KR20210023507A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device. The organic light emitting device comprises: an anode; a hole injection layer; a hole transport layer; a light emitting layer; and a cathode. The present invention may improve the efficiency, low driving voltage, and/or the lifespan characteristics of the organic light emitting device.

Description

Organic light emitting device TECHNICAL FIELD

The present invention relates to an organic light emitting device.

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

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

On the other hand, in recent years, in order to reduce process cost, an organic light emitting device using a solution process, especially an inkjet process, has been developed instead of a conventional deposition process. In the early days, an attempt was made to develop an organic light-emitting device by coating all organic light-emitting device layers by a solution process, but the current technology has limitations, so only HIL, HTL, and EML in the form of a regular structure are carried out as a solution process, and the later process is the existing deposition process. A hybrid process that utilizes is being studied.

Accordingly, the present invention provides a novel organic light-emitting device material that can be used in an organic light-emitting device and at the same time can be used in a solution process, and an organic light-emitting device using the same.

Korean Patent Publication No. 10-2000-0051826

The present invention includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode, the hole injection layer comprises a cured product of the compound represented by the following formula (1), and the hole transport layer is represented by the following formula (2). It provides an organic light emitting device comprising a cured product of the compound:

[Formula 1]

In Formula 1,

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

Ar ₁ is each independently, substituted or unsubstituted C _6-60 aryl,

Ar ₂ is each independently a substituted or unsubstituted C _6-60 aryl,

Each L ₂ is independently a single bond, a substituted or unsubstituted C _1-10 alkylene, or a substituted or unsubstituted C _6-60 arylene,

Each R ₁ is independently hydrogen or deuterium; halogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

n is each independently an integer of 0 to 3,

Each R is independently a photocurable group; Or a thermosetting group,

[Formula 2]

In Chemical Formula 2,

L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted arylene; Or a substituted or unsubstituted heteroarylene,

L' ₃ and L' ₄ are each independently a single bond; Or substituted or unsubstituted alkylene,

L' ₅ is a single bond; Or a substituted or unsubstituted arylene,

R _'1 to R' ₆ are each independently hydrogen, heavy hydrogen; halogen; Nitrile; Silyl group; Boron group; Substituted or unsubstituted alkyl; Substituted or unsubstituted cycloalkyl; Substituted or unsubstituted alkoxy; Substituted or unsubstituted alkenyl; Substituted or unsubstituted aryl; Substituted or unsubstituted alkylamine; Substituted or unsubstituted arylamine; Substituted or unsubstituted heteroarylamine; Substituted or unsubstituted arylheteroarylamine; Or a substituted or unsubstituted heteroaryl,

Ar' ₁ is hydrogen; Substituted or unsubstituted aryl; Substituted or unsubstituted alkylamine; Substituted or unsubstituted arylamine; Substituted or unsubstituted heteroarylamine; Substituted or unsubstituted arylheteroarylamine; Or a substituted or unsubstituted heteroaryl,

X _'1 and X' ₂ is a photocurable group, each independently; Or a thermosetting group,

a1 and a2 are each independently an integer of 0 to 12,

m1 and m2 are each independently an integer of 0 to 5,

m3 and m6 are each independently an integer of 0 to 4,

m4 and m5 are each independently an integer of 0 to 3.

The organic light-emitting device according to the present invention may manufacture a hole injection layer and a hole transport layer by a solution process, and also improve the efficiency, low driving voltage, and/or lifetime characteristics of the organic light-emitting device.

FIG. 1 shows an example of an organic light-emitting device comprising 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 is 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) It shows an example of an organic light-emitting device.

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

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above exemplified substituents. . For example, "a substituent to which two or more substituents are connected" 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 the present 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 ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. 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 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 specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl 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 linear or branched, and the number of carbon atoms 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 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, cycloheptylmethyl, 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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. 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, 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 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 are 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. 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 phenanthrenyl 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,

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

In the present specification, heteroaryl is a heteroaryl containing 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 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, Pyrimidyl group, triazine 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, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ( phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an aralkenyl group, an alkylaryl group, an arylamine group, and an arylsilyl 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 aforementioned alkyl group. In the present specification, the heteroaryl among the heteroarylamines may be described above for heteroaryl. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. 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 above-described heteroaryl 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 the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heteroaryl is not a monovalent group, and the description of the above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

In the present specification, the term "deuterated" means that at least one available hydrogen in each formula is substituted with deuterium. By way of example, being at least 10% deuterated in each formula means that at least 10% of the available hydrogen has been replaced by deuterium. In one example, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% deuterium, or at least 90% deuterium in each formula.

(Positive and negative)

The organic light-emitting device according to the present invention includes an anode and a cathode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode 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); Combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} Conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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

(Hole injection floor)

The organic light-emitting device according to the present invention includes a hole injection layer on the anode, and uses the compound represented by Formula 1 as a material for the hole injection layer, and specifically, the cured product of the compound represented by Formula 1 is hole injected. Use as a layer.

In Chemical Formula 1, preferably, L ₁ is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, vinaphthyldiyl, phenanthrendiyl, spirobifluorenediyl, dimethylfluorenediyl, or diphenyl Fluorenediyl, and L ₁ is unsubstituted or substituted with 1 or 2 C _{1-10 alkyl.}

Preferably, L ₁ is any one selected from the group consisting of:

Preferably, Ar ₁ is each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, or dimethylfluorenyl, and Ar ₁ is unsubstituted, or 1 to 5 deuterium, or halogen Is substituted.

Preferably, Ar ₂ is each independently phenyl, biphenylyl, or naphthyl, and Ar ₂ is unsubstituted or -R; 1 to 5 deuterium; 1 or 2 C _1-10 alkyl; 1 to 5 halogens; C _1-10 alkoxy; C _1-10 alkoxy substituted with C _1-10 alkoxy; C _1-10 haloalkyl; Or it is substituted with phenoxy, and the definition of R is as defined above.

Preferably, _{each L 2} is independently a single bond, butylene, pentylene, hexylene, heptylene, or phenylene.

Preferably, n is 1 and _{each R 1} is independently hydrogen or phenyl.

Preferably, R is -L ₃ -R ₂ and L ₃ is a single bond, -O-, -S-, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, or -CH ₂ OCH ₂ -And R ₂ is any one selected from the group consisting of:

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

At least one hydrogen in Formula 1 may be substituted with deuterium. When hydrogen is replaced with deuterium, the chemical properties of the compound hardly change. However, since the atomic weight of deuterium is twice that of hydrogen, the physical properties of the compound can change.

In addition, the present invention provides a method for preparing a compound represented by Formula 1, such as the following Scheme 1:

[Scheme 1]

In Reaction Scheme 1, the rest except for X are as defined above, and X is halogen and more preferably bromo or chloro. The reaction is an amine substitution reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, the hole injection layer according to the present invention may further include a compound represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

n1 and n2 are each independently an integer of 1 to 3, provided that n1+n2 is 4,

이고, Ar" ₁ is

ego,

R" is a photocurable group; or a thermosetting group,

Each R" ₁ is independently hydrogen, halogen, or C _1-60 haloalkyl,

n3 is an integer from 1 to 4,

이고,Ar" ₂ is

ego,

Each R" ₂ is independently hydrogen, halogen, C _1-60 haloalkyl, a photocurable group, or a thermosetting group,

n4 is an integer from 1 to 5.

Preferably, the photocurable group of R"; or the thermosetting group, the content of R defined in Formula 1 above may be applied.

Preferably, _{each R" 1} is independently hydrogen, fluoro, or CF ₃ .

Preferably, Ar" ₁ is any one selected from the group consisting of:

Preferably, R" ₂ is each independently hydrogen, fluoro, CF ₃ , CF(CF ₃ ) ₂ , CF ₂ CF ₂ CF ₂ CF ₃ , a photocurable group, or a thermosetting group. Or, the content of R defined in Formula 1 may be applied to the thermosetting group.

Preferably, Ar" ₂ is any one selected from the group consisting of:

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

In the above, n1 and n2 are as defined in Chemical Formula 3.

At least one hydrogen in Formula 3 may be substituted with deuterium. When hydrogen is replaced with deuterium, the chemical properties of the compound hardly change. However, since the atomic weight of deuterium is twice that of hydrogen, the physical properties of the compound can change.

In addition, the hole injection layer according to the present invention may further include a cationic compound in addition to the compound represented by Formula 3 above. Examples of the cationic compound are as follows.

Meanwhile, the method of forming the hole injection layer according to the present invention is to prepare a cured product by heat treatment or light treatment of the compound represented by Formula 1 (or with the compound represented by Formula 3 and/or cationic compound), This will be described later.

(Hole transport layer)

The organic light emitting device according to the present invention includes a hole transport layer between the hole injection layer and the light emitting layer, and the compound represented by Formula 2 is used as a material for the hole transport layer. Specifically, a cured product of the compound represented by Chemical Formula 2 is used as a hole transport layer.

In the above formula (2), preferably, X _'1 and X' ₂ is any one selected from the group consisting of to independently:

In the above structure, R _'7 is hydrogen; Or a substituted or unsubstituted alkyl, A _'1 to A' ₃ are each independently a substituted or unsubstituted C _1-6 alkyl.

Preferably, _R'7 is hydrogen; Or substituted or unsubstituted C _1-30 alkyl.

Preferably, _R'7 is hydrogen.

Preferably, the A _'1 to A' ₃ are each independently a methyl group; Ethyl group; Propyl group; Isopropyl group; Butyl group; tert-butyl group; Pentyl group; Or a hexyl group.

Preferably, L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene.

Preferably, L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylylene; Or substituted or unsubstituted naphthylene.

Preferably, L' ₁ and L' ₂ are each independently a single bond; Or it is a pentylene group.

Preferably, L' ₃ and L' ₄ are each independently a single bond; Or substituted or unsubstituted C _1-30 alkylene.

Preferably, L' ₃ and L' ₄ are each independently a single bond; Substituted or unsubstituted methylene; Substituted or unsubstituted ethylene; Substituted or unsubstituted propylene; Substituted or unsubstituted butylene; Substituted or unsubstituted pentylene; Or substituted or unsubstituted hexylene.

Preferably, L' ₃ and L' ₄ are each independently a single bond; Methylene; Ethylene; Propylene; Butylene; Pentylene; Or hexylene.

Preferably, L' ₃ and L' ₄ are methylene.

Preferably, a1 and a2 are each an integer of 0 to 6, or an integer of 1 to 6.

In one embodiment, L' ₃ and L' ₄ are methylene, and a1 and a2 are each an integer of 1-6.

Preferably, L' ₅ is a single bond; Or substituted or unsubstituted C _6-60 arylene.

Preferably, L' ₅ is a single bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylylene; Substituted or unsubstituted fluorenylene; Substituted or unsubstituted terphenylene; Or substituted or unsubstituted naphthylene.

Preferably, L' ₅ is a single bond; Phenylene unsubstituted or substituted with a methyl group or an ethyl group; Biphenylylene unsubstituted or substituted with a methyl group or an ethyl group; It is fluorenylene unsubstituted or substituted with a methyl group or an ethyl group.

Preferably, L' ₅ is a single bond; Phenylene; Biphenylylene; Or 9,9-dimethylfluorenylene.

Preferably, R _'1 to R' ₆ is hydrogen; heavy hydrogen; halogen; Silyl group; Boron group; Substituted or unsubstituted C _1-30 alkyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _2-60 heteroaryl.

Preferably, R _'1 to R' ₆ is hydrogen; heavy hydrogen; halogen; Trimethylsilyl; Trimethylboron; methyl; ethyl; profile; Isopropyl; Butyl; t-butyl; Phenyl; Biphenyl; Terphenyl; Naphthyl; 9,9-dimethylfluorenyl; 9,9-diphenylfluorenyl; Carbazole; N-phenylcarbazole; Dibenzofuranyl; Or dibenzothiophenyl.

In one embodiment, R _'1 to R' ₆ is hydrogen.

Preferably, m1 and m2 are each independently an integer of 1 to 5.

Preferably, m3 and m6 are each independently an integer of 1 to 4.

Preferably, m4 and m5 are each independently an integer of 1 to 3.

When each of m1 to m5 is 2 or more, the substituents in parentheses are the same as or different from each other.

Preferably, Ar' ₁ is hydrogen; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _1-30 alkylamine; Substituted or unsubstituted C _6-60 arylamine; Substituted or unsubstituted C _2-60 heteroarylamine; Substituted or unsubstituted C _{8-60 arylheteroarylamine} ; Or substituted or unsubstituted C _2-60 heteroaryl.

Preferably, Ar' ₁ is hydrogen; Substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted fluorenyl; Substituted or unsubstituted N-phenylcarbazole; Substituted or unsubstituted dibenzofuran; Substituted or unsubstituted dibenzothiophene; Substituted or unsubstituted diphenylamine; Substituted or unsubstituted dibiphenylamine; Substituted or unsubstituted N-phenylcarbazolephenylamine; Substituted or unsubstituted N-phenylcarbazolbiphenylamine; Substituted or unsubstituted fluorenylbiphenylamine; Or substituted or unsubstituted diN-phenylcarbazoleamine.

Preferably, Ar' ₁ is hydrogen; Phenyl; Biphenyl; 9,9-dimethylfluorenyl; N-phenylcarbazole; N-phenylcarbazole substituted with a phenyl group; N-phenylcarbazole substituted with a phenyl group substituted with a t-butyl group; Dibenzofuran; Dibenzothiophene; Diphenylamine; Diphenylamine substituted with a diphenylamine group; Dibiphenylamine; N-phenylcarbazolephenylamine; N-phenylcarbazolebiphenylamine; 9,9-dimethylfluorenylbiphenylamine; Or diN-phenylcarbazoleamine.

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

At least one hydrogen in Formula 2 may be substituted with deuterium. When hydrogen is replaced with deuterium, the chemical properties of the compound hardly change. However, since the atomic weight of deuterium is twice that of hydrogen, the physical properties of the compound can change.

On the other hand, the compound represented by Formula 2 can be prepared by the same method as in Scheme 2 below as an example:

[Scheme 2]

)를 의미한다.In Scheme 2, except for Y, the rest are as defined above, and Y is halogen and more preferably bromo or chloro. In addition, the BPin is boronic acid pinacol ester (Boronic acid pinacol ester,

Means ).

The reaction is an amine substitution reaction or a Suzuki coupling reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction or Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

Meanwhile, the method of forming the hole transport layer according to the present invention is to prepare a cured product by heat treatment or light treatment of the polymer, which will be described later.

(Luminescent layer)

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

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

(Electron transport layer)

The organic light-emitting device according to the present invention may include an electron transport layer on the emission layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

(Electron injection layer)

The organic light emitting device according to the present invention may include an electron injection layer between an electron transport layer (or a light emitting layer) and a cathode, if necessary.

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 for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

(Organic Light-Emitting Element)

The organic light-emitting device according to the present invention may be a normal type organic light-emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention may be an inverted type organic light-emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light-emitting device comprising 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. In this structure, the hole injection layer includes a cured product of the compound represented by Formula 1, and the hole transport layer includes a cured product of the compound represented by Formula 2.

2 is 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). It shows an example of an organic light-emitting device. In this structure, the hole injection layer includes a cured product of the compound represented by Formula 1, and the hole transport layer includes a cured product of the compound represented by Formula 2.

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 above-described materials.

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, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.

In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing 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.

In addition to such a 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.

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

In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

(Coating composition)

Meanwhile, the hole injection layer and the hole transport layer according to the present invention may be formed by a solution process, respectively. To this end, the present invention is a coating composition for forming a hole injection layer comprising a compound represented by Formula 1 and a solvent; And it provides a coating composition for forming a hole transport layer comprising a compound represented by the formula (2) and a solvent.

The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the compound according to the present invention, and examples include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o -Chlorine solvents such as dichlorobenzene; Ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohol and its derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide solvents such as dimethyl sulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate solvents such as butyl benzoate and methyl-2-methoxybenzoate; Tetralin; Solvents, such as 3-phenoxy-toluene, are mentioned. In addition, the above-described solvent may be used alone or in combination of two or more solvents.

Preferably, the solvent of the coating composition for forming the hole injection layer and the solvent of the coating composition for forming the hole transport layer are different from each other.

Further, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy within the above range. In addition, it is preferable that the concentration of the compound according to the present invention in the coating composition is 0.1 wt/v% to 20 wt/v%.

In addition, the coating composition may further include one or two or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide Peroxides such as oxide, bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, and benzoyl peroxide, or azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexyl nitrile. There is an azo system, but it is not limited thereto.

As the photoinitiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxyethoxy ) Phenyl-(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1- Phenyl propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) Acetophenone-based or ketal-based photopolymerization initiators such as oxime; Benzoin ether photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Benzophenone photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, and 4-benzoylphenyl ether; Thioxanthone photopolymerization initiators, such as 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichloro thioxanthone; And ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, Other photoinitiators such as bis(2,4-dimethoxy benzoyl)-2,4,4-trimethyl pentylphosphine oxide, but are not limited thereto.

Moreover, what has a photopolymerization accelerating effect can also be used individually or in combination with the said photoinitiator. For example, triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl benzoic acid (2-dimethylamino), 4,4'-dimethylaminobenzophenone, etc. Not limited.

In addition, the present invention provides a method of forming a hole injection layer and a hole injection layer using the above-described coating composition. Specifically, coating the above-described hole injection layer-forming coating composition on the anode by a solution process; And heat-treating or light-treating the coated coating composition. In addition, coating the above-described hole transport layer-forming coating composition on the hole injection layer by a solution process; And heat-treating or light-treating the coated coating composition.

The solution process is to use the coating composition according to the present invention described above, and means spin coating, dip coating, doctor blading, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In the heat treatment step, the heat treatment temperature is preferably 150 to 230°C. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen. In addition, it may further include evaporating the solvent between the coating step and the heat treatment or light treatment step.

The fabrication of the organic light emitting device according to the present invention described above will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Production Example-HIL Host]

Preparation Example 1-1: Preparation of compound 1-1

Compound 1-1' (1.58 g, 3.74 mmol), N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (572 mg. 1.7 mmol), and sodium tert-butoxide Toluene was added to the flask containing the side (980 mg, 10.2 mmol). The flask containing the reaction product was immersed in an oil bath at 90° C., and then Pd(P(tBu) ₃ ) ₂ (43 mg, 0.085 mmol) was added and returned for 1 hour. Water was added to stop the reaction, followed by extraction with dichloromethane, and then the organic layer was dried with _{MgSO 4.} After removing the organic solvent using a vacuum rotary concentrator, the residue was purified by column to prepare compound 1-1 (950 mg, yield 55%, HPLC purity 99.5%).

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.71 (d, 2H), 7.65 (d, 2H), 7.42 (d, 4H), 7.35 (d, 4H), 7.27-7.20 (m, 18H), 7.17 -7.13 (m, 4H), 7.11-7.06 (m, 14H), 7.03 (t, 2H), 6.70-6.64 (dd, 2H), 5.69 (d, 2H), 5.19 (d, 2H)

Preparation Example 1-2: Preparation of Compound 1-2

Compound 1-2' (1.37 g, 3.03 mmol), N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (464 mg. 1.38 mmol), and sodium tert-butoxide Toluene was added to the flask containing the side (769 mg, 8.3 mmol). The flask containing the reactant was immersed in an oil bath at 90° C., and then Pd(P(tBu) ₃ ) ₂ (36 mg, 0.085 mmol) was added and returned for 1 hour. Water was added to stop the reaction, followed by extraction with dichloromethane, and then the organic layer was dried with _{MgSO 4.} After removing the organic solvent using a vacuum rotary concentrator, the residue was purified by column to prepare compound 1-2 (500 mg, yield 34%, HPLC purity 99.8%).

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.70 (d, 2H), 7.63 (d, 2H), 7.43 (d, 4H), 7.37 (t, 2H), 7.30-7.20 (m, 14H), 7.15 -7.05 (m, 14H), 7.02 (t, 2H), 6.93 (s, 4H), 6.86 (s, 2H), 6.71-6.65 (dd, 2H), 5.70 (d, 2H), 5.20 (d, 2H) ), 2.15 (s, 6H), 1.57 (s, 6H)

Preparation Example 1-3: Preparation of compound 1-3

Compound 1-3' (2.32 g, 5.0 mmol), 2,2'-dibromo-9,9'-spirobi (fluorene) (948 mg. 2.0 mmol), and sodium tert-butoxide (960) mg, 10.0 mmol) was added toluene. The flask containing the reaction product was immersed in an oil bath at 90° C., and then Pd(P(tBu) ₃ ) ₂ (72 mg, 0.14 mmol) was added and returned for 1 hour. Water was added to stop the reaction, followed by extraction with dichloromethane, and then the organic layer was dried with _{MgSO 4.} After removing the organic solvent using a vacuum rotary concentrator, the residue was purified by column to prepare compound 1-3 (1.46 g, yield 59%, HPLC purity 99.2%).

¹ H NMR 500 MHz, CDCl ₃ ): δ 7.74-7.69 (m, 4H), 7.68-7.63 (m, 2H), 7.62-7.56 (m, 2H), 7.39 (td, 2H), 7.33 (ddddd, 4H) ), 7.26 (tdd, 6H), 7.19-7.04 (m, 12H), 7.04-6.90 (m, 14H), 6.85 (d, 2H), 6.76-6.68 (m, 4H), 6.65-6.55 (m, 2H) ), 5.78-5.70 (m, 2H), 5.25 (dq, 2H), 2.16 (s, 6H), 1.57 (s, 6H)

Preparation Example 1-4: Preparation of compound 1-4

Compound 1-4' (1.6 g, 4.2 mmol), N4,N4'-di(naphthalen-1-yl)-[1,1'-biphenyl]-4,4'-diamine (873 mg, 2.0 mmol) , And sodium tert-butoxide (769 mg, 8.0 mmol) into a flask containing toluene and bubbling with nitrogen. The flask containing the reaction product was immersed in an oil bath at 100° C., and then Pd(P(tBu) ₃ ) ₂ (82 mg, 0.16 mmol) was added and returned for 12 hours. Water was added to stop the reaction, followed by extraction with dichloromethane, and then the organic layer was dried with _{MgSO 4.} After removing the organic solvent using a vacuum rotary concentrator, the residue was purified by column to prepare compound 1-4 (1.2 g, yield 53%, HPLC purity 99.1%).

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.90-7.88 (m, 2H), 7.87 (dd, 2H), 7.79-7.75 (m, 2H), 7.64 (dt, 2H), 7.59 (dd, 2H) , 7.49-7.41 (m, 4H), 7.37-7.30 (m, 12H), 7.22-7.11 (m, 8H), 7.09-7.03 (m, 4H), 7.02-6.96 (m, 6H), 6.64 (dd, 2H), 5.67 (dd, 2H), 5.18 (dd, 2H)

[Production Example-HTL]

Preparation Example 2-1: Preparation of Compound 2-1

Step 1) Preparation of Intermediate 2-a

To 500mL 1-neck RBF, 2-bromo-9H-fluoren-9-one (20g, 77.2mmol) was added and dissolved in THF 250ml. 38 ml of 3.0M PhMgBr dissolved in diethyl ether was added in an ice bath. After reacting for about 1 hour, it was quenched with NH ₄ Cl. Water was further added, and the organic layer was extracted using ethyl acetate (EA). The obtained organic layer was dried over MgSO ₄ , concentrated, and purified by column to obtain compound 2-a-1.

2-a-1 (20g, 60mmol) was added to 500mL 1-neck RBF, and 150ml of dichloromethane was added to dissolve it. Triethylsilane (14ml, 90mmol) and trifluoroacetic acid (7ml, 24mmol) were added dropwise and stirred for 24 hours. After being adsorbed by dropping silica gel, compound 2-a-2 was obtained by column with hexane.

In 100 mL 1-neck RBF, 2-a-2 (2.8g, 8.7mmol) and 4-((6-bromohexyl)oxy)benzaldehyde [4-((6-bromohexyl)oxy)benzaldehyde] (2.7g, 9.6mmol), tetrabutylammonium bromide (0.14g, 0.44mmol) was added, and toluene 20ml was added to dissolve. After raising the temperature to about 50°C, degassing was performed for about 30 minutes, and then 7ml of 15wt% NaOH was added and reacted at 60°C for about 18 hours. After the reaction was terminated by adding ammonium chloride, water was added, and the organic layer was extracted using ethyl acetate (EA). The obtained organic layer was dried with MgSO ₄ , concentrated, and recrystallized using MC (methylene chloride) and ethanol to obtain compound 2-a-3.

_{CH 3} PPh ₃ Br (5.4 g, 15.16 mmol) was added to 100 mL 1-neck RBF, and 20 mL of THF was added, followed by stirring. 5.7 ml of 2.5M n-BuLi was slowly added dropwise in an ice bath and reacted for about 30 minutes. Compound 2-a-3 (2.5g, 4.7mmol) dissolved in 20 mL of THF in an ice bath was slowly added and reacted for about 3 hours. After the reaction was terminated with water, more water was added, and the organic layer was extracted using ethyl acetate (EA). The obtained organic layer was dried with Na ₂ SO ₄ , concentrated, and then subjected to flash column to obtain Intermediate 2-a.

Step 2) Preparation of Intermediate 2-b

Benzophenone (20g, 109.8mmol) and 4-bromoaniline (20.8g, 120.7mmol) were added to 1L 1-neck RBF, and 350ml of toluene was added and dissolved. Activated molecular sieve was added and reacted at 120° C. for about 24 hours. The temperature was lowered and the molecular sieve was removed by filtering while washing with ether. The filtrate was concentrated and recrystallized using methanol to obtain compound 2-b-1.

500mL 1-neck RBF (9-phenyl-9H-carbazol-3-yl) boronic acid [(9-phenyl-9Hcarbazol-3-yl)boronic acid] (4.69g, 16.4mmol), 2-b-1 (5g, 14.87mmol), K ₂ CO ₃ (6.16g, 44.6mmol), Pd(PPh ₃ ) ₄ (0.17g, 0.15mmol) was added and N _{2 was} purged. 55 ml of toluene, 25 ml of ethanol, and 25 ml of water were added to dissolve the reactants, respectively, and reflux was installed to raise the temperature to 90° C. and reacted for about 18 hours. After lowering the reaction temperature and adding water, the organic layer was extracted using EA. MgSO ₄ was added to dry it, and charcoal was added to adsorb Palladium, followed by filtering through celite and silica, respectively, and then concentrated. Recrystallized from methanol (Methanol) to obtain compound 2-b-2.

2-b-2 (7.3g, 14.6mmol) was added to 250mL 1-neck RBF, and 50ml of THF was added to dissolve it. About 0.2 ml of 1N HCl was added and stirred at room temperature for 3 hours. K ₂ CO ₃ aqueous solution was added to neutralize the reaction, and the organic layer was extracted using ethylacetate (EA). The reaction solution was concentrated and purified by column to obtain Intermediate 2-b.

Step 3) Preparation of compound 2-1

2-b (3.01g, 5.74mmol) was added to 100mL 1-neck RBF 1, dissolved in 45ml of p-xylene, and then N ₂ degassed. (RBF1) Add 2-a (0.94g, 2.8mmol), NaOtBu (1.34g, 14mmol), Pd(PtBu ₃ ) ₂ (0.07g, 0.14mmol) to 100mL 1-neck RBF and purging _{N 2} I did it. (RBF2) Using a cannula, the solution contained in RBF 1 was put into RBF 2, the reaction temperature was raised to 90°C, and the mixture was stirred for about 1 hour. After lowering the temperature to room temperature, and precipitated in ethanol (Ethanol), the insoluble portion was worked-up using water and EA. The organic layer was extracted, dried with MgSO 4, and palladium was adsorbed using charcoal, and then filtered through celite and silica, respectively. The solution was concentrated and purified by flash column to obtain compound 2-1.

MS: [M+H] ⁺ = 1219.8

Preparation Example 2-2: Preparation of Compound 2-2

Step 1) Preparation of Intermediate 2-c

In 250mL 1-neck RBF, 2-bromo-9H-fluoren-9-one (5g, 19.3mmol), (4-chlorophenyl) boronic acid [(4 -chlorophenyl)boronic acid] (3.3g, 21.2mmol), K ₂ CO ₃ (8g, 57.9mmol), Pd(PPh ₃ ) ₄ (0.22g, 0.193mmol) into toluene, ethanol, Water was dissolved in 60ml, 20ml, and 20ml, respectively. The temperature was raised to 90° C. and refluxed to react for about 2 hours. The temperature was lowered, water was added, and the organic layer was extracted using EA. Dry with MgSO ₄ , palladium was adsorbed and removed using charcoal, and filtered through celite and silica, respectively. The reaction solution was concentrated and recrystallized using methanol to obtain compound 2-c-1.

Thereafter, an intermediate 2-c was obtained in the same manner as in the preparation method of compound 2-a, except that compound 2-c-1 was used instead of 2-bromo-9H-fluoren-9-one.

Step 2) Preparation of compound 2-2

Compound 2-2 was prepared in the same manner as in the preparation method of compound 2-1, except that the intermediate 2-c was used instead of the intermediate 2-a.

MS: [M+H] ⁺ = 1372.8

Preparation Example 2-3: Preparation of Compound 2-3

To 250 mL 1-neck RBF N,N-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'- Biphenyl]-4-amine[N,N-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-(1,1'-biphenyl] -4-amine) (1.64g, 2.86mmol), Intermediate 1 (3g, 5.7mmol), K ₂ CO ₃ (1.58g, 11.44mmol), Pd(PPh ₃ ) ₄ (0.03g, 0.028mmol) and toluene (toluene), ethanol, and water were dissolved in 20ml, 5ml, and 5ml respectively. The temperature was raised to 90° C. and refluxed to react for about 2 hours. The temperature was lowered, water was added, and the organic layer was extracted using EA. Dry with MgSO ₄ , palladium was adsorbed and removed using charcoal, and filtered through celite and silica, respectively. The reaction solution was concentrated and purified by flash column to synthesize compound 2-3.

MS: [M+H] ⁺ = 1206.8

[Production Example-HIL Dopant]

Preparation Example 3-1: Preparation of compound 3-1

Step 1) Preparation of compound 3-1'

Mg (193 mg, 7.92 mmol), I ₂ (4 mg) and THF (10 mL) were added to a 100 mL round bottom flask under a nitrogen atmosphere and stirred for 30 minutes. 4-bromostyrene (1.04 mL, 7.92 mmol) was added, and a water bath at 30° C. was placed under a round bottom flask and stirred for a day. It was confirmed that the reaction solution became black and Mg was dissolved therein. Ether (5 mL) was added to dilute the reaction solution. Tris(pentafluorophenyl)borane (1 g, 3.96 mmol) was dissolved in ether (5 mL) and slowly added to the reaction solution for 30 minutes. The solution was stirred for one day. Na ₂ CO ₃ (0.1 M, 80 mL, 8.0 mmol) was slowly added to the reaction solution. The organic solvent was extracted using ethyl acetate (20 mL × 3) and the residual water was removed with _{MgSO 4.} In order to additionally remove residual water and impurities, it was distilled with benzene using Dean-stock. When about 10 mL of the solvent remained, the solution was cooled and filtered to prepare compound 3-1' (1.6 g, yield 64%).

Step 2) Preparation of compound 3-1

Compound 3-1' (100 mg, 0.16 mmol), distilled water (10 mL), and Ph ₂ ICl (60 mg, 0.19 mmol) were added to a 25 mL round bottom flask and stirred for 1 hour. Acetone (15 mL) was added to the reaction solution to cause precipitation, and the precipitate was filtered and dried to prepare compound 3-1 (140 mg, yield 100%).

MS: [MH] ^- = 615 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

Preparation Example 3-2: Preparation of compound 3-2

Step 1) Preparation of compound 3-2'

To a 250 mL round-bottom flask, methyltriphenyl potassium bromide (13.90 g, 38.91 mmol) and THF (100 mL) were added and stirred at 0°C for 30 minutes. To the reaction solution, n-BuLi (15.6 mL, 38.91 mmol, 2.5 M in Hexane) was slowly added, followed by stirring at 0° C. for 30 minutes. 4-formyl-2,3,5,6-tetrafluoro-1-bromobenzene (5.0 g, 19.47 mmol, in 30 mL THF) was slowly added to the reaction solution at 0°C. The reaction solution was stirred while slowly raising the temperature to room temperature. After 3 hours, ether (100 mL) and a _{saturated solution of NH 4} Cl (400 mL) were added to the reaction solution. The organic solvent was extracted using ether (200 mL×2) and the residual water was removed with _{MgSO 4.} Ethyl acetate:hexane = 1:9 (v:v) by column to prepare compound 3-2' (1.29 g, yield 26%).

Step 2) Preparation of compound 3-2''

Mg (95 mg, 3.92 mmol), THF (10 mL) and I ₂ (4 mg) were added to a 25 mL round bottom flask, followed by stirring. Compound 3-2' (1.0 g, 3.92 mmol) was added to the reaction solution and stirred at room temperature. After 10 hours, the solution turned black and Mg was completely dissolved, and ether (10 mL) and BCl ₃ (1.3 mL, 1.3 mmol, 1M in hexane solution) were added over 30 minutes. After the reaction solution was stirred for one day, Na ₂ CO ₃ (30 mL, 3.0 mmol, 0.1 M in H ₂ O) was added. After extracting the synthetic material with ethyl acetate (10 mL × 3), residual water was removed with _{MgSO 4.} After removing all of the solvent, water was completely removed with Dean-stock using benzene, and the solid was filtered to prepare compound 3-2'' (340 mg, yield 28%).

Step 3) Preparation of compound 3-2

In a 25 mL round bottom flask, compound 3-2'' (200 mg, 0.27 mmol), 1-(4-vinylbenzyl)pyridin-1-ium chloride (69 mg, 0.30 mmol), H ₂ O (10 mL), Methylene chloride (10 mL) was added and stirred vigorously for 30 minutes. The organic solvent was extracted using ether (10 mL × 3) and the residual water was removed with _{MgSO 4.} The solvent was removed and dried in vacuo to prepare compound 3-2 (247 mg, yield 100%).

MS: [MH] ^- = 711 (negative mode)

MS: [M+H] ⁺ = 196 (positive mode)

Preparation Example 3-3: Preparation of compound 3-3

Step 1) Preparation of compound 3-3'

In a 50 mL round bottom flask, add 1-bromo-2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)benzene (2 g, 7.84 mmol) in THF (20 mL). ) And stirred at -78°C for 30 minutes. N-BuLi in hexane (3.45 mL, 8.63 mmol, 2.5 M) was slowly added to the solution and stirred at -78°C for 30 minutes. To the reaction solution, BCl ₃ (2.6 mL, 2.61 mmol, 1 M in hexane solution) was added at -78°C over 15 minutes. The temperature was slowly raised to room temperature and the reaction solution was stirred for one day, and then water (30 mL) was added. After extracting the synthetic material with ethyl acetate (10 mL × 3), all the solvent was removed. Water was completely removed with Dean-stock using benzene, and the solid was filtered to prepare compound 3-3' (800 mg, yield 43%).

Step 2) Preparation of compound 3-3

Compound 3-3' (400 mg, 0.56 mmol), diphenyliodonium chloride (176 mg, 0.56 mmol), water (10 mL), and acetone (10 mL) were added to a 25 mL round bottom flask and vigorously 30 Stir for a minute. Extracted with dichloromethane (10 mL × 3) to remove the solvent and dried to prepare compound 3-3 (552 mg, yield 100%).

MS: [MH] ^- = 711 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

Preparation Example 3-4: Preparation of compound 3-4

Step 1) Preparation of compound 3-4'

Potassium carbonate (10.4 g, 75.3 mmol) was added to a 500 mL round bottom flask, and DMF (200 ml) was added. 2,3,5,6-tetrafluorophenol (10.0 g, 60.22 mmol) was added to the flask and stirred at 60° C. for 30 minutes. 4-vinylbenzyl chloride (7.66 g, 50.18 mmol) was slowly added to the reaction solution, followed by stirring at 60° C. for 16 hours. Then, water (300 mL) and ethyl acetate (200 ml) were added. The organic layer was extracted using ethyl acetate (200 mL × 2), and residual water was removed with _{MgSO 4.} By column with ethyl acetate:hexane = 1:9 (v:v), compound 3-4' (11.2 g, yield 79%) was prepared.

Step 2) Preparation of compound 3-4''

Compound 3-4' (10 g, 35.43 mmol) was added to a 250 ml round bottom flask, and ether (130 ml) was added thereto, followed by stirring. The reaction solution was cooled to -78[deg.] C. and stirred for 30 minutes. n-BuLi (17 ml, 42.52 mmol, 2.5 M in Hexane) was slowly injected over 30 minutes. Then it was stirred for 1 hour. BCl ₃ (8.15 ml, 8.15 mmol, 1 M in Hexane) was slowly added over 30 minutes. The reaction solution was slowly raised to room temperature. After the reaction solution was stirred for one day, water (200 ml) was added. After extracting the synthetic material with ether (100 mL × 3), all the solvent was removed. Thereafter, water was completely removed with Dean-stock using benzene, and the solid was filtered to prepare compound 3-4'' (6.2 g, yield 66%).

Step 3) Preparation of compound 3-4

In a 25 mL round bottom flask, add compound 3-4'' (6.2 g, 5.42 mmol), diphenylidoonium chloride (2.57 g, 8.13 mmol), water (50 mL), and acetone (10 mL) and vigorously Stir for 30 minutes. The organic solvent was extracted using methylene chloride (20 mL × 3) and the solvent was removed. Methylene chloride: acetone = 9:1 (v:v) by column to prepare compound 3-4 (5.0 g, yield 65%).

MS: [MH] ^- = 1135 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

[Device example]

Example 1

The glass substrate on which ITO was deposited to a thickness of 1500 Å was ultrasonically cleaned for 10 minutes using an acetone solvent. Then, the detergent was added to the dissolved distilled water, washed for 10 minutes with ultrasonic waves, and then repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol for 10 minutes, and then dried. The substrate was then transported to a glove box.

On the ITO transparent electrode prepared as described above, a 2 wt% cyclohexanone solution containing the previously prepared compound 1-1 and compound 3-1 in a weight ratio of 8:2 was spin-coated and heat-treated at 230° C. for 30 minutes to a thickness of 60 nm. A hole injection layer was formed. A toluene solution containing 0.8 wt% of Compound 2-1 prepared above was spin-coated on the hole injection layer to form a hole transport layer having a thickness of 140 nm.

After being transferred to a vacuum evaporator, the following Compound A and the following Compound B were vacuum deposited on the hole transport layer at a weight ratio of 9:1 to form a light emitting layer having a thickness of 30 nm. The following Compound C was vacuum-deposited on the emission layer to form an electron injection and transport layer having a thickness of 40 nm. LiF having a thickness of 0.5 nm and aluminum having a thickness of 100 nm were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of organic material was maintained at 0.4 ~ 1.0 Å/sec, the deposition rate of LiF of the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-8 ~ 5×10 ^-6 torr was maintained.

Examples 2 to 9 and Comparative Examples 1 to 2

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Table 1 was used instead of compound 1-1, compound 3-1, and/or compound 2-1, respectively.

In Table 1, compounds 4 and 5 are as follows.

For the organic light emitting device prepared in the above Examples and Comparative Examples, driving voltage, current efficiency, power efficiency, and lifetime were measured at a current density of ^{10 mA/cm 2, and the results are shown in Table 1 below.} In this case, LT95 means the time (hr) when the luminance becomes 95% compared to the initial luminance.

HIL Host HIL Dopant HTL Driving voltage
(V) Current efficiency
(cd/A) Power efficiency
(lm/W) LT95
(hr) Example 1 Compound 1-1 Compound 3-1 Compound 2-1 6.62 4.41 2.10 79 Example 2 Compound 1-1 Compound 3-4 Compound 2-3 6.46 4.20 2.04 92 Example 3 Compound 1-2 Compound 3-1 Compound 2-1 6.62 4.41 2.09 86 Example 4 Compound 1-2 Compound 3-2 Compound 2-2 6.3 4.56 2.28 69 Example 5 Compound 1-2 Compound 3-3 Compound 2-3 6.41 4.91 2.41 108 Example 6 Compound 1-3 Compound 3-3 Compound 2-2 6.63 5.24 2.48 126 Example 7 Compound 1-3 Compound 3-4 Compound 2-3 6.14 5.10 2.61 91 Example 8 Compound 1-4 Compound 3-2 Compound 2-1 6.38 5.41 2.67 84 Example 9 Compound 1-4 Compound 3-3 Compound 2-2 6.89 4.19 1.91 98 Comparative Example 1 Compound 1-1 Compound 3-1 Compound 4 7.43 2.84 1.20 49 Comparative Example 2 Compound 5 Compound 3-3 Compound 2-3 7.52 3.43 1.43 64

As shown in Table 1 above, the device using the compound represented by Formula 1 and the compound represented by Formula 3 as a hole injection layer, and using the compound represented by Formula 2 as a hole transport layer has characteristics of low voltage, high efficiency, and long life. It can be confirmed that it appears.

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

Claims (21)

Including an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode,
The hole injection layer includes a cured product of the compound represented by the following formula (1),
The hole transport layer comprises a cured product of the compound represented by the following formula (2),
Organic Light-Emitting Element:
[Formula 1]

In Formula 1,
L ₁ is substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
Ar ₁ is each independently, substituted or unsubstituted C _6-60 aryl,
Ar ₂ is each independently a substituted or unsubstituted C _6-60 aryl,
Each L ₂ is independently a single bond, a substituted or unsubstituted C _1-10 alkylene, or a substituted or unsubstituted C _6-60 arylene,
Each R ₁ is independently hydrogen or deuterium; halogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
n is each independently an integer of 0 to 3,
Each R is independently a photocurable group; Or a thermosetting group,
[Formula 2]

In Chemical Formula 2,
L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted arylene; Or a substituted or unsubstituted heteroarylene,
L' ₃ and L' ₄ are each independently a single bond; Or substituted or unsubstituted alkylene,
L' ₅ is a single bond; Or a substituted or unsubstituted arylene,
R _'1 to R' ₆ are each independently hydrogen, heavy hydrogen; halogen; Nitrile; Silyl group; Boron group; Substituted or unsubstituted alkyl; Substituted or unsubstituted cycloalkyl; Substituted or unsubstituted alkoxy; Substituted or unsubstituted alkenyl; Substituted or unsubstituted aryl; Substituted or unsubstituted alkylamine; Substituted or unsubstituted arylamine; Substituted or unsubstituted heteroarylamine; Substituted or unsubstituted arylheteroarylamine; Or a substituted or unsubstituted heteroaryl,
Ar' ₁ is hydrogen; Substituted or unsubstituted aryl; Substituted or unsubstituted alkylamine; Substituted or unsubstituted arylamine; Substituted or unsubstituted heteroarylamine; Substituted or unsubstituted arylheteroarylamine; Or a substituted or unsubstituted heteroaryl,
X _'1 and X' ₂ is a photocurable group, each independently; Or a thermosetting group,
a1 and a2 are each independently an integer of 0 to 12,
m1 and m2 are each independently an integer of 0 to 5,
m3 and m6 are each independently an integer of 0 to 4,
m4 and m5 are each independently an integer of 0 to 3.
The method of claim 1,
L ₁ is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, binaphthyldiyl, phenanthrendiyl, spirobifluorenediyl, dimethylfluorenediyl, or diphenylfluorenediyl,
Wherein L ₁ is unsubstituted or substituted with 1 or 2 C _{1-10 alkyl,}
Organic light emitting device.
The method of claim 1,
L ₁ is any one selected from the group consisting of,
Organic Light-Emitting Element:

The method of claim 1,
Ar ₁ is each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, or dimethylfluorenyl,
Ar ₁ is unsubstituted or substituted with 1 to 5 deuterium, or halogen,
Organic light emitting device.
The method of claim 1,
Ar ₂ is each independently phenyl, biphenylyl, or naphthyl,
Ar ₂ is unsubstituted or -R; 1 to 5 deuterium; 1 or 2 C _1-10 alkyl; 1 to 5 halogens; C _1-10 alkoxy; C _1-10 alkoxy substituted with C _1-10 alkoxy; C _1-10 haloalkyl; Or substituted with phenoxy,
The definition of R is as defined in claim 1,
Organic light emitting device.
The method of claim 1,
Each L ₂ is independently a single bond, butylene, pentylene, hexylene, heptylene, or phenylene,
Organic light emitting device.
The method of claim 1,
n is 1,
Each R ₁ is independently hydrogen or phenyl,
Organic light emitting device.
The method of claim 1,
R is -L ₃ -R ₂ ,
L ₃ is a single bond, -O-, -S-, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, or -CH ₂ OCH ₂ -,
R ₂ is any one selected from the group consisting of,
Organic Light-Emitting Element:

The method of claim 1,
The compound represented by Formula 1 is any one compound selected from the group consisting of:
Organic Light-Emitting Element:

The method of claim 1,
Wherein X _'1 and X' ₂ is composed of any one selected from the group consisting of to, each independently,
Organic Light-Emitting Element:

In the above structure,
R _'7 is hydrogen; Or substituted or unsubstituted alkyl,
A _'1 to A' ₃ are each independently a substituted or unsubstituted C _1-6 alkyl.
The method of claim 1,
L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylylene; Or a substituted or unsubstituted naphthylene,
Organic light emitting device.
The method of claim 1,
Ar' ₁ is hydrogen; Substituted or unsubstituted aryl; Substituted or unsubstituted arylamine; Or a substituted or unsubstituted heteroaryl,
Organic light emitting device.
The method of claim 1,
Formula 2 is any one selected from the group consisting of,
Organic Light-Emitting Element:

The method of claim 1,
The hole injection layer further comprises a compound represented by the following formula (3),
Organic Light-Emitting Element:
[Formula 3]

In Chemical Formula 3,
n1 and n2 are each independently an integer of 1 to 3, provided that n1+n2 is 4,
Ar" ₁ is

ego,
R" is a photocurable group; or a thermosetting group,
Each R" ₁ is independently hydrogen, halogen, or C _1-60 haloalkyl,
n3 is an integer from 1 to 4,
Ar" ₂ is

ego,
Each R" ₂ is independently hydrogen, halogen, C _1-60 haloalkyl, a photocurable group, or a thermosetting group,
n4 is an integer from 1 to 5.
The method of claim 14,
Each R" ₁ is independently hydrogen, fluoro, or CF ₃ ,
Organic light emitting device.
The method of claim 14,
Ar" ₁ is any one selected from the group consisting of,
Organic Light-Emitting Element:

Above,
R" is as defined in claim 14.
The method of claim 14,
R" ₂ are each independently hydrogen, fluoro, CF ₃ , CF (CF ₃ ) ₂ , CF ₂ CF ₂ CF ₂ CF ₃ , a photocurable group, or a thermosetting group,
Organic light emitting device.
The method of claim 14,
Ar" ₂ is any one selected from the group consisting of,
Organic Light-Emitting Element:

Above,
R" is as defined in claim 14.
The method of claim 14,
The compound represented by Formula 3 is any one selected from the group consisting of,
Organic Light-Emitting Element:

Above,
n1 and n2 are as defined in claim 14.
The method of claim 1,
At least one of Formula 1 and Formula 2 is at least 10% deuterated,
Organic light emitting device.
The method of claim 14,
Formula 3 is at least 10% deuterated,
Organic light emitting device.

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