above, the structures of the compounds indicated by the symbols in Examples and Comparative Examples below were as follows.

Example  One

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and distilled water was used for Millipore Co. As the product filter, distilled water filtered secondarily was used. After washing the ITO for 30 minutes, the ultrasonic cleaning was repeated 10 times with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On the prepared ITO transparent electrode, P1 described above was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. HTM1, a material that transports holes, is vacuum deposited to a thickness of 100 mm2 to form a hole transport layer, and in turn, HTM1 as a red first host, RM1 as a second host (7: 3 weight ratio) and dopant D1 (2 weight%) Was vacuum-deposited to a thickness of 100 MPa, and then green hosts H2 and H3 (7: 3 weight ratio) and dopant D2 (20% by weight) were vacuum-deposited to a thickness of 400 MPa. Then, an E1 compound was deposited to a thickness of 250 Å to form an electron transport layer, and then E2 and Li (2%) were vacuum-deposited to a thickness of 100 으로 as an n-type charge forming layer, and a cathode of 1,000 Å was deposited to deposit aluminum. To form an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, lithium was 0.2 Å / sec, and aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

Example  2 ~ 42

Prepared in the same manner as in Example 1, except that the materials shown in Tables 1 and 2 were used in the same manner.

Comparative example  One

An organic light emitting device was manufactured in the same manner as in Example 1, except that HT1 was used instead of HTM1 as the hole transport layer and only the green light emitting layer was laminated to the same thickness without laminating the red light emitting layer.

Comparative example  2

In Example 1, the organic light emitting device was manufactured by the same method except that HT1 was used instead of HTM1 for the hole transport layer and the first host.

Comparative example  3

In Comparative Example 2, an organic light emitting device was manufactured in the same manner, except that the ratio of the first host and the second host was 5: 5 instead of 7: 3.

The materials used in Examples 1 to 42 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below.

Example  43

On the ITO transparent electrode prepared in the same manner as in Example 1, P2 was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. HTM1, a material that transports holes, is vacuum deposited to a thickness of 100 형성 to form a hole transport layer, and in turn, HTM1 as a red first host, RM5 (7: 3 weight ratio) and dopant D1 (2 weight percent) as a second host Was vacuum-deposited to a thickness of 100 MPa, and then green hosts H2 and H3 (7: 3 weight ratio) and dopant D2 (20% by weight) were vacuum-deposited to a thickness of 400 MPa. Then, the E1 compound was deposited to a thickness of 250 Å to form an electron transport layer, and then E2 and Li (2%) were vacuum-deposited to a thickness of 100 으로 as an n-type charge forming layer, and aluminum was deposited at a thickness of 1,000 알루미늄 to deposit the cathode. To form an organic light emitting device. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, lithium was 0.2 Å / sec, and aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

Example  44 ~ 84

It was prepared in the same manner as in Example 43, except that the materials described in Tables 3 and 4 were used in the same manner.

Comparative example  4

An organic light-emitting device was manufactured in the same manner as in Example 43, except that HT1 was used instead of HTM1 as the hole transport layer and only the green light-emitting layer was laminated to the same thickness without laminating the red light-emitting layer.

Comparative example  5

An organic light emitting device was manufactured in the same manner as in Example 43, except that HT1 was used instead of HTM1 for the hole transport layer and the first host.

Comparative example  6

In Comparative Example 5, an organic light emitting device was manufactured in the same manner, except that the ratio of the first host and the second host was 5: 5 instead of 7: 3.

The materials used in Examples 43 to 84 and Comparative Examples 4 to 6 are shown in Tables 3 and 4 below.

Example  85

On the ITO transparent electrode prepared in the same manner as in Example 1, the above-mentioned HTM3 was thermally vacuum-deposited to a thickness of 100 Pa to form a hole injection layer, but the compound P3 was doped to a doping concentration of 3%, and the material transporting holes thereon HTM3 is vacuum-deposited to a thickness of 100Å to form a hole transport layer, followed by vacuum deposition of HTM1 as a red first host, RM2 (7: 3 weight ratio) and dopant D1 (2% by weight) as a thickness of 100Å in turn. Then, the green hosts H2 and H3 (weight ratio 7: 3) and dopant D2 (20% by weight) were vacuum deposited to a thickness of 400 MPa. Then, the E1 compound was deposited to a thickness of 250 Å to form an electron transport layer, and then E2 and Li (2%) were vacuum-deposited to a thickness of 100 으로 as an n-type charge forming layer, and a cathode of 1,000 Å was deposited to deposit aluminum. To form an organic light emitting device. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, lithium was 0.2 Å / sec, and aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

Example  86 to 126

An organic light emitting diode was manufactured according to the same method as Example 85 except for using the materials shown in Tables 5 and 6 below.

Comparative example  7

An organic light emitting device was manufactured in the same manner as in Example 85, except that HT1 was used instead of HTM1 as the hole injection layer and the hole transport layer, and only the green light emitting layer was laminated to the same thickness without laminating the red light emitting layer.

Comparative example  8

An organic light emitting device was manufactured in the same manner as in Example 85 except that HT1 was used instead of HTM1 for the hole injection layer, the hole transport layer, and the first host.

Comparative example  9

In Comparative Example 8, an organic light emitting device was manufactured in the same manner, except that the ratio of the first host and the second host was 5: 5 instead of 7: 3.

The materials used in Examples 85 to 126 and Comparative Examples 7 to 9 are shown in Tables 5 and 6.

[White EL element]

Example  127

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and distilled water was used for Millipore Co. As the product filter, distilled water filtered secondarily was used. After washing the ITO for 30 minutes, the ultrasonic cleaning was repeated 10 times with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

<Formation of green light-emitting element>

On the prepared ITO transparent electrode, P1 described above was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. On top of that, HTM1, a material for transporting holes, is vacuum-deposited to a thickness of 100 Å to form a hole transport layer, in turn, HTM1 as a red first host, RM1 as a second host (7: 3 weight ratio), and dopant D1 (2 weight%). Was vacuum-deposited to a thickness of 100 MPa, and then green hosts H2 and H3 (7: 3 weight ratio) and dopant D2 (20% by weight) were vacuum-deposited to a thickness of 400 MPa. Then, the E1 compound was deposited to a thickness of 250 Pa to form an electron transport layer, and then E2 and Li (2%) were vacuum-deposited to a thickness of 100 Pa as an n-type charge forming layer, and then P1 described above as a p-type charge forming layer. Was formed to a thickness of 50 MPa.

<Formation of blue light emitting element>

Blue was formed as a second light emitting unit following the charge forming layer. HTM1, a material that transports holes on the charge forming layer, is vacuum-deposited to a thickness of 900 Å to form a hole transport layer and HT2 is formed as a hole control layer. Vacuum deposited. Then, the E3 compound was formed as an electron transport layer at a thickness of 300 로 in 1: 1 with Alq3, and then sequentially formed by depositing a 10 Å thick lithium fluoride (LiF) and 800 Å thick aluminum to form a cathode to form a white organic EL device. Was prepared. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, lithium fluoride was maintained at 0.2 Å / sec, and aluminum was maintained at a deposition rate of 3 to 7 Å / sec. In addition, the structure of the used material was as follows.

Example  128-142 and Comparative example  10 ~ 12

An organic light emitting diode was manufactured according to the same method as Example 127 except for using the material described in Table 7 below.

The materials used in Examples 127 to 142 and Comparative Examples 10 to 12 are shown in Table 7. In addition, the properties of each organic light emitting device were evaluated, and the results are shown in Table 7.

1: substrate 2: anode
3: hole transport layer 4: light emitting layer
4-1: first light emitting layer 4-2: second light emitting layer
5: electron transport layer 6: cathode
7: hole injection layer 8: electron injection layer

Claims (11)

anode;
Hole transport layer;
A red light emitting layer;
Green light emitting layer;
Electron transport layer; And
A cathode,
The hole transport material included in the hole transport layer and the first host included in the red light emitting layer are represented by the following Chemical Formula 1 or Chemical Formula 2,
The second host included in the red light emitting layer is represented by the following Chemical Formula 3 or Chemical Formula 4,
Single or stacked organic light emitting devices:
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
L ₁ , and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or C _5-60 heteroarylene containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,
L ₃ is a single bond; Or substituted or unsubstituted C _6-60 arylene,
G ₁ , G ₂ , G ₃ and G ₄ are each independently, substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S, or a substituted or unsubstituted monocyclic or polycyclic ring in combination with an adjacent group. To form,
Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl,
R ₁₀₁ to R ₁₀₅ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,
r ₁₀₁ is an integer from 1 to 4,
r ₁₀₂ is an integer from 1 to 3,
r ₁₀₃ is an integer from 1 to 3,
r ₁₀₄ is an integer from 1 to 4,
r ₁₀₅ is an integer from 1 to 4,
When r ₁₀₁ to r ₁₀₅ are each 2 or more, structures in parentheses of 2 or more are the same or different from each other,
a, b and z are integers from 0 to 4,
When a, b, and z are each 2 or more, structures in parentheses of 2 or more are the same or different from each other,
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
Ar ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; A substituted or unsubstituted C _6-60 arylalkyl group; Substituted or unsubstituted C _6-60 arylalkenyl,
R ₁₀₁ to R ₁₀₄ and R ₁₀₆ to R ₁₀₈ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S; Or two of R ₁₀₆ to R ₁₀₈ are bonded to each other to include a substituted or unsubstituted C _6-60 aromatic ring, or any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S Form a C _5-60 heteroaromatic ring,
R ₁₀₉ is hydrogen, substituted or unsubstituted C _6-60 aryl, or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,
L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene;
r ₁₀₁ is an integer from 1 to 4,
r ₁₀₂ is an integer from 1 to 3,
r ₁₀₃ is an integer from 1 to 3,
r ₁₀₄ is an integer from 1 to 4,
r ₁₀₆ is an integer from 1 to 2,
r ₁₀₇ is an integer from 1 to 4,
r ₁₀₈ is an integer from 1 to 4,
When r ₁₀₁ to r ₁₀₄ and r ₁₀₆ to r ₁₀₉ are each 2 or more, structures in two or more parentheses are the same or different from each other.
According to claim 1,
Wherein the hole transport material and the first host are the same or different from each other,
Organic light emitting device.
According to claim 1,
G ₁ , G ₂ , G ₃ and G ₄ are each independently methyl or phenyl,
Organic light emitting device.
According to claim 1,
L ₁ , L ₂ and L ₃ are each independently any one selected from the group consisting of,
Organic light emitting device:

In the above,
R ₁ is each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of N, O and S.
According to claim 1,
Ar ₃ is any one selected from the group consisting of,
Organic light emitting device:

In the above,
R ₈ is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthioxy; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-60 alkyl sulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; Substituted or unsubstituted amines; Substituted or unsubstituted phosphine oxide; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising any one or more hetero atoms selected from the group consisting of N, O and S.
According to claim 1,
R ₁₀₁ to R ₁₀₅ of Formulas 1 and 2 are each independently hydrogen, phenyl, biphenyl, or naphthyl,
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,
The compound represented by Formula 2 is any one selected from the group consisting of,
Organic light emitting device:

According to claim 1,
The compound represented by Formula 3 is any one selected from the group consisting of,
Organic light emitting device:

According to claim 1,
The compound represented by Formula 4 is any one selected from the group consisting of,
Organic light emitting device:

According to claim 1,
The red light emitting layer further comprises a compound represented by the formula (5),
Organic light emitting device:
[Formula 5]

In Chemical Formula 5,
n1 is 1 or 2,
R ' ₁ to R' ₄ are each independently hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,
XY is an auxiliary ligand.

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