KR20220040178A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device. The organic light emitting device includes: an anode; a cathode; a light emitting layer between the anode and the cathode; and a hole transport layer between the anode and the light emitting layer. It is possible to improve the efficiency, low driving voltage and/or lifespan characteristics of the organic light emitting device.

Description

Organic light emitting device

The present invention relates to an organic light emitting device.

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

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

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

Meanwhile, in recent years, organic light emitting devices using a solution process, particularly an inkjet process, have been developed instead of the conventional deposition process in order to reduce process costs. In the early days, all organic light emitting device layers were coated with a solution process to develop an organic light emitting device, but the current technology has limitations, so only HIL, HTL, and EML are processed as a solution process, and the subsequent process is a hybrid that utilizes the existing deposition process. (hybrid) process is being studied.

Accordingly, the present invention provides a novel material for an organic light emitting device 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 is to provide an organic light emitting device.

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

anode,

cathode,

a light emitting layer between the anode and the cathode; and

and a hole transport layer between the anode and the light emitting layer,

The hole transport layer includes a polymer including a repeating unit represented by the following formula (1),

The light emitting layer includes a compound represented by the following formula (2) and a compound represented by the following formula (3),

Organic light emitting device:

[Formula 1]

In Formula 1,

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

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

each R ₁ is independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl, provided that at least one of R ₁ is substituted or unsubstituted C _1-10 alkyl;

R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl;

[Formula 2]

In Formula 2,

X' is a substituted or unsubstituted naphthalene ring fused with two adjacent rings,

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 containing any one or more heteroatoms selected from the group consisting of N, O and S,

B′ ₁ and B′ ₂ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,

Ar' ₁ and Ar' ₂ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

Y′ ₁ and Y′ ₂ are the same as each other and are O or C(R′ _a )(R′ _b ), wherein R′ _a and R′ _b are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-60 alkyl; Or a substituted or unsubstituted C _6-60 aryl,

R′ ₁ to R′ ₄ are all hydrogen; or two adjacent ones of R' ₁ to R' ₄ combine with each other to form a benzene ring, and the remainder is hydrogen,

R' ₅ to R' ₈ are all hydrogen; or two adjacent ones of R' ₅ to R' ₈ combine with each other to form a benzene ring, and the rest are hydrogen,

[Formula 3]

In Formula 3,

Ar" ₁ is C _6-60 aryl substituted with one or more deuterium; or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium; ,

Ar" ₂ is C _6-60 aryl substituted with one or more deuterium; or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium; ,

R" is deuterium,

n" is an integer from 0 to 8;

In the organic light emitting device according to the present invention, the hole transport layer and the light emitting layer can be manufactured by a solution process, and the efficiency, low driving voltage, and/or lifespan characteristics of the organic light emitting device can be improved.

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

Hereinafter, it will be described in more detail to help 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.

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

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

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

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

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

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

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

etc. can be However, the present invention 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 is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, 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), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

(Anode and Cathode)

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

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

(hole injection layer)

The organic light emitting diode according to the present invention may include a hole injection layer between the anode and the light emitting layer, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

(hole transport layer)

The organic light emitting diode according to the present invention includes a hole transport layer between the anode (or hole injection layer) and the light emitting layer, and in particular, the hole transport layer includes a polymer including a repeating unit represented by Formula 1 above.

In Formula 1, preferably L is each independently substituted or unsubstituted C _6-12 arylene. More preferably, each L is independently phenylene or biphenyldiyl. Preferably, L are equal to each other.

Preferably, each Ar is independently substituted or unsubstituted C _6-12 aryl. More preferably, each Ar is independently phenyl or biphenylyl, wherein Ar is unsubstituted or substituted with C _1-10 alkyl, or N(C _6-60 aryl) ₂ .

Preferably, Ar is biphenylyl, wherein Ar is unsubstituted or substituted with methyl, ethyl, propyl, or N(phenyl) ₂ .

Preferably, Ar are identical to each other.

Preferably, each R ₁ is independently straight-chain C _1-6 alkyl. More preferably, each R ₁ is independently methyl, ethyl, propyl, butyl, pentyl, or hexyl.

Preferably, each R ₂ is independently straight-chain C _1-4 alkyl. More preferably, each R ₂ is independently methyl.

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

In addition, the repeating unit represented by the formula (1) is derived from a compound represented by the following formula (1-1).

[Formula 1-1]

In Formula 1-1, definitions other than X are the same as defined above, and X is halogen and more preferably bromo or chloro.

The compound represented by Chemical Formula 1-1 may be prepared by the preparation method shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, definitions other than X are the same as defined above, and X is halogen and more preferably bromo or chloro.

Steps 1-1 and 1-2 in Scheme 1 are amine substitution reactions, respectively, and are reactions prepared by reacting with a palladium catalyst in the presence of a base. The reactive group for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

The polymer may further include a repeating unit represented by the following Chemical Formula 1':

[Formula 1']

In Formula 1',

L' is each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,

Z is C, Si, N, Si (phenyl), or an n-valent substituted or unsubstituted C _6-60 aromatic ring,

n is 3 or 4, with the proviso that if Z is C or Si then n is 4 and if Z is N or Si(phenyl) then n is 3,

* indicates the point of attachment within the polymer.

The repeating unit represented by Formula 1' is a branched repeating unit, and when included in the polymer structure according to the present invention, the polymer structure is branched to improve solubility in a solvent.

Preferably, each L' is independently a single bond; or phenylene.

Preferably, Z is C, N, Si, or trivalent benzene.

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

In addition, the repeating unit represented by Formula 1' is derived from a compound represented by Formula 1'-1 below.

[Formula 1'-1]

In Formula 1'-1, definitions other than X' are the same as defined above, and X' is halogen, and more preferably bromo or chloro.

The polymer may further include a repeating unit represented by the following formula (1):

[Formula 1"]

In Formula 1",

Ar" is substituted or unsubstituted C _6-60 aryl,

* indicates the point of attachment within the polymer.

The terminal group represented by Formula 1" is an aromatic cyclic terminal group, and when included in the polymer structure according to the present invention, solubility in a solvent may be improved.

Preferably, Ar″ is phenyl or biphenylyl, wherein Ar″ is unsubstituted or substituted with C _1-10 alkyl, a photocurable group, or a thermosetting group.

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

.

.

In addition, the repeating unit represented by Formula 1" is derived from a compound represented by Formula 1"-1 below.

[Formula 1"-1]

In Formula 1"-1, definitions other than X" are the same as defined above, and X" is halogen and more preferably bromo or chloro.

The polymer according to the present invention may be prepared by polymerizing the monomer represented by Chemical Formula 1-1. In addition, the polymer according to the present invention may be prepared by polymerizing the above-described monomer represented by Formula 1-1 and the monomer represented by Formula 1'-1. In addition, the polymer according to the present invention can be prepared by polymerizing the above-mentioned monomer represented by Formula 1-1, the monomer represented by Formula 1'-1, and the monomer represented by Formula 1"-1. Preferably , The polymer according to the present invention is a random copolymer including the repeating unit.

In the polymer according to the present invention, when the repeating unit of Chemical Formula 1' is included, preferably, 10 to 50 moles of the repeating unit of Chemical Formula 1' relative to 100 moles of the repeating unit represented by Chemical Formula 1 is included. More preferably, 15 moles or more, 20 moles or more, 25 moles or more, or 30 moles or more of the repeating unit of Formula 1' relative to 100 moles of the repeating unit represented by Formula 1 are included; 45 moles or less, 40 moles or less, or 35 moles or less.

In the polymer according to the present invention, when the repeating unit of Formula 1" is included, preferably, the amount of the repeating unit of Formula 1" is 20 to 65 moles relative to 100 moles of the repeating unit represented by Formula 1 above. More preferably, 25 moles or more, 30 moles or more, 35 moles or more, or 40 moles or more are included in the repeating unit of Formula 1" relative to 100 moles of the repeating unit represented by Formula 1; 60 moles or less, or 55 moles included below.

In addition, by adjusting the reaction molar ratio of the monomer represented by Formula 1-1, the monomer represented by Formula 1′-1, and/or the monomer represented by Formula 1″-1, the molar ratio of the polymer can be adjusted. .

Preferably, the polymer has a weight average molecular weight (Mw; g/mol) of 3,000 to 1,000,000, more preferably 10,000 or more, 20,000 or more, 30,000 or more, 40,000 or more, 50,000 or more, 60,000 or more, 70,000 or more, or 80,000 or more. more than; 500,000 or less, 400,000 or less, 300,000 or less, 200,000 or less, or 150,000 or less.

Preferably, the molecular weight distribution (PDI; Mw/Mn) of the polymer is 1 to 10, more preferably 1.5 or more, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, or 2.5 or more; 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, or 5.0 or less.

(Light emitting layer)

The light emitting layer of the organic light emitting device according to the present invention includes a host and a dopant, and in particular, the compound represented by Formula 2 as a dopant and the compound represented by Formula 3 as a host.

Formula 2 may be represented by Formula 2-1 or Formula 2-2 below:

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, L′ ₁ , L′ ₂ , B′ ₁ , B′ ₂ , Ar′ ₁ , Ar′ ₂ , Y′ ₁ , Y′ ₂ , and R′ ₁ to R′ ₈ is as defined in Formula 2.

Preferably, L′ ₁ and L′ ₂ are both single bonds.

Preferably, B' ₁ and B' ₂ are each independently a single bond, phenylene, biphenylene, or naphthalenediyl;

The B′ ₁ and B′ ₂ are unsubstituted or substituted with one or more C _1-10 alkyl. In this case, C _1-10 alkyl may be methyl.

Preferably, B′ ₁ and B′ ₂ are identical to each other and are a single bond, phenylene, dimethylphenylene, biphenylene, or naphthalenediyl.

Preferably, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenyl, naphthyl, benzofuranyl, dimethylfluorenyl, or dibenzofuranyl;

and Ar' ₁ and Ar' ₂ are unsubstituted or substituted with one or more C _1-10 alkyl. In this case, C _1-10 alkyl may be methyl or t-butyl.

Preferably, Ar′ ₁ and Ar′ ₂ are identical to each other and are phenyl, t-butylphenyl, biphenyl, naphthyl, benzofuranyl, dimethylfluorenyl, or dibenzofuranyl.

Preferably, Y′ ₁ and Y′ ₂ are identical to each other and are C(R′ _a )(R′ _b ), wherein R′ _a and R′ _b are each independently hydrogen; heavy hydrogen; or substituted or unsubstituted C _1-60 alkyl.

Preferably, Y′ ₁ and Y′ ₂ are identical to each other and are O or C(CH ₃ ) ₂ .

In one preferred embodiment, Y′ ₁ and Y′ ₂ are O; R' ₁ to R' ₈ are all hydrogen.

및

부분은 하기 중 어느 하나로 표시될 수 있다:In another preferred embodiment, Y′ ₁ and Y′ ₂ are C(CH ₃ ) ₂ ; adjacent two of R' ₁ to R' ₄ combine with each other to form a benzene ring, and the remainder is hydrogen; Adjacent two of R' ₅ to R' ₈ combine with each other to form a benzene ring, and the remainder is hydrogen. In this case, Formula 2

and

A portion may be represented by any of the following:

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

Meanwhile, the compound represented by Chemical Formula 2 may be prepared by the same method as in Scheme 2 below.

[Scheme 2]

In Scheme 2, definitions other than X' _a are the same as defined above, X' _a is halogen, and preferably X' _a is bromo, chloro, or iodo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. In addition, when the reactants of step 1 and step 2 are the same, step 2 may be omitted. The manufacturing method may be more specific in Preparation Examples to be described later.

In Formula 3, preferably, Ar" ₁ is naphthyl substituted with one or more deuterium, or naphthylphenyl substituted with one or more deuterium. In this case, the naphthyl may be substituted with 1 to 7 deuterium. and naphthylphenyl may be substituted with 1 to 11 deuterium.

Preferably, Ar" ₂ is naphthylphenyl substituted with one or more deuterium, or dibenzofuranyl substituted with one or more deuterium, wherein said naphthylphenyl may be substituted with 1 to 11 deuterium; Dibenzofuranyl may be substituted with 1 to 7 deuterium.

Preferably, the deuterium substitution rate of Formula 3 is 60 to 100%. The 'deuterium substitution rate' refers to the number of substituted deuterium relative to the total number of hydrogens that may exist in Formula 3 above. Preferably, the deuterium substitution rate of Formula 3 is 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 99% or less, 98% or less, 97% or more. or less, 96% or less, 95% or less, 94% or less, 93% or less, or 92% or less.

Preferably, the formula 3 is represented by any one of the following formulas 3-1 to 3-4:

[Formula 3-1]

In Formula 3-1,

o+p+q+r is an integer from 21 to 23;

[Formula 3-2]

In Formula 3-2,

o+p+q+r is an integer from 21 to 23;

[Formula 3-3]

In Formula 3-3,

o+p+q is an integer from 14 to 22, preferably an integer from 17 to 20,

[Formula 3-4]

In Formula 3-4,

o+p+q+r is an integer of 20-26, Preferably it is an integer of 21-23.

Meanwhile, the compound represented by Formula 3 may be prepared by treating the non-deuterated compound represented by Formula 3 with a deuterated solvent, such as benzene-D6, in the presence of an H/D exchange catalyst.

The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, in the light emitting layer according to the present invention, the weight ratio of the compound represented by Formula 2 to the compound represented by Formula 3 is preferably 1 to 10: 99 to 90.

(electron transport layer)

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. 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 may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

(electron injection layer)

The organic light emitting diode according to the present invention may include an electron injection layer between the electron transport layer (or the light emitting layer) and the 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 on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

(organic light emitting 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. Also, 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 the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

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

The organic light emitting diode according to the present invention may be manufactured using 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 stacking 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 conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming an organic 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 this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

(Coating composition)

On the other hand, the hole transport layer and the light emitting layer according to the present invention can be formed by a solution process, respectively.

To this end, the present invention provides a coating composition for forming a hole transport layer comprising a polymer including a repeating unit represented by the formula (1). In addition, the present invention provides a coating composition for forming a light emitting layer comprising the compound represented by the formula (2) and the compound represented by the formula (3).

Each solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the polymer or compound according to the present invention, and for example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chloroform chlorine-based solvents such as benzene and o-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, and 1,2-hexanediol alcohols and derivatives thereof; 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 butylbenzoate and methyl-2-methoxybenzoate; tetralin; and solvents such as 3-phenoxy-toluene. In addition, the above-mentioned solvents may be used alone or as a mixture of two or more solvents.

In addition, the viscosity of each coating composition is preferably 1 cP to 10 cP, and coating is easy in the above range. In addition, the concentration of the polymer or compound according to the present invention in each coating composition is preferably 0.1 wt/v% to 20 wt/v%, respectively.

In addition, the present invention provides a method of forming a hole transport layer and a light emitting layer using the above-described coating composition. Specifically, coating the above-described coating composition for forming a light emitting layer in a solution process; and heat-treating the coated coating composition.

The solution process uses the coating composition according to the present invention as described above, and refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The heat treatment temperature in the heat treatment step is preferably 150 to 230 ℃. 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, the step of evaporating the solvent between the coating step and the heat treatment step may be further included.

The above-described manufacturing 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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Production Example 1]

Preparation 1-1: Synthesis of compound H1

With reference to Synthesis Example 1 of KR 2016-0131947, compound H1 was prepared by the following method.

Compounds M1 (0.712 mmol), M2 (0.264 mmol), and XL1 (0.343 mmol) were added to a scintillation vial and dissolved in 11 mL of toluene. Bis (1,5-cyclooctadiene) nickel (0) (2.42 mmol) was charged to a clean and dry 50 mL Schlenk tube. 2,2'-dipyridyl (2.42 mmol) and 1,5-cyclooctadiene (2.42 mmol) were weighed into a scintillation vial and dissolved in 5.5 mL of N,N'-dimethylformamide and 11 mL of toluene. dissolved. The solution was added to a Schlenk tube, which was then inserted into an aluminum block and heated to an internal temperature of 50°C. The catalyst system was held at 50° C. for 30 minutes. A solution of the monomer in toluene was added to the Schlenk tube and the tube sealed.

The polymerization mixture was stirred at 50 °C for 180 min. The Schlenk tube was then removed from the block and allowed to cool to room temperature. The contents were poured into HCl/methanol (5 % v/v, concentrated HCl). After stirring for 45 minutes, the polymer was collected by vacuum filtration and dried under high vacuum. The polymer was dissolved in toluene (1% wt/v) and passed through a column containing basic aluminum oxide (6 grams) layered on silica gel (6 grams). The polymer/toluene filtrate was concentrated (2.5% wt/v toluene) and triturated with 3-pentanone. The toluene/3-pentanone solution was decanted from the semi-solid polymer, which was then dissolved in 15 mL of toluene and poured into stirring methanol to form copolymer H1 (a1:b1:e1 molar ratio = 54:20:26, Mw = 130,700, [η] = 47 ml/g) was obtained in 60% yield.

The weight average molecular weight (Mw) and intrinsic viscosity ([η]) of the prepared copolymer were measured using a multi-angle light scattering detector and an in-line viscometer as a detector, and using THF as a solvent, gel permeation chromatography (GPC).

Preparation 1-2: Synthesis of compound H2

Copolymer H2 (a1:b1:e2 molar ratio = 52: in the same manner as in Preparation Example 1-1 except that the compounds M1 (0.686 mmol), M2 (0.264 mmol), and XL2 (0.369 mmol) were used as monomer 20:28, Mw = 191,700, [η] = 54 ml/g) was prepared.

Preparation 1-3: Synthesis of compound H3

Copolymer H3 (a1:b1:e1 molar ratio = 58:20:22) in the same manner as in Preparation Example 1-1, except that compounds M1 (0.765 mmol), M2 (0.264 mmol), and XL1 (0.290 mmol) were used. , Mw = 199,000, [η] = 56 ml/g) was prepared.

[Production Example 2]

Preparation Example 2-1: Preparation of Intermediate 1-4

1) Preparation of Intermediate 1-1

1,5-dibromonaphthalene-2,6-diol (25g, 79mmol), tert-Butyldimethylsilyl chloride (35.5g, 236mmol), imidazole (21g, 315mmol) was added, and 300mL of dimethylformamide was added. The mixture was stirred at room temperature for about 3 hours, and when the reaction was completed, the organic layer was separated by extraction with ethyl acetate and water. The organic layer was concentrated under reduced pressure, followed by precipitation with ethanol, and then filtered to obtain Intermediate 1-1 (40 g, yield 94%).

2) Preparation of Intermediate 1-2

Intermediate 1-1 (15.6g, 29mmol), (4-chloro-2-fluorophenyl)boronic acid (10g, 57mmol) was added to a 500 mL round-bottom flask in a nitrogen atmosphere, and 150mL of toluene was added. While stirring at room temperature, sodium carbonate (13g, 120mmol), Aliquat 336 (0.58g, 1.43mmol) and 60mL of water were added and bubbled with nitrogen. Pd(Amphos)Cl2 (0.04g, 0.06mmol) was added, the temperature of the reactor was raised to 90 ^o C, and the mixture was stirred for 4 hours. Upon completion of the reaction, the temperature was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain Intermediate 1-2 (7.7 g, yield 41%).

3) Preparation of Intermediate 1-3

Intermediate 1-2 (7.7 g, 12 mmol) and 100 mL of dimethylformamide were placed in a 250 mL round-bottom flask in a nitrogen atmosphere. An ice bath was installed, and NaH (1.4 g, 36 mmol) was slowly added at 0 ^o C and stirred at room temperature. When the reaction was completed, water was added to quench the reaction, and the organic layer was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain Intermediate 1-3 (4.8 g, yield 96%).

4) Preparation of Intermediate 1-4

Intermediate 1-3 (6.6 g, 16 mmol), potassium carbonate (5.5 g, 40 mmol) and 100 mL of methylpyrrolidone were placed in a 250 mL round-bottom flask under a nitrogen atmosphere. The temperature was raised to about 200 ^o C and reacted for 24 hours. When the reaction was completed, the reaction was lowered to room temperature, washed with water, tetrahydrofuran, and ethanol in that order, and filtered to obtain Intermediate 1-4 (4.5 g, yield 75%).

Preparation Example 2-2: Preparation of Intermediate 1-5

Intermediate 1-5 in the same manner as in Preparation Example 5, except that 3,7-dibromonaphthalene-2,6-diol was used instead of 1,5-dibromonaphthalene-2,6-diol was prepared.

Preparation 2-3: Preparation of Intermediate 2-1

9-bromo-11,11-dimethyl-11H-benzo[a]fluorene (9.4g, 29mmol), 4-(tert-butyl)aniline (4.5ml, 29mmol), sodium tert- Butoxide (8.3 g, 86 mmol) and bis (tri-tert-butylphosphine) palladium (0.15 g, 0.3 mmol) were added, and toluene 100 mL was added. The temperature of the reactor was raised to 80 ^o C and stirred for 24 hours. When the reaction was completed, the temperature was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain Intermediate 2-1 (7.8 g, 20 mmol).

Preparation Example 2-4: Preparation of Intermediate 2-2

Intermediate 2-2 was prepared in the same manner as in Preparation Example 2-3, except that [1,1'-biphenyl]-4-amine was used instead of 4-(tert-butyl)aniline.

Preparation Example 2-5: Preparation of Intermediate 2-3

Intermediate 2-3 was prepared in the same manner as in Preparation Example 2-3, except that 6-(benzofuran-2-yl)naphthalen-2-amine was used instead of 4-(tert-butyl)aniline.

Preparation Example 2-6: Preparation of Intermediate 2-4

In Preparation Example 2-5, the same method was used except that 2-bromo-11,11-dimethyl-11H-benzo[b]fluorene was used instead of 9-bromo-11,11-dimethyl-11H-benzo[a]fluorene. Intermediate 2-4 was prepared.

Preparation Example 2-7: Preparation of Intermediate 2-5

In the same manner as in Preparation Example 2-5, except that 9-bromo-7,7-dimethyl-7H-benzo[c]fluorene was used instead of 9-bromo-11,11-dimethyl-11H-benzo[a]fluorene. Intermediate 2-5 was prepared.

Preparation Example 2-8: Preparation of Intermediate 2-6

3-bromodibenzo[b,d]furan (29mmol), 9,9-dimethyl-9H-fluoren-2-amine (29mmol), sodium tert-butoxide (86mmol), bis(tri -tert-butylphosphine)palladium (0.3mmol) was added, and toluene 100mL was added. The temperature of the reactor was raised to 80 ^o C and stirred for 24 hours. When the reaction was completed, the temperature was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain Intermediate 2-6.

Preparation Example 2-9: Preparation of Intermediate 2-7

Intermediate 2-7 was prepared in the same manner as in Preparation Example 2-5, except that 3-bromodibenzo[b,d]furan was used instead of 9-bromo-11,11-dimethyl-11H-benzo[a]fluorene.

Preparation Example 2-10: Preparation of Compound 1

Intermediate 1-4 (0.75 g, 2 mmol), Intermediate 2-1 (1.7 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain Compound 1.

MS[M+H] ⁺ = 1086.51

Preparation 2-11: Preparation of compound 2

Intermediate 1-4 (0.75 g, 2 mmol), Intermediate 2-2 (1.8 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain Compound 2.

MS[M+H] ⁺ = 1126.45

Preparation Example 2-12: Preparation of compound 3

Intermediate 1-4 (0.75 g, 2 mmol), Intermediate 2-3 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 3.

MS[M+H] ⁺ = 1307.47

Preparation 2-13: Preparation of compound 4

Intermediate 1-4 (0.75 g, 2 mmol), Intermediate 2-4 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 4.

MS[M+H] ⁺ = 1307.47

Preparation Example 2-14: Preparation of compound 5

Intermediate 1-4 (0.75 g, 2 mmol), Intermediate 2-5 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 5.

MS[M+H] ⁺ = 1307.47

Preparation Example 2-15: Preparation of compound 6

Intermediate 1-5 (0.75 g, 2 mmol), Intermediate 2-1 (1.7 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 6.

MS[M+H] ⁺ = 1086.51

Preparation Example 2-16: Preparation of compound 7

Intermediate 1-5 (0.75 g, 2 mmol), Intermediate 2-2 (1.8 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 7.

MS[M+H] ⁺ = 1126.45

Preparation Example 2-17: Preparation of compound 8

Intermediate 1-5 (0.75 g, 2 mmol), Intermediate 2-3 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 8.

MS[M+H] ⁺ = 1307.47

Preparation Example 2-18: Preparation of compound 9

Intermediate 1-5 (0.75 g, 2 mmol), Intermediate 2-4 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 9.

MS[M+H] ⁺ = 1307.47

Preparation Example 2-19: Preparation of compound 10

Intermediate 1-5 (0.75 g, 2 mmol), Intermediate 2-5 (2.2 g, 4.4 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.05 g, 0.1) in a 250 mL flask under nitrogen atmosphere mmol), sodium tert butoxide (0.4 g, 4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 10.

MS[M+H] ⁺ = 1307.47

Preparation Example 2-20: Preparation of compound 11

In a 250 mL flask under nitrogen atmosphere, Intermediate 1-4 (2 mmol), Intermediate 2-6 (4.4 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.1 mmol), sodium tertbutoxide (4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 11.

MS[M+H] ⁺ = 1054.38

Preparation 2-21: Preparation of compound 12

In a 250 mL flask under nitrogen atmosphere, Intermediate 1-4 (2 mmol), Intermediate 2-7 (4.4 mmol), bis(tri-tert-butylphosphine)palladium (0) (0.1 mmol), sodium tertbutoxide (4.4 mmol) and toluene (50 mL) were added and stirred at 100° C. for 5 hours. Upon completion of the reaction, the reaction was cooled to room temperature, and the material was extracted using dichloromethane and water, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography separation using normal hexane and dichloromethane, and then the solvent was removed to obtain compound 12.

MS[M+H] ⁺ = 1154.34

[Production Example 3]

Preparation 3-1: Preparation of compound AD

1) Preparation of compound A

Compound Aa (1.0 eq.) and Compound Ab (1.03 eq.) were placed in a round bottom flask and dissolved in toluene (0.3 M). K ₂ CO ₃ (2.1 eq.) dissolved in water was injected, and Aliquat 336 (2.5 mol%) dissolved in toluene was injected. Pd(amPhos)Cl ₂ (0.1 mol%) was added dropwise under a bath temperature of 80° C. and stirred overnight. After the reaction, the reactant was cooled to room temperature, diluted sufficiently in EtOAc, and washed with EtOAc/brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound A (94% yield).

MS: [M+H] ⁺ = 507.

2) Preparation of compound AD

Compound A (5.0 g, 1.0 eq.) was placed in a round bottom flask under a nitrogen atmosphere and dissolved in benzene-D6 (150 eq.). TfOH (2.0 eq.) was slowly added dropwise to the reaction and stirred at 25° C. for 2 hours. D ₂ O was added dropwise to the reactant to terminate the reaction, and potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq) was added dropwise to adjust the pH of the aqueous layer to 9-10. The organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound AD (96% yield, deuterated product o+p+q+r=21-23).

MS: [M+H] ⁺ = 529.

Preparation 3-2: Preparation of compound BD

1) Preparation of compound B

Compound Ba (1.0 eq.) and Compound Bb (1.03 eq.) were placed in a round bottom flask and dissolved in toluene (0.3 M). K ₂ CO ₃ (2.1 eq.) dissolved in water was injected, and Aliquat 336 (2.5 mol%) dissolved in toluene was injected. At a bath temperature of 80° C., Pd(amPhos)Cl ₂ (0.1 mol%) was added dropwise and stirred overnight. After the reaction, the reactant was cooled to room temperature, diluted sufficiently in EtOAc, and washed with EtOAc/brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound B (92% yield).

MS: [M+H] ⁺ = 507.

2) Preparation of compound BD

Compound B (1.0 eq.) was placed in a round bottom flask under a nitrogen atmosphere and dissolved in benzene-D6 (150 eq.). TfOH (2.0 eq.) was slowly added dropwise to the reaction and stirred at 25° C. for 2 hours. D ₂ O was added dropwise to the reactant to terminate the reaction, and potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq) was added dropwise to adjust the pH of the aqueous layer to 9-10. The organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound BD (97% yield, deuterated product o+p+q+r=21-23).

MS: [M+H] ⁺ = 529.

Preparation 3-3: Preparation of compound CD

1) Preparation of compound C

Compound Ca (1.0 eq.) and compound Cb (1.03 eq.) were placed in a round bottom flask and dissolved in toluene (0.3 M). K ₂ CO ₃ (2.1 eq.) dissolved in water was injected, and Aliquat 336 (2.5 mol%) dissolved in toluene was injected. At a bath temperature of 80° C., Pd(amPhos)Cl ₂ (0.1 mol%) was added dropwise and stirred overnight. After the reaction, the reactant was cooled to room temperature, diluted sufficiently in EtOAc, and washed with EtOAc/brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound C (88% yield).

MS: [M+H] ⁺ = 470.

2) Preparation of compound CD

Compound C (1.0 eq.) was placed in a round bottom flask under a nitrogen atmosphere and dissolved in benzene-D6 (300 eq.). TfOH (5.0 eq.) was slowly added dropwise to the reaction and stirred at 25° C. for 2 hours. D ₂ O was added dropwise to the reactant to terminate the reaction, and potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq) was added dropwise to adjust the pH of the aqueous layer to 9-10. The organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound CD (97% yield, deuterated product s+p+r=21-22).

MS: [M+H] ⁺ = 492.

Preparation 3-4: Preparation of compound DD

1) Preparation of compound D

Compound Da (1.0 eq.) and compound Db (1.03 eq.) were placed in a round bottom flask and dissolved in toluene (0.3 M). K ₂ CO ₃ (2.1 eq.) dissolved in water was injected, and Aliquat 336 (2.5 mol%) dissolved in toluene was injected. At a bath temperature of 80° C., Pd(amPhos)Cl ₂ (0.1 mol%) was added dropwise and stirred overnight. After the reaction, the reactant was cooled to room temperature, diluted sufficiently in EtOAc, and washed with EtOAc/brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound D (92% yield).

MS: [M+H] ⁺ = 546.

2) Preparation of compound DD

Compound D (1.0 eq.) was placed in a round bottom flask under a nitrogen atmosphere and dissolved in benzene-D6 (300 eq.). TfOH (5.0 eq.) was slowly added dropwise to the reaction and stirred at 25° C. for 2 hours. D ₂ O was added dropwise to the reactant to terminate the reaction, and potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq) was added dropwise to adjust the pH of the aqueous layer to 9-10. The organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound DD (97% yield, deuterated product s+p+q+r=23-24).

MS: [M+H] ⁺ = 570.

[Element example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl and acetone and dried. After washing the substrate for 5 minutes, the substrate was transported to a glove box.

On the ITO transparent electrode, a coating composition in which the following compound O and the following compound P (weight ratio of 2:8) were dissolved in cyclohexanone at a concentration of 20 wt/v% (4000 rpm) was spin-coated (4000 rpm) and at 200 °C for 30 minutes A hole injection layer having a thickness of 400 Å was formed by heat treatment (curing).

A coating composition obtained by dissolving compound H1 (Mw: 130,700) prepared in Preparation Example 1-1 in toluene at a concentration of 6 wt/v% above the hole injection layer was spin-coated (4000 rpm) and heat-treated at 200° C. for 30 minutes. A hole transport layer having a thickness of 200 Å was formed.

On the hole transport layer, Compound 1 prepared in Preparation Example 2-10 and Compound AD prepared in Preparation Example 3-1 (weight ratio of 2:98) were dissolved in cyclohexanone at a concentration of 2 wt/v% in cyclohexanone coating composition was spin-coated (4000 rpm) and heat-treated at 180° C. for 30 minutes to form a light emitting layer with a thickness of 400 Å.

After transferring to a vacuum evaporator, the following compound R was vacuum deposited on the light emitting layer to form an electron injection and transport layer having a thickness of 350 Å. An anode was formed by sequentially depositing LiF to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of 0.3 Å/sec for LiF and 2 Å/sec for aluminum was maintained, and the vacuum degree during deposition was 2×10 ^-7 to 5 ×10 ^-8 torr was maintained.

Examples 2 to 144

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 1 to 12 were used for the hole transport layer and the light emitting layer, respectively.

Comparative Examples 1 to 52

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 13 to 17 were used for the hole transport layer and the light emitting layer, respectively. In Tables 13 to 17, compounds Q (Mn: 27,900; Mw: 35,600; measured by GPC using PC Standard using Agilent 1200 series), A, C, and S are as follows, respectively.

Experimental example

By applying a current to the organic light emitting device prepared in the Examples and Comparative Examples, the driving voltage, external quantum efficiency (EQE) and lifespan at a current density of 10 mA/cm ² are measured, and the result is It is shown in Tables 1 to 12 below. At this time, the external quantum efficiency (EQE) was calculated as "(the number of emitted photons)/(the number of injected charge carriers) * 100", and T90 is the time it takes for the luminance to decrease from the initial luminance (500 nit) to 90%. means

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 1 H1 compound AD compound 1 4.4 5.09 255 Example 2 H1 compound AD compound 2 4.5 5.0 243 Example 3 H1 compound AD compound 3 4.48 5.42 276 Example 4 H1 compound AD compound 4 4.3 5.33 253 Example 5 H1 compound AD compound 5 4.1 6.01 223 Example 6 H1 compound AD compound 6 4.02 5.98 278 Example 7 H1 compound AD compound 7 4.01 6.3 198 Example 8 H1 compound AD compound 8 4.66 5.9 201 Example 9 H1 compound AD compound 9 4.95 5.78 230 Example 10 H1 compound AD compound 10 4.32 5.22 221 Example 11 H1 compound AD compound 11 4.44 5.54 219 Example 12 H1 compound AD compound 12 4.6 6.23 220

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 13 H1 compound BD compound 1 4.92 5.78 203 Example 14 H1 compound BD compound 2 4.23 5.67 245 Example 15 H1 compound BD compound 3 4.11 5.33 265 Example 16 H1 compound BD compound 4 4.23 5.20 201 Example 17 H1 compound BD compound 5 4.45 5.49 211 Example 18 H1 compound BD compound 6 5.01 6.01 190 Example 19 H1 compound BD compound 7 4.43 5.98 209 Example 20 H1 compound BD compound 8 4.27 5.0 199 Example 21 H1 compound BD compound 9 4.97 5.76 243 Example 22 H1 compound BD compound 10 4.33 6.12 254 Example 23 H1 compound BD compound 11 4.56 5.98 212 Example 24 H1 compound BD compound 12 4.64 6.01 230

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 25 H1 compound CD compound 1 4.87 6.01 243 Example 26 H1 compound CD compound 2 4.44 6.23 254 Example 27 H1 compound CD compound 3 4.39 6.05 265 Example 28 H1 compound CD compound 4 5.10 5.98 277 Example 29 H1 compound CD compound 5 4.22 5.77 276 Example 30 H1 compound CD compound 6 4.30 6.8 243 Example 31 H1 compound CD compound 7 4.98 5.7 254 Example 32 H1 compound CD compound 8 5.01 5.65 266 Example 33 H1 compound CD compound 9 5.2 5.4 287 Example 34 H1 compound CD compound 10 4.76 5.99 291 Example 35 H1 compound CD compound 11 4.87 6.18 208 Example 36 H1 compound CD compound 12 4.54 6.33 267

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 37 H1 compound DD compound 1 4.85 5.87 259 Example 38 H1 compound DD compound 2 4.53 6.33 276 Example 39 H1 compound DD compound 3 4.23 6.05 266 Example 40 H1 compound DD compound 4 4.44 5.98 256 Example 41 H1 compound DD compound 5 4.09 5.77 298 Example 42 H1 compound DD compound 6 4.98 5.34 278 Example 43 H1 compound DD compound 7 5.01 6.02 209 Example 44 H1 compound DD compound 8 5.03 6.99 280 Example 45 H1 compound DD compound 9 4.87 6.03 301 Example 46 H1 compound DD compound 10 4.11 5.78 284 Example 47 H1 compound DD compound 11 4.76 5.81 215 Example 48 H1 compound DD compound 12 4.35 6.3 240

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 49 H2 compound AD compound 1 4.54 6.9 276 Example 50 H2 compound AD compound 2 4.23 5.99 288 Example 51 H2 compound AD compound 3 4.39 6.79 295 Example 52 H2 compound AD compound 4 4.98 7.01 293 Example 53 H2 compound AD compound 5 4.55 7.32 291 Example 54 H2 compound AD compound 6 4,65 6.91 330 Example 55 H2 compound AD compound 7 4.99 6.11 298 Example 56 H2 compound AD compound 8 4.22 7.02 301 Example 57 H2 compound AD compound 9 4.32 7.89 322 Example 58 H2 compound AD compound 10 4.73 5.09 343 Example 59 H2 compound AD compound 11 4.34 5.8 276 Example 60 H2 compound AD compound 12 4.91 5.24 255

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 61 H2 compound BD compound 1 4.98 6.89 230 Example 62 H2 compound BD compound 2 4.78 7.01 278 Example 63 H2 compound BD compound 3 4.03 7.11 298 Example 64 H2 compound BD compound 4 5.05 5.92 302 Example 65 H2 compound BD compound 5 4.71 5.23 382 Example 66 H2 compound BD compound 6 4.86 5.08 312 Example 67 H2 compound BD compound 7 4.99 6.24 290 Example 68 H2 compound BD compound 8 4.01 6.40 289 Example 69 H2 compound BD compound 9 4.33 6.23 234 Example 70 H2 compound BD compound 10 4.59 6.98 209 Example 71 H2 compound BD compound 11 4.67 6.03 199 Example 72 H2 compound BD compound 12 4.65 6.05 200

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 73 H2 compound CD compound 1 4.87 6.22 230 Example 74 H2 compound CD compound 2 4.29 6.34 243 Example 75 H2 compound CD compound 3 4.23 5.88 212 Example 76 H2 compound CD compound 4 4.27 6.65 244 Example 77 H2 compound CD compound 5 4.01 6.89 265 Example 78 H2 compound CD compound 6 4.56 7.01 298 Example 79 H2 compound CD compound 7 4.99 7.22 277 Example 80 H2 compound CD compound 8 4.84 5.34 243 Example 81 H2 compound CD compound 9 4.89 5.90 265 Example 82 H2 compound CD compound 10 4.21 6.34 209 Example 83 H2 compound CD compound 11 4.56 6.22 200 Example 84 H2 compound CD compound 12 4.65 6.5 230

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 85 H2 compound DD compound 1 4.22 6.07 301 Example 86 H2 compound DD compound 2 4.76 6.22 323 Example 87 H2 compound DD compound 3 4.87 6.33 298 Example 88 H2 compound DD compound 4 5.03 6.12 278 Example 89 H2 compound DD compound 5 5.12 6.34 308 Example 90 H2 compound DD compound 6 4.88 6.43 311 Example 91 H2 compound DD compound 7 4.39 6.12 294 Example 92 H2 compound DD compound 8 4.11 7.01 265 Example 93 H2 compound DD compound 9 4.92 7.11 223 Example 94 H2 compound DD compound 10 4.23 7.09 318 Example 95 H2 compound DD compound 11 4.33 6.58 286 Example 96 H2 compound DD compound 12 4.35 7.03 288

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 97 H3 compound AD compound 1 4.32 6.96 320 Example 98 H3 compound AD compound 2 4.0 6.76 342 Example 99 H3 compound AD compound 3 4.88 7.01 298 Example 100 H3 compound AD compound 4 4.12 7.12 304 Example 101 H3 compound AD compound 5 4.02 7.02 301 Example 102 H3 compound AD compound 6 4.99 6.98 298 Example 103 H3 compound AD compound 7 5.01 6.44 278 Example 104 H3 compound AD compound 8 5.11 6.50 314 Example 105 H3 compound AD compound 9 5.02 6.91 334 Example 106 H3 compound AD compound 10 4.30 7.01 320 Example 107 H3 compound AD compound 11 4.23 6.45 297 Example 108 H3 compound AD compound 12 4.54 7.01 299

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 109 H3 compound BD compound 1 4.23 7.9 340 Example 110 H3 compound BD compound 2 4.01 7.32 353 Example 111 H3 compound BD compound 3 4.55 7.43 301 Example 112 H3 compound BD compound 4 4.34 7.76 298 Example 113 H3 compound BD compound 5 4.30 7.01 283 Example 114 H3 compound BD compound 6 4.12 6.98 303 Example 115 H3 compound BD compound 7 4.08 7.21 311 Example 116 H3 compound BD compound 8 4.87 7.33 288 Example 117 H3 compound BD compound 9 5.01 6.92 300 Example 118 H3 compound BD compound 10 4.34 6.01 302 Example 119 H3 compound BD compound 11 4.5 6.21 267 Example 120 H3 compound BD compound 12 4.86 6.18 300

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 121 H3 compound CD compound 1 4.33 6.98 230 Example 122 H3 compound CD compound 2 4.54 6.78 211 Example 123 H3 compound CD compound 3 4.34 6.99 298 Example 124 H3 compound CD compound 4 4.67 6.57 300 Example 125 H3 compound CD compound 5 4.98 7.02 303 Example 126 H3 compound CD compound 6 4.31 7.00 323 Example 127 H3 compound CD compound 7 4.01 7.91 311 Example 128 H3 compound CD compound 8 4.02 7.23 299 Example 129 H3 compound CD compound 9 4.23 6.93 293 Example 130 H3 compound CD compound 10 4.26 6.88 277 Example 131 H3 compound CD compound 11 4.56 6.31 287 Example 132 H3 compound CD compound 12 4.71 6.28 298

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Example 133 H3 compound DD compound 1 4.56 6.12 299 Example 134 H3 compound DD compound 2 4.39 6.54 291 Example 135 H3 compound DD compound 3 4.39 6.14 233 Example 136 H3 compound DD compound 4 4.99 7.12 302 Example 137 H3 compound DD compound 5 4.10 7.02 300 Example 138 H3 compound DD compound 6 4.23 7.11 298 Example 139 H3 compound DD compound 7 4.89 6.98 277 Example 140 H3 compound DD compound 8 4.56 6.88 263 Example 141 H3 compound DD compound 9 4.30 6.98 302 Example 142 H3 compound DD compound 10 4.55 6.30 315 Example 143 H3 compound DD compound 11 4.29 6.1 278 Example 144 H3 compound DD compound 12 4.81 6.03 288

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Comparative Example 1 compound Q compound A compound 1 5.09 5.3 130 Comparative Example 2 compound Q compound A compound 2 5.11 5.45 112 Comparative Example 3 compound Q compound A compound 3 5.02 5.12 102 Comparative Example 4 compound Q compound A compound 4 5.32 5.07 100 Comparative Example 5 compound Q compound A compound 5 5.13 4.99 129 Comparative Example 6 compound Q compound A compound 6 5.3 4.78 105 Comparative Example 7 compound Q compound A compound 7 5.5 5.02 98 Comparative Example 8 compound Q compound A compound 8 5.01 4.87 102 Comparative Example 9 compound Q compound A compound 9 5.3 5.51 105 Comparative Example 10 compound Q compound A compound 10 5.45 4.98 99 Comparative Example 11 compound Q compound A compound 11 5.23 5.3 120 Comparative Example 12 compound Q compound A compound 12 5.11 5.22 133

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Comparative Example 13 compound Q compound C compound 1 5.2 5.6 192 Comparative Example 14 compound Q compound C compound 2 5.34 5.3 198 Comparative Example 15 compound Q compound C compound 3 5.01 5.08 156 Comparative Example 16 compound Q compound C compound 4 5.02 5.63 143 Comparative Example 17 compound Q compound C compound 5 5.34 5.4 164 Comparative Example 18 compound Q compound C compound 6 5.4 5.51 123 Comparative Example 19 compound Q compound C compound 7 5.11 5.59 133 Comparative Example 20 compound Q compound C compound 8 4.98 5.03 156 Comparative Example 21 compound Q compound C compound 9 5.1 5.22 187 Comparative Example 22 compound Q compound C compound 10 5.02 5.34 123 Comparative Example 23 compound Q compound C compound 11 5.2 5.6 181 Comparative Example 24 compound Q compound C compound 12 4.99 5.8 177

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Comparative Example 25 H3 compound A compound 1 5.2 6.31 205 Comparative Example 26 H3 compound A compound 2 5.22 6.67 198 Comparative Example 27 H3 compound A compound 3 5.1 6.42 210 Comparative Example 28 H3 compound A compound 4 4.92 6.16 195 Comparative Example 29 H3 compound A compound 5 5.34 6.44 188 Comparative Example 30 H3 compound A compound 6 5.11 7.13 187 Comparative Example 31 H3 compound A compound 7 5.03 6.35 196 Comparative Example 32 H3 compound A compound 8 4.81 6.47 157 Comparative Example 33 H3 compound A compound 9 5.28 6.53 200 Comparative Example 34 H3 compound A compound 10 5.37 6.74 206 Comparative Example 35 H3 compound A compound 11 4.83 6.23 204 Comparative Example 36 H3 compound A compound 12 4.63 6.46 190

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Comparative Example 37 H3 compound C compound 1 4.8 6.24 177 Comparative Example 38 H3 compound C compound 2 5.53 6.22 165 Comparative Example 39 H3 compound C compound 3 5.12 6.31 184 Comparative Example 40 H3 compound C compound 4 5.24 6.42 170 Comparative Example 41 H3 compound C compound 5 4.87 6.78 168 Comparative Example 42 H3 compound C compound 6 5.13 6.98 172 Comparative Example 43 H3 compound C compound 7 4.91 6.63 158 Comparative Example 44 H3 compound C compound 8 4.8 6.49 179 Comparative Example 45 H3 compound C compound 9 5.32 6.61 163 Comparative Example 46 H3 compound C compound 10 5.11 6.78 169 Comparative Example 47 H3 compound C compound 11 5.2 6.88 172 Comparative Example 48 H3 compound C compound 12 4.89 6.31 175

hole
transport layer light emitting layer
host light emitting layer
dopant drive voltage
(V @10mA/cm ² ) EQE
(% @10mA/cm ² ) Lifetime (T90)
(hr @500nit) Comparative Example 49 H3 compound AD compound S 4.78 5.75 98 Comparative Example 50 H3 compound BD compound S 4.3 5.48 83 Comparative Example 51 H3 compound CD compound S 4.51 5.92 85 Comparative Example 52 H3 compound DD compound S 4.93 5.21 92

From the above results, the organic light emitting device of the present invention includes a polymer including a repeating unit represented by Formula 1 in the hole transport layer, and includes the compound represented by Formula 2 and the compound represented by Formula 3 in the light emitting layer. It can be seen that the driving voltage is shown, and quantum efficiency and lifespan characteristics are excellent.

1: Substrate 2: Anode
3: hole transport layer 4: light emitting layer
5: Cathode 6: Hole injection layer
7: electron transport layer 8: electron injection layer

Claims (16)

anode,
cathode,
a light emitting layer between the anode and the cathode; and
and a hole transport layer between the anode and the light emitting layer,
The hole transport layer includes a polymer including a repeating unit represented by the following formula (1),
The light emitting layer comprises a compound represented by the following formula (2) and a compound represented by the following formula (3),
Organic light emitting device:
[Formula 1]

In Formula 1,
L is each independently substituted or unsubstituted C _6-60 aryl,
Ar is each independently substituted or unsubstituted C _6-60 aryl,
each R ₁ is independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl, provided that at least one of R ₁ is substituted or unsubstituted C _1-10 alkyl;
R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl;
[Formula 2]

In Formula 2,
X' is a substituted or unsubstituted naphthalene ring fused with two adjacent rings,
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 containing any one or more heteroatoms selected from the group consisting of N, O and S,
B′ ₁ and B′ ₂ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
Ar' ₁ and Ar' ₂ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
Y′ ₁ and Y′ ₂ are the same as each other and are O or C(R′ _a )(R′ _b ), wherein R′ _a and R′ _b are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-60 alkyl; Or a substituted or unsubstituted C _6-60 aryl,
R′ ₁ to R′ ₄ are all hydrogen; or two adjacent ones of R' ₁ to R' ₄ combine with each other to form a benzene ring, and the remainder is hydrogen,
R' ₅ to R' ₈ are all hydrogen; or two adjacent ones of R' ₅ to R' ₈ combine with each other to form a benzene ring, and the rest are hydrogen,
[Formula 3]

In Formula 3,
Ar" ₁ is C _6-60 aryl substituted with one or more deuterium; or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium; ,
Ar" ₂ is C _6-60 aryl substituted with one or more deuterium; or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium; ,
R" is deuterium,
n" is an integer from 0 to 8;
According to claim 1,
L is each independently phenylene, or biphenyldiyl,
organic light emitting device.
According to claim 1,
Ar is each independently phenyl or biphenylyl,
wherein Ar is unsubstituted or substituted with C _1-10 alkyl, or N(C _6-60 aryl) ₂ ,
organic light emitting device.
The method of claim 1,
Ar is biphenylyl,
Ar is unsubstituted or substituted with methyl, ethyl, propyl, or N(phenyl) ₂ ,
organic light emitting device.
According to claim 1,
each R ₁ is independently methyl, ethyl, propyl, butyl, pentyl, or hexyl;
organic light emitting device.
According to claim 1,
each R ₂ is independently methyl;
organic light emitting device.
The method of claim 1,
Formula 1 is represented by any one selected from the group consisting of,
Organic light emitting device:

According to claim 1,
Formula 2 is represented by the following Formula 2-1 or Formula 2-2,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, L′ ₁ , L′ ₂ , B′ ₁ , B′ ₂ , Ar′ ₁ , Ar′ ₂ , Y′ ₁ , Y′ ₂ , and R′ ₁ to R′ ₈ is as defined in Paragraph 1.
The method of claim 1,
L' ₁ and L' ₂ are both single bonds,
organic light emitting device.
The method of claim 1,
B' ₁ and B' ₂ are each independently a single bond, phenylene, biphenylene, or naphthalenediyl;
wherein B′ ₁ and B′ ₂ are unsubstituted or substituted with one or more C _1-10 alkyl,
organic light emitting device.
According to claim 1,
Ar′ ₁ and Ar′ ₂ are each independently phenyl, biphenyl, naphthyl, benzofuranyl, dimethylfluorenyl, or dibenzofuranyl,
wherein Ar′ ₁ and Ar′ ₂ are unsubstituted or substituted with one or more C _1-10 alkyl,
organic light emitting device.
According to claim 1,
Y′ ₁ and Y′ ₂ are the same as each other and are O or C(CH ₃ ) ₂ ,
organic light emitting device.
The method of claim 1,
Formula 2 is represented by any one selected from the group consisting of:
Organic light emitting device:

According to claim 1,
Ar" ₁ is naphthyl substituted with one or more deuterium, or naphthylphenyl substituted with one or more deuterium;
organic light emitting device.
According to claim 1,
Ar" ₂ is naphthylphenyl substituted with one or more deuterium, or dibenzofuranyl substituted with one or more deuterium;
organic light emitting device.
The method of claim 1,
Formula 3 is represented by any one of the following Formulas 3-1 to 3-4,
Organic light emitting device:
[Formula 3-1]

In Formula 3-1,
o+p+q+r is an integer from 21 to 23,
[Formula 3-2]

In Formula 3-2,
o+p+q+r is an integer from 21 to 23,
[Formula 3-3]

In Formula 3-3,
o+p+q is an integer from 17 to 20,
[Formula 3-4]

In Formula 3-4,
o+p+q+r is an integer from 21 to 23;

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