KR20210024966A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light-emitting diode. The organic light-emitting diode includes 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 a compound represented by the following formula 1, and the hole transport layer includes the cured product of a polymer including a repeating unit represented by the following chemical formula 2-1 and a repeating unit represented by the following chemical formula 2-2. The present invention can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting diode.

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 multilayer 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, in particular an inkjet process, instead of a conventional deposition process has been developed. 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 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 relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.

In order to solve the above problems, 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 includes a cured product of the compound represented by the following formula (1),

The hole transport layer comprises a cured product of a polymer comprising a repeating unit represented by the following formula 2-1 and a repeating unit represented by the following formula 2-2,

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 including 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 2-1]

In Formula 2-1,

R _'1 to R' ₃ are each independently hydrogen, or C _1-10 alkyl,

L' ₁ is substituted or unsubstituted C _6-60 arylene; -(Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _6-60 arylene)-; -(Substituted or unsubstituted C _6-60 arylene)-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted C _6-60 arylene)-; -(Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _1-10 alkylene)-O-; Or -(substituted or unsubstituted C _6-60 arylene)-(substituted or unsubstituted C _1-10 alkylene)-O-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted Cyclic C _6-60 arylene)-,

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

Ar' ₁ to Ar' ₄ are each independently a substituted or unsubstituted C _{6-60 aryl, or a substituted or unsubstituted C 2-} including any one or more selected from the group consisting of N, O and S ₆₀ heteroaryl or Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are bonded to each other to form a C _6-60 aromatic ring; Or to form _{a C 2-60} heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

Ra is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S,

x is the mole fraction of the repeating unit represented by Formula 2-1 in the polymer,

[Formula 2-2]

In Formula 2-2,

R _'4 to R' ₆ are each independently hydrogen, or C _1-10 alkyl,

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

R'is a photocurable group; Or a thermosetting group,

y is the mole fraction of the repeating unit represented by Formula 2-2 in the polymer.

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.
Figure 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 the understanding of 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be 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, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and 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 heterocycle 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% deuterated 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 multi-layered 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 Formula 1, preferably, L ₁ is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, binapthyldiyl, phenanthrendiyl, spirobifluorenediyl, dimethylfluorenediyl, diphenylflu Orendiyl, or tetraphenylfluorenediyl, 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 substituted with phenoxy, 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 -, -CH ₂ OCH _2- , -N(phenyl)-, or -O(CH ₂ ) ₆ -, and R ₂ is any one selected from the group consisting of:

.

.

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

.

.

Such, the compound represented by Formula 1 may be at least 10% deuterated. Alternatively, the compound represented by Formula 1 may be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated.

In addition, the present invention provides a method for preparing a compound represented by Formula 1 as shown in 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 group,

n1 and n2 are as defined in Chemical Formula 3.

Such, the compound represented by Formula 3 may be at least 10% deuterated. Alternatively, the compound represented by Formula 3 may be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated.

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:

.

.

These ionic compounds may be at least 10% deuterated. Preferably, the ionic compound may be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated.

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 Chemical Formula 1 (or with the compound and/or cationic compound represented by Chemical Formula 3), This will be described later.

(Hole transport layer)

The organic light emitting device according to the present invention comprises a hole transport layer between the hole injection layer and the light emitting layer, and a polymer including a repeating unit represented by Formula 2-1 and a repeating unit represented by Formula 2-2 is used in the hole transport layer. Used as a material. Specifically, the cured product of the polymer is used as a hole transport layer.

Formula 2-1 may be represented by the following Formula 2-1-1:

[Formula 2-1-1]

In Formula 2-1-1,

R _'1 to R' _3, L _'1 to L' _3, Ar _'1 to Ar' ₄ and a description of the Ra is as defined in the formula 2-1.

In the formula 2-1, preferably, R _'1 to R' ₃ is hydrogen, or methyl, each independently, all of which are more preferably hydrogen.

Preferably, L' ₁ is substituted or unsubstituted C _6-20 arylene; -(Substituted or unsubstituted C _6-20 arylene)-O-(substituted or unsubstituted C _6-20 arylene)-; -(Substituted or unsubstituted C _6-20 arylene)-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted C _6-20 arylene)-; -(Substituted or unsubstituted C _6-20 arylene)-O-(substituted or unsubstituted C _1-10 alkylene)-O-; Or -(substituted or unsubstituted C _6-20 arylene)-(substituted or unsubstituted C _1-10 alkylene)-O-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted A cyclic C _6-20 arylene)-, and

More preferably, L′ ₁ is phenylene, -(phenylene)O(phenylene)-, -(phenylene)(CH ₂ ) ₆ (phenylene)-; -(Phenylene)O(CH ₂ ) ₆ O-; Or -(phenylene)CH ₂ OCH ₂ (phenylene)-,

Most preferably, L' ₁ is any one selected from the group consisting of:

.

.

Preferably, L' ₂ and L' ₃ are each independently a single bond; Substituted or unsubstituted C _6-20 arylene, more preferably, L' ₂ and L' ₃ are each independently a single bond or phenylene, and most preferably, L' ₂ and L' ₃ are Each independently, a single bond or 1,4-phenylene.

Preferably, Ar' ₁ to Ar' ₄ each independently include any one or more selected from the group consisting of substituted or unsubstituted _{C 6-20 aryl, or substituted or unsubstituted N, O, and S. Or} C 2-20 heteroaryl, Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are bonded to each other to form a C _6-20 aromatic ring; Or to form _{a C 2-20} heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,

을 형성하고,More preferably, Ar' ₁ to Ar' ₄ are each independently phenyl, biphenylyl, biphenylyl substituted with N,N-diphenylamino, or dimethylfluorenyl, or Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are combined with each other

To form,

을 형성한다:Most preferably, Ar' ₁ to Ar' ₄ are each independently, any one selected from the group consisting of, Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are combined with each other

Forms:

.

.

을 형성한다:Preferably, Ar' ₁ and Ar' ₃ are phenyl or biphenylyl, and Ar' ₂ and Ar' ₄ are any one selected from the group consisting of; Ar' ₁ and Ar' ₂ , and Ar' ₃ and Ar' ₄ are combined with each other

Forms:

.

.

Preferably, Ra is hydrogen, C _1-10 alkyl, or C _6-20 aryl, and more preferably, Ra is hydrogen, methyl, or phenyl.

Preferably, Formula 2-1 is any one selected from the group consisting of repeating units represented by:

.

.

Such, the repeating unit represented by Formula 2-1 may be deuterated by at least 10%. Or the repeating unit represented by Formula 2-1 is at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated. I can.

Meanwhile, the compound represented by Formula 2-1 is derived from a monomer represented by Formula 2-1':

[Formula 2-1']

In Formula 2-1',

R _'1 to R' _3, L _'1 to L' _3, Ar _'1 to Ar' ₄ and a description of the Ra is as defined in the formula 2-1.

The compound represented by Formula 2-1' can be prepared by the same manufacturing method as the following Scheme 2-1-1, and in the compounds represented by Formula 2-1', L' ₁ is -(phenylene)CH _{In the case of 2} OCH ₂ (phenylene)-, for example, it may be prepared by the same production method as in Reaction Scheme 2-1-2, and other compounds may be prepared similarly.

[Scheme 2-1-1]

[Scheme 2-1-2]

2-1-1 In the above scheme, X 'rest was defined except ₁ is as defined above, X' ₁ is a halogen or -OTf, preferably, iodo, bromo, chloro, or -OTf. Step 1 of Scheme 2-1-1 is an amine substitution reaction, and it is preferable to react 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. In addition, step 2 is a Wittig reaction, in which a ketone or an aldehyde is reacted with inylide to form an alkene. The reactor for the Wittig reaction can be changed according to what is known in the art.

2-1-2 In the above scheme, X 'rest was defined except ₂ are as defined above, X' ₂ is a halogen or -OTf, preferably, iodo, bromo, chloro, or -OTf. Step 1 of Reaction Scheme 2-1-2 is a reduction reaction of an aldehyde to which hydrogen is added, and NaBH ₃ , LiAlH _{4 , H 2 in the} presence of a metal catalyst may be used, and a reactor for the aldehyde reduction reaction is known in the art. It can be changed according to the bar. In addition, step 2 is a nucleophilic substitution reaction, which is a kind of substitution reaction in which an alcohol is alkoxylated through the addition of a base to generate a nucleophile and then reacted with a halogen substituent as a leaving group. The reactor for the nucleophilic substitution reaction can be changed as known in the art.

The manufacturing method may be more specific in the manufacturing examples to be described later.

The repeating unit represented by Formula 2-2 includes R', which is a curable reactive group.

Preferably, a photocurable group of R'; Alternatively, the content of R defined in Formula 1 may be applied to the thermosetting group.

Preferably, R _'4 to R' ₆ is hydrogen, or methyl, each independently, all of which are more preferably hydrogen.

Preferably, L' ₄ is a single bond, a substituted or unsubstituted C _6-20 arylene, more preferably a single bond, or phenylene, most preferably a single bond or 1,4-phenyl It's Len.

Preferably, Formula 2-2 is any one selected from the group consisting of repeating units represented by:

.

.

Such, the repeating unit represented by Formula 2-2 may be at least 10% deuterated. Or the repeating unit represented by Formula 2-2 is at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated. I can.

Preferably, at least one of Formula 1, Formula 2-1, and Formula 2-2 may be deuterated by at least 10%.

Meanwhile, the repeating unit of Formula 2-2 is derived from a monomer represented by Formula 2-2':

[Formula 2-2']

'In, R' Formula 2-2 ₄ to R _'6 and L' ₄ are as defined in Formula 2-2.

The compound represented by Chemical Formula 2-2' can be prepared by a manufacturing method as shown in Scheme 2-2 below.

[Reaction Scheme 2-2]

In the above reaction schemes 2-2, X 'rest was defined except ₃ are as defined above, X' ₃ is halogen, preferably bromo, or chloro. Reaction Scheme 2-2 is a Suzuki coupling reaction, in which a palladium catalyst and a base are reacted to prepare a compound represented by Formula 2-2'. The manufacturing method may be more specific in the manufacturing examples to be described later.

The polymer according to the present invention can be prepared by polymerizing the monomer represented by Formula 2-1' and the monomer represented by Formula 2-2'. Preferably, the polymer according to the present invention is a random copolymer containing the repeating unit.

In the polymer according to the present invention, x and y are mole fractions of the repeating unit of Formula 2-1 and the repeating unit of Formula 2-2 in the polymer, and x: y is 0.5 to 0.99: 0.01 to 0.5, preferably , 0.5~0.9: 0.1~0.5. By controlling the reaction molar ratio of the monomer represented by Formula 2-1' and the monomer represented by Formula 2-2', the molar ratio of the polymer may be adjusted.

Preferably, the weight average molecular weight of the polymer is 5,000 to 300,000 g/mol, more preferably 5,000 to 100,000 g/mol.

In this specification, the terms "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" are converted values for standard polystyrene measured using a gel permeation chromatograph (GPC). In the present specification, the term "molecular weight" means a weight average molecular weight unless otherwise specified.

For example, the molecular weight is measured using an Agilent PL-GPC 220 instrument equipped with a 300 mm long PLgel MIXED-B column (Polymer Laboratories). The measurement temperature was 35°C, THF was used as a solvent, and the flow rate was measured at a rate of 1 mL/min. The sample is prepared to a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The values of Mw and Mn are derived with reference to the calibration curve formed using the polystyrene standard. The molecular weight (g/mol) of the polystyrene standard is 2,000/ 10,000/ 30,000/ 70,000/ 200,000/ 700,000/ 2,000,000/ 4,000,000/ 10,000,000.

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 receiving electrons from the cathode and transferring them to the emission layer 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 such a structure, the hole injection layer includes a compound represented by Formula 1, and the hole transport layer includes a repeating unit represented by Formula 2-1, a repeating unit represented by Formula 2-2, and the formula It includes a polymer containing a repeating unit represented by 2-3.

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 such a structure, the hole injection layer includes a compound represented by Formula 1, and the hole transport layer includes a repeating unit represented by Formula 2-1, a repeating unit represented by Formula 2-2, and the formula It includes a polymer containing a repeating unit represented by 2-3.

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.

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 polymer including the repeating unit represented by the formula 2-1 and the repeating unit represented by the formula 2-2.

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.

In addition, 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, benzoyl peroxide, or azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl 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 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 reactant 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, extracted with dichloromethane, and dried over _{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., 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., 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 a1

4-(biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)phenylboronic acid (12 g, 25 mmol), Pd(PPh ₃ ) ₄ (578 mg, 0 5 mmol) and K ₂ CO ₃ (6.9 g, 50 mmol) were added to a round bottom flask and then replaced with nitrogen. 1,3-dibromo-5-fluorobenzene [1,3-dibromo-5-fluorobenzene] (1.26 mL, 10 mmol), THF (Tetrahydrofuran, 40 mL) and H ₂ O (10 mL) were added. Then, the mixture was stirred at 90 °C for 12 hours. After the reaction was completed, extraction was performed with ethyl acetate and water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to remove the organic solvent, and the residue was purified by column to obtain 9.5 g (yield: 98%) of intermediate a1.

Step 2) Preparation of intermediate a2

NaH (60 wt%, 420 mg, 10.5 mmol) was put in a round bottom flask, followed by nitrogen substitution. After adding NMP (N-Methylpyrrolidone, 8.8 mL), it was cooled to 0 °C. A solution in which 3-bromocarbazole (2.6 g, 10.5 mmol) was dissolved in NMP (8.8 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 30 minutes. A solution of intermediate a1 (6.8 g, 7 mmol) dissolved in NMP (17 mL) was added to the reaction mixture, followed by stirring at 220° C. for 2 hours. After the reaction was completed, extraction was performed with ethyl acetate and water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to remove the organic solvent, and the residue was purified by column to obtain 5 g (yield: 60%) of intermediate a2.

Step 3) Preparation of intermediate a3

Intermediate a2 (4 g, 3.35 mmol), 4-formylphenyl boronic acid (750 mg, 5 mmol), Pd(PPh ₃ ) ₄ (196 mg, 0.17 mmol) and K ₂ CO ₃ (1.4 g, 10 mmol) Was placed in a round bottom flask, and then replaced with nitrogen. After adding THF (13.4 mL) and H ₂ O (3.4 mL), the mixture was stirred at 90° C. for 4 hours. After the reaction was completed, extraction was performed with ethyl acetate and water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to remove the organic solvent, and the residue was purified by column to obtain 2.87 g (yield: 70%) of intermediate a3.

Step 4) Preparation of compound 2-1

CH ₃ PPh ₃ Br (1.57g, 4.4 mmol) and THF (12 mL) were put in a round bottom flask, replaced with nitrogen, and cooled to 0 °C. After adding KOtBu (494 mg, 4.4 mmol) to the reaction mixture, it was substituted with nitrogen and stirred at 0° C. for 20 minutes. A solution of intermediate a3 (2.68 g, 2.2 mmol) dissolved in THF (10 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 40 minutes. After the reaction was completed, extraction was performed with ethyl acetate and water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to remove the organic solvent, and the residue was purified by column to obtain 2.25 g (yield: 84%) of compound 2-1.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 8.40 (s, 1H), 8.21 (d, 1H), 7.95 (s, 1H), 7.77 (s, 2H), 7.71 (d, 3H) 7.66- 7.50 (m, 20H), 7.46-7.38 (m, 7H), 7.33-7.20 (m, 17H), 7.11 (d, 2H), 6.78 (dd, 1H), 5.80 (d, 1H), 5.26 (d, 2H), 1.41 (s, 12H)

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

Step 1) Preparation of intermediate b1

Add intermediate a3 (2.44 g, 2 mmol) to a round bottom flask and dissolve in MeOH (5 mL) and THF (5 mL). While maintaining the reaction mixture at room temperature, sodium borohydride (227 mg, 6 mmol) was added little by little, followed by stirring at room temperature for 30 minutes. After the reaction was completed, extraction was performed with ethyl acetate and water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to obtain 2.1 g (yield: 86%) of intermediate b1.

Step 2) Preparation of compound 2-2

Sodium hydride (60 wt%, 112 mg, 2.8 mmol) was put in a round bottom flask and then replaced with a nitrogen atmosphere. After adding anhydrous DMF (3.5 mL), it was cooled to 0 °C. A solution of intermediate b1 (1.71 g, 1.4 mmol) dissolved in anhydrous DMF (3.5 mL) was slowly added to the reaction mixture, followed by stirring at 0° C. for 1 hour. After adding 4-vinylbenzyl chloride (0.39 mL, 2.8 mmol), the temperature was raised to 60 °C and stirred for 4 hours. After completion of the reaction, the mixture was extracted with ethyl acetate water. After collecting the organic layer, the organic layer was dried using _{MgSO 4 and filtered.} The filtrate was dried with a vacuum rotary concentrator to blow away an organic solvent, and the residue was purified by column to obtain 1.22 g (yield: 65%) of compound 2-2.

¹ H NMR (500 MHz, CDCl3): δ 8.40 (s, 1H), 8.21 (d, 1H), 7.95 (s, 1H), 7.77 (s, 2H), 7.71 (d, 3H) 7.66-7.50 (m , 22H), 7.46-7.38 (m, 7H), 7.33-7.20 (m, 19H), 7.11 (d, 2H), 6.69 (dd, 1H), 5.73 (d, 1H), 5.21 (d, 1H), 4.50 (s, 2H), 4.48 (s, 2H), 1.41 (s, 12H)

Preparation Example 2-3: Preparation of Polymer C1

Compound 2-1 (973 mg, 0.8 mmol) and azobisisobutyronitrile (1.3 mg, 0.008 mmol) were put in a round bottom flask and dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. The mixture was stirred at 70° C. for 6 hours. After completion of the reaction, it was diluted with THF (5 mL) and added to ethyl acetate (70 mL). The precipitate is filtered and washed with ethyl acetate. The obtained solid was dried to obtain 620 mg (yield: 64%) of a polymer C1. (Mw=102591, Mn=45941; Number average molecular weight and weight average molecular weight measured by GPC using PS standard using Agilent 1200 series)

Preparation Example 2-4: Preparation of Polymer C2

Compound 2-1 (973 mg, 0.8 mmol) and 3-(4-vinylphenyl)bicyclo[4.2.0]octa-1(6),2,4-triene (41 mg, 0.2 mmol), azobi After placing isobutyronitrile (1.3 mg, 0.008 mmol) in a round bottom flask, dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. The mixture was stirred at 70° C. for 6 hours. After completion of the reaction, it was diluted with THF (5 mL) and added to ethyl acetate (70 mL). The precipitate is filtered and washed with ethyl acetate. The obtained solid was dried to obtain 730 mg (yield: 72%) of a polymer C2. (Mw=90410, Mn=48393; Number average molecular weight and weight average molecular weight measured by GPC using PS standard using Agilent 1200 series)

Preparation Example 2-5: Preparation of Polymer C3

Compound 2-2 (1.07 g, 0.8 mmol) and 3-(4-vinylphenyl)bicyclo[4.2.0]octa-1(6),2,4-triene (41 mg, 0.2 mmol), azobi After placing isobutyronitrile (1.3 mg, 0.008 mmol) in a round bottom flask, dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. The mixture was stirred at 70° C. for 6 hours. After completion of the reaction, it was diluted with THF (5 mL) and added to ethyl acetate (70 mL). The precipitate is filtered and washed with ethyl acetate. The obtained solid was dried to give 689 mg (yield: 62%) of a polymer C3. (Mw=108187, Mn=78944; Number average molecular weight and weight average molecular weight were measured by GPC using PS standard using Agilent 1200 series)

[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, followed by vigorously stirring 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 compound 3- 2 (247 mg, yield 100%) was prepared.

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 the 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 °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

Compound 3-4" (6.2 g, 5.42 mmol), diphenylidoonium chloride (2.57 g, 8.13 mmol), water (50 mL), and acetone (10 mL) were added to a 25 mL round bottom flask and vigorously 30 The organic solvent was extracted using methylene chloride (20 mL * 3), and the solvent was removed, methylene chloride: acetone = 9:1 (v:v) column, compound 3-4 (5.0 g, Yield 65%) was prepared.

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

MS: [M+H] ⁺ = 281 (positive mode)

Preparation Example A: Preparation of Comparative Compound 1

2-Bromo-9,9-diphenyl-9H-fluorene (1.49 g, 3.74 mmol), N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (572 mg. 1.7 mmol), and sodium tert-butoxide (980 mg, 10.2 mmol) were added toluene. The flask containing the reactant 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 Comparative Compound 1 (870 mg, HPLC purity 99.0%).

MS: [M+H] ⁺ = 969

Preparation B: Preparation of Comparative Compound 2

Bromonaphthalene (774 mg, 3.74 mmol), N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (572 mg. 1.7 mmol), and sodium tert-butoxide ( 980 mg, 10.2 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 (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 Comparative Compound 2 (830 mg, HPLC purity 99.0%).

MS: [M+H] ⁺ = 589

Preparation C: Preparation of Comparative Polymer 1

Step 1) Preparation of compound d1'

300 g of 2,2'-dibromo-9,9'-spirobifluorene (50 g, 105.4 mmol, 1.0,eq) and 4-vinylphenylboronic acid (31.2 g, 211 mmol, 2.0 eq) It was dissolved in tetrahydrofuran (THF) and stirred for 10 minutes in a 80°C bath. K ₂ CO ₃ (37.89 g, 274 mmol, 2.60 eq) was dissolved in 300 mL of water and added dropwise for 10 minutes. Pd catalyst (3.66 g, 3.2 mmol, 0.03 eq) was added under reflux. After stirring for 2 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography through n-hexane (n-Hex) and ethyl acetate (EA), and recrystallized with tetrahydrofuran (THF) and ethanol, a white solid compound d1' (22.8 g) was prepared.

MS: [M+H] ⁺ = 496

Step 2) Preparation of monomer d1

Compound d1' (2.4 g, 5.0 mmol, 1.0 eq) and compound d2' (2.82 g, 5.0 mmol, 1.0 eq) were dissolved in 20 ml of 1,4-dioxane (1,4-Dioxane) at 120° C. It was stirred for 30 minutes in a water bath. After dissolving K ₂ CO ₃ (5.10 g, 37 mmol, 1.75 eq) in 40 mL of water, the solution was added dropwise for 10 minutes while maintaining an internal temperature of 90°C. Pd catalyst (0.077 g, 0.15 mmol, 0.03 eq) was added under reflux. After stirring for 1 hour, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried under vacuum. After purification by column chromatography through n-hexane (n-Hex) and dichloromethane (DCM), the monomer d1 was prepared by recrystallization from n-hexane (n-Hex).

MS: [M+H] ⁺ = 854.5

Step 3) Preparation of Comparative Polymer 1

Monomer 1 (500 mg) and azobisisobutyronitrile (AIBN) (1.2 mg) were added to ethyl acetate (EA) and reacted at 25° C. for 12 hours under nitrogen substitution. The precipitate generated after the reaction was filtered to prepare Comparative Polymer 1.

The number average molecular weight of the prepared Comparative Polymer 1 was 37,100 g/mol, and the weight average molecular weight was 78,600 g/mol. At this time, the molecular weight was measured by GPC using PS Standard using the Agilent 1200 series.

[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 washing 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 above, a 2 wt% cyclohexanone solution containing the previously prepared compound 1-2 and compound 3-3 in a weight ratio of 8:2 was spin-coated and heat-treated at 230° C. for 30 minutes to a thickness of 600 Å. A hole injection layer was formed. A toluene solution containing 0.8 wt% of the previously prepared polymer C2 was spin-coated on the hole injection layer to form a hole transport layer having a thickness of 1400 Å.

After being transferred to a vacuum evaporator, the following Compound A and the following Compound B were vacuum-deposited at a weight ratio of 9:1 on the hole transport layer to form a light emitting layer having a thickness of 300 Å. The following Compound C was vacuum-deposited on the emission layer to form an electron injection and transport layer having a thickness of 400 Å. LiF having a thickness of 5 Å and aluminum having a thickness of 1000 Å were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of organic materials 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 ~ Maintained 5 * 10 ^-6 torr.

Examples 2 to 29

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 below were used instead of Compound 1-2, Compound 3-3, and/or Polymer C2.

Comparative Examples 1 to 6

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 below were used instead of Compound 1-2, Compound 3-3, and/or Polymer C2.

Experimental example

For the organic light-emitting device prepared in the above example, 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, LT90 means the time (hr) that the luminance becomes 90% compared to the initial luminance.

HIL Host HIL Dopant HTL Driving voltage
(V) Current efficiency
(cd/A) Power efficiency
(lm/W) LT90
(hr) Example 1 Compound 1-2 Compound 3-3 Polymer C2 4.27 5.98 4.40 530 Example 2 Compound 1-2 Compound 3-3 Polymer C3 4.21 6.11 4.56 545 Example 3 Compound 1-4 Compound 3-3 Polymer C3 4.09 6.20 5.55 610 Example 4 Compound 1-1 Compound 3-1 Polymer C2 4.62 5.40 3.67 450 Example 5 Compound 1-1 Compound 3-1 Polymer C3 4.51 5.42 3.77 435 Example 6 Compound 1-1 Compound 3-2 Polymer C2 4.53 5.42 3.76 449 Example 7 Compound 1-1 Compound 3-2 Polymer C3 4.49 5.44 3.80 460 Example 8 Compound 1-1 Compound 3-3 Polymer C2 4.29 5.69 4.16 510 Example 9 Compound 1-1 Compound 3-3 Polymer C3 4.30 5.75 4.20 521 Example 7 Compound 1-1 Compound 3-4 Polymer C2 4.47 5.52 3.88 490 Example 8 Compound 1-1 Compound 3-4 Polymer C3 4.53 5.56 3.85 475 Example 9 Compound 1-2 Compound 3-1 Polymer C2 4.45 5.45 3.85 482 Example 10 Compound 1-2 Compound 3-1 Polymer C3 4.32 5.48 3.98 477 Example 11 Compound 1-2 Compound 3-2 Polymer C2 4.45 5.61 3.96 502 Example 12 Compound 1-2 Compound 3-2 Polymer C3 4.43 5.65 4.00 514 Example 13 Compound 1-2 Compound 3-4 Polymer C2 4.40 5.80 4.14 531 Example 14 Compound 1-2 Compound 3-4 Polymer C3 4.35 5.76 4.16 520 Example 15 Compound 1-3 Compound 3-1 Polymer C2 4.33 5.41 3.92 462 Example 16 Compound 1-3 Compound 3-1 Polymer C3 4.35 5.35 3.86 453 Example 17 Compound 1-3 Compound 3-2 Polymer C2 4.41 5.69 4.05 493 Example 18 Compound 1-3 Compound 3-2 Polymer C3 4.39 5.56 3.98 478 Example 19 Compound 1-3 Compound 3-3 Polymer C2 4.19 6.02 4.51 550 Example 20 Compound 1-3 Compound 3-3 Polymer C3 4.25 6.05 4.47 526 Example 21 Compound 1-3 Compound 3-4 Polymer C2 4.30 5.78 4.22 511 Example 22 Compound 1-3 Compound 3-4 Polymer C3 4.33 5.82 4.22 531 Example 23 Compound 1-4 Compound 3-1 Polymer C2 4.50 5.60 3.91 497 Example 24 Compound 1-4 Compound 3-1 Polymer C3 4.39 5.53 3.96 503 Example 25 Compound 1-4 Compound 3-2 Polymer C2 4.29 5.79 4.24 509 Example 26 Compound 1-4 Compound 3-2 Polymer C3 4.35 5.85 4.22 513 Example 27 Compound 1-4 Compound 3-3 Polymer C2 4.12 6.15 4.69 617 Example 28 Compound 1-4 Compound 3-4 Polymer C2 4.21 5.98 4.46 520 Example 29 Compound 1-4 Compound 3-4 Polymer C3 4.23 6.01 4.46 556 Comparative Example 1 Compound 1-1 Compound 3-1 Polymer C1 4.89 5.27 4.23 430 Comparative Example 2 Compound 1-2 Compound 3-3 Polymer C1 4.40 5.89 4.79 400 Comparative Example 3 Comparative compound 1 Compound 3-1 Comparative polymer 1 4.9 5.10 3.27 13 Comparative Example 4 Compound 1-1 Compound 3-2 Comparative compound 2 4.7 6.16 4.12 75 Comparative Example 5 Comparative compound 1 Compound 3-3 Polymer C2 4.6 6.2 4.23 52 Comparative Example 6 Comparative compound 1 Compound 3-3 Polymer C3 4.7 6.3 4.21 67

As shown in Table 1, the cured product of the compound represented by Formula 1 was used as a host material for the hole injection layer, and the repeating unit represented by Formula 2-1 and the repeating unit represented by Formula 2-2 were used. The organic light-emitting device of the embodiment in which the cured product of the containing polymer is used as the material for the hole transport layer, and the cured product of the polymer not containing the repeating unit represented by Chemical Formula 2-1 and/or 2-2 is used as the material Compared to the organic light-emitting device, the driving voltage, efficiency, and lifetime characteristics are improved, and in particular, it can be seen that the lifetime is remarkably improved.

In addition, the organic light-emitting device of the embodiment of the present invention uses a compound instead of a polymer as a material for the hole transport layer, or a compound not including a curing group as a host material for the hole injection layer. It shows improved properties, and in particular, it can be seen that the lifespan is remarkably improved.

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 (28)

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 a polymer comprising a repeating unit represented by the following formula 2-1 and a repeating unit represented by the following formula 2-2,
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 including 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 2-1]

In Formula 2-1,
R _'1 to R' ₃ are each independently hydrogen, or C _1-10 alkyl,
L' ₁ is substituted or unsubstituted C _6-60 arylene; -(Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _6-60 arylene)-; -(Substituted or unsubstituted C _6-60 arylene)-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted C _6-60 arylene)-; -(Substituted or unsubstituted C _6-60 arylene)-O-(substituted or unsubstituted C _1-10 alkylene)-O-; Or -(substituted or unsubstituted C _6-60 arylene)-(substituted or unsubstituted C _1-10 alkylene)-O-(substituted or unsubstituted C _1-10 alkylene)-(substituted or unsubstituted Cyclic C _6-60 arylene)-,
L' ₂ and L' ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene including any one or more selected from the group consisting of N, O and S,
Ar' ₁ to Ar' ₄ are each independently a substituted or unsubstituted C _{6-60 aryl, or a substituted or unsubstituted C 2-} including any one or more selected from the group consisting of N, O and S ₆₀ heteroaryl or Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are bonded to each other to form a C _6-60 aromatic ring; Or to form _{a C 2-60} heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
Ra is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S,
x is the mole fraction of the repeating unit represented by Formula 2-1 in the polymer,
[Formula 2-2]

In Formula 2-2,
R _'4 to R' ₆ are each independently hydrogen, or C _1-10 alkyl,
L' ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene,
R'is a photocurable group; Or a thermosetting group,
y is the mole fraction of the repeating unit represented by Formula 2-2 in the polymer.
The method of claim 1,
L ₁ is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, binaphthyldiyl, phenanthrendiyl, spirobifluorenediyl, dimethylfluorenediyl, diphenylfluorenediyl, or tetraphenylfluorenediyl ego,
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 -, -CH ₂ OCH ₂ -, -N(phenyl)-, or -O(CH ₂ ) ₆ -is,
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,
x: y is 0.5 ~ 0.99: 0.01 ~ 0.5,
Organic light emitting device.
The method of claim 1,
L' ₁ is phenylene, -(phenylene)O(phenylene)-, -(phenylene)(CH ₂ ) ₆ (phenylene)-; -(Phenylene)O(CH ₂ ) ₆ O-; Or -(phenylene)CH ₂ OCH ₂ (phenylene)-phosphorus,
Organic light emitting device.
The method of claim 1,
L' ₂ and L' ₃ are each independently a single bond or phenylene,
Organic light emitting device.
The method of claim 1,
Ar' ₁ to Ar' ₄ are each independently phenyl, biphenylyl, biphenylyl substituted with N,N-diphenylamino, or dimethylfluorenyl, or Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are combined with each other

To form,
Organic light emitting device.
The method of claim 1,
Ar' ₁ to Ar' ₄ are each independently, any one selected from the group consisting of, Ar' ₁ and Ar'₂; Or Ar' ₃ and Ar' ₄ are combined with each other

To form,
Organic Light-Emitting Element:

.
The method of claim 1,
Ar' ₁ and Ar' ₃ are phenyl or biphenylyl, and Ar' ₂ and Ar' ₄ are any one selected from the group consisting of; Ar' ₁ and Ar' ₂ , and Ar' ₃ and Ar' ₄ are combined with each other

To form,
Organic Light-Emitting Element:

.
The method of claim 1,
Ra is hydrogen, methyl, or phenyl,
Organic light emitting device.
The method of claim 1,
Formula 2-1 is any one selected from the group consisting of repeating units represented by the following,
Organic Light-Emitting Element:

.
The method of claim 1,
L' ₄ is a single bond or phenylene,
Organic light emitting device.
The method of claim 1,
Formula 2-2 is any one selected from the group consisting of repeating units represented by the following,
Organic Light-Emitting Element:

.
The method of claim 1,
The weight average molecular weight of the polymer is 5,000 to 1,000,000 g/mol,
Organic light emitting device.
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 21,
Each R" ₁ is independently hydrogen, fluoro, or CF ₃ ,
Organic light emitting device.
The method of claim 21,
Ar" ₁ is any one selected from the group consisting of,
Organic Light-Emitting Element:

.
The method of claim 21,
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 21,
Ar" ₂ is any one selected from the group consisting of,
Organic Light-Emitting Element:

.
The method of claim 21,
The compound represented by Formula 3 is any one selected from the group consisting of the following,
Organic Light-Emitting Element:

In the above group,
n1 and n2 are as defined in claim 21.
The method of claim 1,
At least one of Formula 1, Formula 2-1, and Formula 2-2 is at least 10% deuterated,
Organic light emitting device.
The method of claim 21,
Formula 3 is at least 10% deuterated,
Organic light emitting device.

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