阅读说明：本技术 有机发光器件 (Organic light emitting device ) 是由 黄民浩 李志永 李浩奎 徐锡材 金光显 裵在顺 李载澈 申旨娟 李根洙 于 2020-08-12 设计创作，主要内容包括：本公开内容提供了有机发光器件。(The present disclosure provides an organic light emitting device.)

1. An organic light emitting device comprising:

an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode,

wherein the hole injection layer comprises a cured product of a compound represented by the following chemical formula 1, and

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

[ chemical formula 1]

In the chemical formula 1, the first and second organic solvents,

L₁is substituted or unsubstituted C_6-60An arylene group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S_2-60A heteroarylene group, a heteroaryl group,

Ar₁each independently is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

Ar₂each independently is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

L₂each independently a single bond, substituted or unsubstituted C_1-10Alkylene, or substituted or unsubstituted C_6-60An arylene group, a cyclic or cyclic alkylene group,

R₁each is independentThe site is hydrogen; deuterium; halogen; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

each n is independently an integer of 0 to 3,

each R is independently a photocurable group; or a thermosetting group,

[ chemical formula 2-1]

In the chemical formula 2-1,

R'₁to R'₃Each independently is hydrogen or C_1-10An alkyl group, a carboxyl group,

L'₁is substituted or unsubstituted C_6-60An arylene group; - (substituted or unsubstituted C)_6-60Arylene) -O- (substituted or unsubstituted C_6-60Arylene) -; - (substituted or unsubstituted C)_6-60Arylene) - (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-60Arylene) -; - (substituted or unsubstituted C)_6-60Arylene) -O- (substituted or unsubstituted C_1-10Alkylene) -O-; or- (substituted or unsubstituted C_6-60Arylene) - (substituted or unsubstituted C_1-10Alkylene) -O- (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-60Arylene) -,

L'₂and L'₃Each independently is a single bond; substituted or unsubstituted C_6-60An arylene group; or substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60A heteroarylene group, a heteroaryl group,

Ar'₁to Ar'₄Each independently is substituted or unsubstituted C_6-60Aryl, orOr substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60Heteroaryl, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form C_6-60An aromatic ring, or C comprising any one or more selected from N, O and S_2-60A heteroaromatic ring which is capable of forming a heterocyclic ring,

ra is hydrogen; deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_3-60A cycloalkyl group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

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

[ chemical formula 2-2]

In the chemical formula 2-2,

R'₄to R'₆Each independently is hydrogen or C_1-10An alkyl group, a carboxyl group,

L'₄is a single bond; substituted or unsubstituted C_6-60An arylene group, a cyclic or cyclic alkylene group,

r' is a photocurable group; or a thermosetting group, and

y is a mole fraction of the repeating unit represented by chemical formula 2-2 in the polymer.

2. The organic light emitting device according to claim 1,

wherein L is₁Is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, binaphthyldiyl, phenanthrenediyl, spirobifluorenediyl, dimethylfluorenediyl, diphenylfluorenediyl, or tetraphenylfluorenediyl, and

said L₁Being unsubstituted or substituted by oneOr two C_1-10Alkyl substitution.

3. The organic light emitting device according to claim 1,

wherein L is₁Is any one selected from the following:

4. the organic light-emitting device according to claim 1,

wherein Ar is₁Each independently of the others, phenyl, biphenyl, naphthyl, phenanthryl or dimethylfluorenyl, and

ar is₁Unsubstituted or substituted with 1 to 5 deuterium, or halogen.

5. The organic light emitting device according to claim 1,

wherein Ar is₂Each independently of the other is phenyl, biphenyl or naphthyl,

ar is₂Is unsubstituted or substituted by: -R; 1 to 5 deuterium; 1 or 2C_1-10An alkyl group; 1 to 5 halogens; c_1-10An alkoxy group; substituted by C_1-10C of alkoxy_1-10An alkoxy group; c_1-10A haloalkyl group; or phenoxy group, and

r is as defined in claim 1.

6. The organic light emitting device according to claim 1,

wherein L is₂Each independently a single bond, butylene, pentylene, hexylene, heptylene, or phenylene.

7. The organic light emitting device according to claim 1,

wherein n is 1, and

R₁each independently hydrogen or phenyl.

8. The organic light emitting device according to claim 1,

wherein R is-L₃-R₂，

L₃Is a single bond, -O-, -S-, -CH₂-、-CH₂O-、-OCH₂-、-CH₂OCH₂-, -N (phenyl) -, or-O (CH)₂)₆-, and

R₂is any one selected from the following:

9. the organic light emitting device according to claim 1,

wherein the compound represented by chemical formula 1 is any one compound selected from the group consisting of:

10. the organic light emitting device according to claim 1,

wherein x: y is 0.5 to 0.99:0.01 to 0.5.

11. The organic light emitting device according to claim 1,

wherein L'₁Are phenylene, - (phenylene) O (phenylene) -, - (phenylene) (CH)₂)₆(phenylene) -, - (phenylene) O (CH)₂)₆O-, or- (phenylene) CH₂OCH₂(phenylene) -.

12. The organic light emitting device according to claim 1,

wherein L'₂And L'₃Each independently a single bond or phenylene.

13. The organic light emitting device according to claim 1,

wherein Ar'₁To Ar'₄Each independently is phenyl, biphenyl substituted with N, N-diphenylamino, or dimethylfluorenyl, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form

14. The organic light emitting device according to claim 1,

wherein Ar'₁To Ar'₄Each independently is any one selected from the following, or

Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form

15. The organic light emitting device according to claim 1,

wherein Ar'₁And Ar'₃Is phenyl or biphenyl, Ar'₂And Ar'₄Is any one selected from the following, or

Ar'₁And Ar'₂And Ar'₃And Ar'₄Are bonded to each other to form

16. The organic light emitting device according to claim 1,

wherein Ra is hydrogen, methyl or phenyl.

17. The organic light emitting device according to claim 1,

wherein the chemical formula 2-1 is any one selected from repeating units represented by the following formulae:

18. the organic light emitting device according to claim 1,

wherein L'₄Is a single bond or phenylene.

19. The organic light emitting device according to claim 1,

wherein the chemical formula 2-2 is any one selected from repeating units represented by the following formulae:

20. the organic light emitting device according to claim 1,

wherein the weight average molecular weight of the polymer is 5,000g/mol to 1,000,000 g/mol.

21. The organic light emitting device according to claim 1,

wherein the hole injection layer further comprises a compound represented by the following chemical formula 3:

[ chemical formula 3]

In the chemical formula 3, the first and second organic solvents,

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

Ar"₁is composed of

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

R"₁each independently is hydrogen, halogen or C_1-60A halogenated alkyl group,

n3 is an integer from 1 to 4,

Ar"₂is composed of

R"₂Each independently of the others is hydrogen, halogen, C_1-60Haloalkyl, a photocurable group or a thermosetting group, and

n4 is an integer from 1 to 5.

22. The organic light emitting device of claim 21,

wherein R "₁Each independently hydrogen, fluorine or CF₃。

23. The organic light emitting device of claim 21,

wherein Ar "₁Is any one selected from the following:

24. the organic light emitting device of claim 21,

wherein R "₂Each independently of the others being hydrogen, fluorine, CF₃、CF(CF₃)₂、CF₂CF₂CF₂CF₃A photocurable group or a thermosetting group.

25. The organic light emitting device of claim 21,

wherein Ar "₂Is any one selected from the following:

26. the organic light emitting device of claim 21,

wherein the compound represented by chemical formula 3 is any one selected from the group consisting of:

in the above group, the first and second substrates are,

n1 and n2 are as defined in claim 21.

27. The organic light emitting device according to claim 1,

wherein at least one of the chemical formula 1, the chemical formula 2-1, and the chemical formula 2-2 is at least 10% deuterated.

28. The organic light emitting device of claim 21,

wherein the chemical formula 3 is at least 10% deuterated.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2019-.

The present disclosure relates to organic light emitting devices.

Background

In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, excellent brightness, a driving voltage, and a response speed, and thus many studies have been made.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layer structure including different materials to improve efficiency and stability of the organic light emitting device, and for example, the organic material layer 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 the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer, electrons are injected from a cathode into the organic material layer, and when the injected holes and electrons meet each other, excitons are formed, and light is emitted when the excitons fall to a ground state again.

There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.

Meanwhile, recently, in order to reduce process costs, organic light emitting devices using a solution method, particularly an inkjet method, instead of a conventional deposition method have been developed. In the initial stage of development, an attempt to develop an organic light emitting device by coating all organic light emitting device layers through a solution method has been made, but the current technology has limitations. Therefore, only the HIL, the HTL, and the EML are processed by a solution method in the layer device structure, and as a subsequent process, a hybrid process using a conventional deposition method is being studied.

In this regard, in the present disclosure, there are provided a new material for an organic light emitting device that can be used for an organic light emitting device and, at the same time, can be used for a solution method, and an organic light emitting device using the same.

[ Prior art documents ]

[ patent document ]

(patent document 1) Korean unexamined patent publication No. 10-2000-0051826

Disclosure of Invention

Technical problem

An object of the present disclosure is to provide an organic light emitting device having a low driving voltage, high light emitting efficiency, and excellent lifetime.

Technical scheme

In order to achieve the above object, there is provided an organic light emitting device including: an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode,

wherein the hole injection layer comprises a cured product of a compound represented by the following chemical formula 1, and

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

[ chemical formula 1]

In the chemical formula 1, the first and second,

L₁is substituted or unsubstituted C_6-60An arylene group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S_2-60A heteroarylene group, a heteroaryl group,

Ar₁each independently is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

Ar₂each independently is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

L₂each independently a single bond, substituted or unsubstituted C_1-10Alkylene, or substituted or unsubstituted C_6-60An arylene group, a cyclic or cyclic alkylene group,

R₁each independently is hydrogen; deuterium; halogen; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C containing any one or more heteroatoms selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

each n is independently an integer of 0 to 3,

each R is independently a photocurable group; or a thermosetting group,

[ chemical formula 2-1]

In the chemical formula 2-1, the,

R'₁to R'₃Each independently is hydrogen or C_1-10An alkyl group, a carboxyl group,

L'₁is substituted or unsubstituted C_6-60An arylene group; - (substituted or unsubstituted C)_6-60Arylene) -O- (substituted or unsubstituted C_6-60Arylene radical) -; - (substituted or unsubstituted C)_6-60Arylene) - (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-60Arylene) -; - (substituted or unsubstituted C)_6-60Arylene) -O- (substituted or unsubstituted C_1-10Alkylene) -O-; or- (substituted or unsubstituted C_6-60Arylene) - (substituted or unsubstituted C_1-10Alkylene) -O- (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-60Arylene) -,

L'₂and L'₃Each independently is a single bond; substituted or unsubstituted C_6-60An arylene group; or substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60A heteroarylene group, a heteroaryl group,

Ar'₁to Ar'₄Each independently is substituted or unsubstituted C_6-60Aryl, or substituted or unsubstituted C containing one or more members selected from N, O and S_2-60Heteroaryl, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form C_6-60An aromatic ring, or C comprising any one or more selected from N, O and S_2-60A heteroaromatic ring which is capable of forming a heterocyclic ring,

ra is hydrogen; deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_3-60A cycloalkyl group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

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

[ chemical formula 2-2]

In the chemical formula 2-2, the,

R'₄to R'₆Each independently is hydrogen or C_1-10An alkyl group, a carboxyl group,

L'₄is a single bond; substituted or unsubstituted C_6-60An arylene group, a cyclic or cyclic alkylene group,

r' is a photocurable group; or a thermosetting group, and

y is a mole fraction of the repeating unit represented by chemical formula 2-2 in the polymer.

Advantageous effects

The organic light emitting device according to the present disclosure may prepare a hole injection layer or a hole transport layer through a solution process, and may improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device.

Drawings

Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 6.

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

Detailed Description

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

(definition of terms)

As used herein, a symbolMeans a bond to another substituent.

As used herein, the term "substituted or unsubstituted" refers to unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; an alkylsulfonyl group; an arylsulfonyl group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; and heteroaryl comprising at least one of N, O and S atoms, or a substituent that is unsubstituted or linked by two or more of the substituents exemplified above. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, biphenyl can be an aryl group, or it can also be interpreted as a substituent with two phenyl groups attached.

In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structural formula, but is not limited thereto.

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

In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25.

Specifically, the imide group may be a compound having the following structural formula, but is not limited thereto.

In the present disclosure, the silyl group specifically includes, but is not limited to, 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.

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

In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present disclosure, the alkyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is from 1 to 20. According to another embodiment, the carbon number of the alkyl group is from 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. 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-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, n-butyl, 1-ethyl-butyl, pentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3, 2-dimethylbutyl, heptyl, 1-methylhexyl, cyclohexyl, octyl, 1-methyl-pentyl, 2-pentyl, and the like, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present disclosure, the alkenyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to yet another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthyl-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) ethylAlkenyl-1-yl,Phenyl, styryl, and the like, but are not limited thereto.

In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is from 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is from 3 to 20. According to yet another embodiment, the carbon number of the cycloalkyl group is from 3 to 6. Specific examples thereof include 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 disclosure, the aryl group is not particularly limited, but its carbon number is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is from 6 to 30. According to one embodiment, the carbon number of the aryl group is from 6 to 20. As the monocyclic aryl group, the aryl group may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. The polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, and the like,A base,And the like, but are not limited thereto.

In the present disclosure, the fluorenyl group may be substituted, and two substituents may be connected to each other to form a spiro ring structure. In the case of the fluorenyl group being substituted, it can formAnd the like. However, the structure is not limited thereto.

In the present disclosure, the heteroaryl group is a heteroaryl group including one or more of O, N, Si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Hetero compoundExamples of aryl groups includeXanthyl, thioxanthyl, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, thienyl,Azolyl group,Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinylAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, isoquinoylOxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.

In the present disclosure, the aryl group of the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the foregoing examples of the aryl group. In the present disclosure, the alkyl groups in the aralkyl, alkylaryl, and alkylamino groups are the same as the foregoing examples of alkyl groups. In the present disclosure, the heteroaryl group in the heteroarylamine may employ the foregoing description of the heteroaryl group. In the present disclosure, the alkenyl group in the aralkenyl group is the same as the foregoing example of the alkenyl group. In the present disclosure, the foregoing description of aryl groups may be applied, except that the arylene group is a divalent group. In the present disclosure, the foregoing description of heteroaryl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the foregoing description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the foregoing description of heteroaryl groups may be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.

In the present disclosure, the term "deuterated" means that at least one of the formulae can be replaced with hydrogen (H) by deuterium (D). In some embodiments, in each formula, at least 10% deuterated means that at least 10% of the available hydrogen is replaced with deuterium. In some embodiments, each formula is at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% deuterated, or at least 90% deuterated.

(Anode and cathode)

An organic light emitting device according to the present disclosure includes an anode and a cathode.

As the anode material, it is generally preferable to use a material having a large work function 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, and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO₂Sb; conducting compounds, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline; and the like, but are not limited thereto.

As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO₂Al; and the like, but are not limited thereto.

(hole injection layer)

The organic light emitting device according to the present disclosure includes a hole injection layer on an anode, wherein the compound represented by chemical formula 1 is used as a material for the hole injection layer, and specifically, a cured product of the compound represented by chemical formula 1 is used as the hole injection layer.

In chemical formula 1, preferably, L₁Is phenylene, biphenyldiyl, terphenyldiyl, phenylnaphthalenediyl, binaphthyldiyl, phenanthrenediyl, spirobifluorenediyl, dimethylfluorenediyl, diphenylfluorenediyl, or tetraphenylfluorenediyl, and L₁Being unsubstituted or via one or two C_1-10Alkyl substitution.

Preferably, L₁Is any one selected from the following:

preferably, Ar₁Each independently is phenyl, biphenyl, naphthyl, phenanthryl or dimethylfluorenyl, and Ar₁Unsubstituted or substituted with 1 to 5 deuterium, or halogen.

Preferably, Ar₂Each independently is phenyl, biphenyl or naphthyl, Ar₂Is unsubstituted or substituted by: -R; 1 to 5 deuterium; 1 or 2C_1-10An alkyl group; 1 to 5 halogens; c_1-10An alkoxy group; substituted by C_1-10C of alkoxy_1-10An alkoxy group; c_1-10A haloalkyl group; or phenoxy, and R is as defined above.

Preferably, L₂Each independently a single bond, butylene, pentylene, hexylene, heptylene, or phenylene.

Preferably, n is 1, and R₁Each independently hydrogen or phenyl.

Preferably, R is-L₃-R₂、L₃Is a single bond, -O-, -S-, -CH₂-、-CH₂O-、-OCH₂-、-CH₂OCH₂-, -N (phenyl) -, or-O (CH)₂)₆-, and R₂Is any one selected from the following:

representative examples of the compound represented by chemical formula 1 are as follows:

the compound represented by chemical formula 1 may be at least 10% deuterated. Alternatively, the compound represented by chemical 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.

According to another embodiment, there is provided a method for preparing a compound represented by chemical formula 1 as shown in the following reaction scheme 1:

[ reaction scheme 1]

In reaction scheme 1, the definition of the remaining substituents other than X is the same as defined above, and X is halogen, and more preferably chlorine or bromine. The reaction is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction may be modified as known in the art. The above preparation method can be further presented in the preparation examples described below.

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

[ chemical formula 3]

In the chemical formula 3, the first and second,

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

Ar"₁is composed of

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

R"₁each independently is hydrogen, halogen or C_1-60A halogenated alkyl group,

n3 is an integer from 1 to 4,

Ar"₂is composed of

R"₂Each independently of the others is hydrogen, halogen, C_1-60Haloalkyl, a photocurable group or a thermosetting group, and

n4 is an integer from 1 to 5.

Preferably, for the photocurable group or thermosetting group of R ″, the contents regarding R defined in the above chemical formula 1 can be applied.

Preferably, R "₁Each independently hydrogen, fluorine or CF₃。

Preferably, Ar'₁Is any one selected from the following:

preferably, R "₂Each independently of the others being hydrogen, fluorine, CF₃、CF(CF₃)₂、CF₂CF₂CF₂CF₃A photocurable group, or a thermosetting group. In this case, for the photocurable group or the thermosetting group, the contents regarding R defined in the above chemical formula 1 may be applied.

Preferably, Ar'₂Is any one selected from the following:

representative examples of the compound represented by chemical formula 3 are as follows:

in the above group, the first and second substrates are,

n1 and n2 are as defined in chemical formula 3.

The compound represented by chemical formula 3 may be at least 10% deuterated. Alternatively, the compound represented by chemical 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.

Further, the hole injection layer according to the present disclosure may further include a cationic compound in addition to the compound represented by chemical formula 3 above. Examples of cationic compounds are as follows:

the ionic compound can be at least 10% deuterated. Preferably, the ionic compound can 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, a method of forming a hole injection layer according to the present disclosure is a method of subjecting the compound represented by chemical formula 1 (or together with the compound represented by chemical formula 3 and/or the cationic compound) to a heat treatment or a light treatment to prepare a cured product, which will be described later.

(hole transport layer)

The organic light emitting device according to the present disclosure includes a hole transport layer between a hole injection layer and a light emitting layer, wherein a polymer including a repeating unit represented by chemical formula 2-1 and a repeating unit represented by chemical formula 2-2 is used as a material for the hole transport layer. Specifically, a cured product of the polymer is used as a hole transport layer.

The chemical formula 2-1 may be represented by the following chemical formula 2-1-1:

[ chemical formula 2-1-1]

In the chemical formula 2-1-1,

R'₁to R'₃、L'₁To L'₃、Ar'₁To Ar'₄And Ra is the same as defined in chemical formula 2-1.

In chemical formula 2-1, preferably, R'₁To R'₃Each independently hydrogen or methyl, and more preferably, R'₁To R'₃All are hydrogen.

Preferably, L'₁Is substituted or unsubstituted C_6-20An arylene group; - (substituted or unsubstituted C)_6-20Arylene) -O- (substituted or unsubstituted C_6-20Arylene) -; - (substituted or unsubstituted C)_6-20Arylene) - (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-20Arylene) -; - (substituted or unsubstituted C)_6-20Arylene) -O- (substituted or unsubstituted C_1-10Alkylene) -O-; or- (substituted or unsubstituted C_6-20Arylene) - (substituted or unsubstituted C_1-10Alkylene) -O- (substituted or unsubstituted C_1-10Alkylene) - (substituted or unsubstituted C_6-20Arylene) -.

More preferably, L'₁Are phenylene, - (phenylene) O (phenylene) -, - (phenylene) (CH)₂)₆(phenylene) -; - (phenylene) O (CH)₂)₆O-; or- (phenylene) CH₂OCH₂(phenylene) -.

Most preferably, L'₁Is any one selected from the following:

preferably, L'₂And L'₃Each independently is a single bond; substituted or unsubstituted C_6-20Arylene, more preferably, L'₂And L'₃Each independently is a single bond or phenylene, and most preferably, L'₂And L'₃Each independently a single bond or 1, 4-phenylene.

Preferably, Ar'₁To Ar'₄Each independently is substituted or unsubstituted C_6-20Aryl, or substituted or unsubstituted C containing one or more members selected from N, O and S_2-20Heteroaryl, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form C_6-20An aromatic ring, or C comprising any one or more selected from N, O and S_2-20A heteroaromatic ring.

More preferably, Ar'₁To Ar'₄Each independently is phenyl, biphenyl substituted with N, N-diphenylamino, or dimethylfluorenyl, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form

Most preferably, Ar'₁To Ar'₄Each independently is any one selected from the following, or Ar'₁And Ar'₂Or Ar'₃And Ar'₄Are bonded to each other to form

Preferably, Ar'₁And Ar'₃Each independently being phenyl or biphenyl, Ar'₂And Ar'₄Is any one selected from the following, or Ar'₁And Ar'₂And Ar'₃And Ar'₄Are bonded to each other to form

Preferably, Ra is hydrogen, C_1-10Alkyl or C_6-20Aryl, more preferably, Ra is hydrogen, methyl or phenyl.

Preferably, chemical formula 2-1 is any one selected from the group consisting of repeating units represented by the following formulae:

the repeating unit represented by chemical formula 2-1 may be at least 10% deuterated. Alternatively, the repeating unit represented by chemical formula 2-1 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.

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

[ chemical formula 2-1' ]

In the chemical formula 2-1',

R'₁to R'₃、L'₁To L'₃、Ar'₁To Ar'₄And Ra is the same as defined in the above chemical formula 2-1.

The compound represented by chemical formula 2-1' may be prepared by a preparation method as shown in the following reaction scheme 2-1-1. In the compound represented by chemical formula 2-1', when L'₁Is- (phenylene) CH₂OCH₂(phenylene) -it may be, for examplePrepared by the preparation method as shown in the following reaction scheme 2-1-2, the other remaining compounds can be prepared in a similar manner.

[ reaction scheme 2-1-1]

[ reaction schemes 2-1-2]

In reaction scheme 2-1-1, except X'₁The remaining substituents other than those defined above are the same as defined above, and X'₁Is halogen or-OTf, and more preferably is iodine, bromine, chlorine or-OTf. Step 1 of reaction scheme 2-1-1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction may be modified as known in the art. Furthermore, step 2 is a Wittig reaction in which a ketone or aldehyde is reacted withYlide reaction to form olefins. The reactive groups used in the Wittig reaction may be modified as known in the art.

In reaction scheme 2-1-2, except X'₂The remaining substituents other than those defined above are the same as defined above, and X'₂Is halogen or-OTf, and more preferably is iodine, bromine, chlorine or-OTf. Step 1 of reaction scheme 2-1-2 is a reduction reaction in which hydrogen is added to an aldehyde, which may use NaBH₃、LiAlH₄In the presence of a metal catalyst₂And the like. The reactive groups used for the reduction reaction of the aldehyde may be modified as known in the art. Further, step 2 is a nucleophilic substitution reaction, which is a substitution reaction in which an alcohol is alkoxylated by addition of a base to produce a nucleophile, and then reacted with a halogen substituent as a leaving group. The reactive group for the nucleophilic substitution reaction may be as defined in the artAs is known in the art.

The above preparation method can be further presented in the preparation examples described below.

The repeating unit represented by chemical formula 2-2 includes R' as a curable reactive group.

Preferably, for the photocurable group or thermosetting group of R', the contents regarding R defined in the above chemical formula 1 can be applied.

Preferably, R'₄To R'₆Each independently hydrogen or methyl, more preferably, R'₄To R'₆All are hydrogen.

Preferably, L'₄Is a single bond, substituted or unsubstituted C_6-20Arylene, more preferably a single bond or phenylene, and most preferably a single bond or 1, 4-phenylene.

Preferably, chemical formula 2-2 is any one selected from the group consisting of repeating units represented by the following formulae:

the repeating unit represented by chemical formula 2-2 may be at least 10% deuterated. Alternatively, the repeating unit represented by chemical formula 2-2 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.

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

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

[ chemical formula 2-2' ]

In chemical formula 2-2', R'₄To R'₆And L'₄As defined in chemical formula 2-2 above.

The compound represented by chemical formula 2-2' may be prepared by a preparation method as shown in the following reaction scheme 2-2.

[ reaction scheme 2-2]

In reaction schemes 2-2, except for X'₃The remaining substituents other than those defined above are the same as defined above, and X'₃Is halogen, preferably bromine or chlorine. Reaction scheme 2-2 is a Suzuki coupling reaction, which is performed in the presence of a palladium catalyst and a base to prepare a compound represented by chemical formula 2-2'. The above preparation method can be further presented in the preparation examples described below.

The polymer according to the present disclosure may be prepared by polymerizing the monomer represented by chemical formula 2-1 'with the monomer represented by chemical formula 2-2'. Preferably, the polymer according to the present disclosure is a random copolymer comprising repeating units.

In the polymer according to the present disclosure, x and y are the mole fraction of the repeating unit of chemical formula 2-1 and the repeating unit of chemical formula 2-2 in the polymer, wherein x: y is 0.5 to 0.99:0.01 to 0.5, preferably 0.5 to 0.9:0.1 to 0.5. The molar ratio of the polymer may be adjusted by adjusting the reaction molar ratio of the monomer represented by chemical formula 2-1 'to the monomer represented by chemical formula 2-2'.

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

As used herein, the terms "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" are values converted to standard polystyrene measured using GPC (gel permeation chromatography). As used herein, unless otherwise specified, the term "molecular weight" means weight average molecular weight.

For example, molecular weight was measured using an Agilent PL-GPC 220 instrument equipped with a PLgel MIXED-B column (300 mm in length) from Polymer Laboratories. Here, the measurement temperature was 35 ℃, THF was used as a solvent, and the flow rate was measured at a rate of 1 mL/min. The sample was prepared at a concentration of 10mg/10mL and then supplied in an amount of 200. mu.L. The values of Mw and Mn were obtained using a calibration curve formed using polystyrene standards. As the polystyrene standard samples, nine kinds of samples each having a molecular weight of 2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 were used.

On the other hand, a method of forming the hole transport layer according to the present disclosure is a method of subjecting a polymer to a heat treatment or a light treatment to prepare a cured product, which will be described later.

(luminescent layer)

The light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specific examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene, having an arylamino group,Diindenopyrene, and the like. The styrylamine compound is a compound substituted with at least one arylvinyl group in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrriamine, styryltretramine, and the like. Further, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

(Electron transport layer)

The organic light emitting device according to the present disclosure 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 the electrons to the light emitting layer, and the electron transport material is a material that can well receive electrons from the cathode and transport the electrons to the light emitting layer, and a material having a large mobility to electrons is suitable. Specific examples thereof include 8-hydroxyquinoline Al complexes; comprising Alq₃The complex of (1); an organic radical compound; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with a predetermined desired cathode material as used according to the prior art. Examples of suitable cathode materials are, in particular, the usual materials having a low work function and being followed by an aluminum or silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, and in each case followed by an aluminum layer or a silver layer.

(Electron injection layer)

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

The electron injection layer is a layer that injects electrons from the electrode, and such a compound is preferable: it has an ability to transport electrons, has an effect of injecting electrons from a cathode, and has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to a hole injection layer, and has an excellent thin film forming ability. Specific examples thereof include fluorenones, anthraquinone dimethanes, diphenoquinones, thiopyran dioxides, and the like,Azole,Diazole, triazole, imidazole,Tetracarboxylic acid, fluorenylidene methane,Anthrone and the like, and derivatives thereof; a metal complex compound; a nitrogen-containing 5-membered ring derivative; and the like, but are not limited thereto.

Examples of the metal complex compounds include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), gallium tris (8-quinolinolato), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), chlorogallium bis (2-methyl-8-quinolinolato), gallium bis (2-methyl-8-quinolino) (o-cresol), aluminum bis (2-methyl-8-quinolino) (1-naphthol), gallium bis (2-methyl-8-quinolino) (2-naphthol), and the like, but are not limited thereto.

(organic light emitting device)

The organic light emitting device according to the present disclosure may be a normal type organic light emitting device in which an anode, at least one organic material layer, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present disclosure may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to one embodiment of the present disclosure is shown in fig. 1 and 2.

Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 6. In such a structure, the hole injection layer includes the compound represented by chemical formula 1, and the hole transport layer includes a polymer including a repeating unit represented by chemical formula 2-1, a repeating unit represented by chemical formula 2-2, and a repeating unit represented by chemical formula 2-3.

Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 7, an electron injection layer 8, and a cathode 6. In such a structure, the hole injection layer includes the compound represented by chemical formula 1, and the hole transport layer includes a polymer including a repeating unit represented by chemical formula 2-1, a repeating unit represented by chemical formula 2-2, and a repeating unit represented by chemical formula 2-3.

The organic light emitting device according to the present disclosure may be manufactured by materials and methods known in the art, except that the above elements are used.

For example, the organic light emitting device according to the present disclosure may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. In this case, the organic light emitting device may be manufactured by: an anode is formed by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can be used as a cathode is deposited on the organic material layer.

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

The organic light emitting device according to the present disclosure may be a front side emission type, a rear side emission type, or a double side emission type, depending on the material used.

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

(coating composition)

Meanwhile, the hole injection layer and the hole transport layer according to the present disclosure may be formed by a solution method, respectively. For this purpose, in some embodiments, there is provided a coating composition for forming a hole injection layer, comprising a compound represented by chemical formula 1 and a solvent; and a coating composition for forming a hole transport layer comprising a polymer including a repeating unit represented by chemical formula 2-1 and a repeating unit represented by chemical 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 disclosure. Examples of the solvent may include chlorine-based solvents such as chloroform, dichloromethane, 1, 2-dichloroethane, 1, 2-trichloroethane,chlorobenzene and o-dichlorobenzene; ether-based solvents, e.g. tetrahydrofuran and bisAn alkane; aromatic hydrocarbon-based solvents such as toluene, xylene, trimethylbenzene and mesitylene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, and 1, 2-hexanediol, and derivatives thereof; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide-based solvents, such as dimethyl sulfoxide; amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; benzoate-based solvents such as butyl benzoate and methyl-2-methoxybenzoate; tetralin; 3-phenoxy-toluene; and so on. Further, the above solvents may be used alone or in a combination of two or more solvents.

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

Further, the viscosity of the coating composition is preferably 1cP to 10cP, and within the above range, the coating is easy. Furthermore, the concentration of the compound according to the present disclosure in the coating composition is preferably 0.1 to 20% w/v.

Further, the coating composition may further include one or two or more additives selected from a thermal polymerization initiator and a photopolymerization initiator.

Examples of the thermal polymerization initiator may include: peroxide initiators, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2, 4-dichlorobenzoyl peroxide, bis-3, 5, 5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide; or azo-based initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, and azobiscyclohexanecarbonitrile, but not limited thereto.

Examples of the photopolymerization initiator may include: acetophenone-based or ketal-based photopolymerization initiators, such as diethoxyacetophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime; benzoin ether-based photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin ethyl ether; benzophenone-based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl and 4-benzoylphenyl ether; thioxanthone-based photopolymerization initiators such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone; and other photopolymerization initiators such as ethylanthraquinone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 4-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, but not limited thereto.

Further, those having a photopolymerization promoting effect may also be used alone or in combination with a photopolymerization initiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl (2-dimethylamino) benzoate, 4' -dimethylaminobenzophenone, and the like, but are not limited thereto.

In another embodiment of the present disclosure, a method for forming a hole injection layer and a hole transport layer using the above-described coating composition is provided. Specifically, the method comprises the following steps: applying the above coating composition for forming a hole injection layer to an anode by a solution method; and subjecting the applied coating composition to a heat treatment or a light treatment. Furthermore, the method comprises the steps of: applying the above-described coating composition for forming a hole transport layer onto a hole injection layer by a solution method; and subjecting the applied coating composition to a heat treatment or a light treatment.

The solution method uses the coating composition according to the present disclosure, and means spin coating, dip coating, blade coating, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

The heat treatment temperature in the heat treatment step is preferably 150 to 230 ℃. In some embodiments, the heat treatment time may be 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In some embodiments, the heat treatment is preferably performed in an inert gas atmosphere, such as argon and nitrogen. Further, a step of evaporating the solvent may be further included between the coating step and the heat treatment or the light treatment.

The preparation of the organic light emitting device according to the present disclosure will be described in detail in the following examples. However, these examples are presented for illustrative purposes only, and the scope of the present disclosure is not limited thereto.

[ preparation example-HIL host ]

Preparation examples 1 to 1: preparation of Compound 1-1

Toluene was charged to accommodate the compounds 1-1 ' (1.58g, 3.74mmol), N4, N4' -diphenyl- [1,1' -biphenyl]-4,4' -diamine (572mg, 1.7mmol) and sodium tert-butoxide (980mg, 10.2mmol) in a flask. The flask containing the reactants was immersed in an oil bath at 90 ℃ and then Pd (P (tBu)₃)₂(43mg, 0.085mmol) and stirred for 1 hour. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. Removing organic solvent by rotary vacuum concentrator, and making residueThe substance was subjected to column purification to obtain Compound 1-1(950mg, yield: 55%, HPLC purity: 99.5%).

¹H NMR(500MHz，CDCl₃)：δ7.71(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 examples 1 to 2: preparation of Compounds 1-2

Toluene was charged to accommodate the compounds 1-2 ' (1.37g, 3.03mmol), N4, N4' -diphenyl- [1,1' -biphenyl]-4,4' -diamine (464mg, 1.38mmol) and sodium tert-butoxide (769mg, 8.3mmol) in a flask. The flask containing the reactants was immersed in an oil bath at 90 ℃ and then Pd (P (tBu)₃)₂(36mg, 0.085mmol) and stirred for 1 hour. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. The organic solvent was removed using a rotary vacuum concentrator, and the residue was subjected to column purification to obtain compound 1-2(500mg, yield: 34%, HPLC purity: 99.8%).

¹H NMR(500MHz，CDCl₃)：δ7.70(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 examples 1 to 3: preparation of Compounds 1-3

Toluene was placed in a flask containing compound 1-3 ' (2.32g, 5.0mmol), 2' -dibromo-9, 9' -spirobi (fluorene) (948mg, 2.0mmol) and sodium tert-butoxide (960mg, 10.0 mmol). Immersing the flask containing the reactant in a solution at 90 deg.CIn an oil bath, then Pd (P (tBu)₃)₂(72mg, 0.14mmol) and stirred for 1 hour. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. The organic solvent was removed using a rotary vacuum concentrator, and the residue was subjected to column purification to obtain compound 1-3(1.46g, yield: 59%, HPLC purity: 99.2%).

¹H NMR(500MHz，CDCl₃)：δ7.74-7.69(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 examples 1 to 4: preparation of Compounds 1-4

Toluene was placed in a container containing the compounds 1-4 ' (1.6g, 4.2mmol), N4, N4' -bis (naphthalen-1-yl) - [1,1' -biphenyl]A flask of-4, 4' -diamine (873mg, 2.0mmol) and sodium tert-butoxide (769mg, 8.0mmol) and sparged with nitrogen. The flask containing the reactants was immersed in an oil bath at 100 ℃ and then Pd (P (tBu)₃)₂(82mg, 0.16mmol) and stirred for 12 h. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. The organic solvent was removed using a rotary vacuum concentrator, and the residue was subjected to column purification to obtain compounds 1-4(1.2g, yield: 53%, HPLC purity: 99.1%).

¹H NMR(500MHz，CDCl₃)：δ7.90-7.88(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)

[ preparation 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 (12g, 25mmol), Pd (PPh)₃)₄(578mg, 0.5mmol) and K₂CO₃(6.9g, 50mmol) was placed in a round bottom flask, which was then purged with nitrogen. To this was added 1, 3-dibromo-5-fluorobenzene (1.26mL, 10mmol), THF (tetrahydrofuran, 40mL) and H₂O (10mL), then stirred at 90 ℃ for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to remove the organic solvent, and then the residue was subjected to column purification to obtain 9.5g (yield: 98%) of intermediate a 1.

Step 2) preparation of intermediate a2

NaH (60 wt%, 420mg, 10.5mmol) was placed in a round bottom flask, which was then purged with nitrogen. NMP (N-methylpyrrolidone, 8.8mL) was added thereto, followed by cooling to 0 ℃. A solution of 3-bromocarbazole (2.6g, 10.5mmol) dissolved in NMP (8.8mL) was slowly added to the reaction mixture, followed by stirring at 0 ℃ for 30 minutes. A solution of intermediate a1(6.8g, 7mmol) dissolved in NMP (17mL) was added to the reaction mixture, which was then stirred at 220 ℃ for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to remove the organic solvent, and the residue was subjected to column purification to obtain 5g (yield: 60%) of intermediate a 2.

Step 3) preparation of intermediate a3

Intermediate a2(4g, 3.35mmol), 4-formylphenylboronic acid (750mg, 5mmol), Pd (PPh)₃)₄(196mg, 0.17mmol) and K₂CO₃(1.4g, 10mmol) was placed in a round bottom flask, which was then purged with nitrogen. To this was added THF (13.4mL) and H₂O (3.4mL), then stirred at 90 ℃ for 4 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to remove the organic solvent, and then the residue was subjected to column purification to obtain 2.87g (yield: 70%) of intermediate a 3.

Step 4) preparation of Compound 2-1

Will CH₃PPh₃Br (1.57g, 4.4mmol) and THF (12mL) were placed in a round bottom flask, then purged with nitrogen and cooled to 0 ℃. KOtBu (494mg, 4.4mmol) was added to the reaction mixture, which was then purged with nitrogen and stirred at 0 ℃ for 20 minutes. A solution of intermediate a3(2.68g, 2.2mmol) dissolved in THF (10mL) was slowly added to the reaction mixture, followed by stirring at 0 ℃ for 40 minutes. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to remove the organic solvent, and then the residue was subjected to column purification to obtain 2.25g (yield: 84%) of compound 2-1.

¹H NMR(500MHz，CD₂Cl₂)：δ8.40(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 examples 2 to 2: preparation of Compound 2-2

Step 1) preparation of intermediate b1

Intermediate a3(2.44g, 2mmol) was placed in a round bottom flask and then dissolved in MeOH (5mL) and THF (5 mL). While the reaction mixture was kept at room temperature, sodium borohydride (227mg, 6mmol) was added little by little, and then the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to obtain 2.1g (yield: 86%) of intermediate b 1.

Step 2) preparation of Compound 2-2

Sodium hydride (60 wt%, 112mg, 2.8mmol) was placed in a round bottom flask and the atmosphere was purged to replace with nitrogen. Anhydrous DMF (3.5mL) was added thereto, followed by cooling to 0 ℃. A solution of intermediate b1(1.71g, 1.4mmol) dissolved in anhydrous DMF (3.5mL) was slowly added to the reaction mixture, which was then stirred at 0 ℃ for 1 hour. After addition of 4-vinylbenzyl chloride (0.39mL, 2.8mmol), the temperature was raised to 60 ℃ and the mixture was stirred for 4 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. After collecting the organic layer, MgSO₄The organic layer was dried and filtered. The filtrate was dried with a rotary vacuum concentrator to blow off the organic solvent. The residue was subjected to column purification to obtain 1.22g (yield: 65%) of compound 2-2.

¹H NMR(500MHz，CDCl₃)：δ8.40(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 examples 2 to 3: preparation of Polymer C1

Compound 2-1(973mg, 0.8mmol) and azobisisobutyronitrile (1.3mg, 0.008mmol) were placed in a round-bottom flask, which was then dissolved in dry toluene (1.6mL) under a nitrogen atmosphere. The mixture was stirred at 70 ℃ for 6 hours. After completion of the reaction, the reaction mixture was diluted with THF (5mL) and then added to ethyl acetate (70 mL). The precipitate was filtered and washed with ethyl acetate. The obtained solid was dried to obtain 620mg (yield: 64%) of polymer C1. (Mw 102591, Mn 45941; number average molecular weight and weight average molecular weight were measured by GPC using PS standards and Agilent1200 series).

Preparation examples 2 to 4: preparation of Polymer C2

Compound 2-1(973mg, 0.8mmol) and 3- (4-vinylphenyl) bicyclo [4.2.0] octa-1 (6),2, 4-triene (41mg, 0.2mmol) and azobisisobutyronitrile (1.3mg, 0.008mmol) were placed in a round bottom flask and then dissolved in anhydrous toluene (1.6mL) under a nitrogen atmosphere. The mixture was stirred at 70 ℃ for 6 hours. After completion of the reaction, the reaction mixture was diluted with THF (5mL) and then added to ethyl acetate (70 mL). The precipitate was filtered and washed with ethyl acetate. The obtained solid was dried to obtain 730mg (yield: 72%) of polymer C2. (Mw 90410, Mn 48393; number average molecular weight and weight average molecular weight were measured by GPC using PS standards and Agilent1200 series).

Preparation examples 2 to 5: preparation of Polymer C3

Compound 2-2(1.07g, 0.8mmol) and 3- (4-vinylphenyl) bicyclo [4.2.0] octa-1 (6),2, 4-triene (41mg, 0.2mmol) and azobisisobutyronitrile (1.3mg, 0.008mmol) were placed in a round bottom flask and then dissolved in anhydrous toluene (1.6mL) under a nitrogen atmosphere. The mixture was stirred at 70 ℃ for 6 hours. After completion of the reaction, the reaction mixture was diluted with THF (5mL) and then added to ethyl acetate (70 mL). The precipitate was filtered and washed with ethyl acetate. The obtained solid was dried to obtain 689mg (yield: 62%) of polymer C3. (Mw 108187, Mn 78944; number and weight average molecular weights were measured by GPC using PS standards and Agilent1200 series)

[ preparation example-HIL dopant ]

Preparation example 3-1: preparation of Compound 3-1

Step 1) preparation of Compound 3-1

Mg (193Mg, 7.92mmol), I under nitrogen atmosphere₂(4mg) and THF (10mL) were placed in a 100mL round-bottom flask and stirred for 30 minutes. 4-bromostyrene (1.04mL, 7.92mmol) was added thereto, and the mixture was stirred for one day while placing a 30 ℃ water bath under the round bottom flask. The dissolution of Mg was determined by blackening the solution. Diethyl ether (5mL) was added to dilute the reaction solution. Tris (pentafluorophenyl) borane (1g, 3.96mmol) was dissolved in diethyl ether (5mL) and slowly added to the reaction solution for 30 min. The solution was stirred for one day. Mixing Na₂CO₃(0.1M, 80mL, 8.0mmol) was slowly added to the reaction solution. The organic solvent was extracted with ethyl acetate (20mL x 3) and MgSO₄The residual water was removed. To additionally remove residual water and impurities, the resultant was distilled with benzene using Dean-stark. When about 10mL of the solvent remained, the solution was cooled and filtered to obtain Compound 3-1' (1.6g, yield: 64%).

Step 2) preparation of Compound 3-1

Compound 3-1' (100mg, 0.16mmol), distilled water (10mL) and Ph₂ICl (60mg, 0.19mmol) was placed in a 25mL round bottom flask and stirred for 1 hour. Acetone (15mL) was added to the reaction solution to cause precipitation, and the precipitate was filtered and dried to give compound 3-1(140mg, yield: 100%).

MS：[M-H]^-615 (negative mode)

MS：[M+H]⁺281 (positive mode)

Preparation examples 3 to 2: preparation of Compound 3-2

Step 1) preparation of Compound 3-2

Methyltriphenylpotassium bromide (13.90g, 38.91mmol) and THF (100mL) were placed in a 250mL round bottom flask and stirred at 0 deg.C for 30 min. n-BuLi (15.6mL, 38.91mmol, 2.5M in hexanes) was added slowly to the reaction solution and stirred at 0 ℃ for 30 min. 4-formyl-2, 3,5, 6-tetrafluoro-1-bromobenzene (5.0g, 19.47mmol, 30mL in THF) was slowly added to the reaction solution at 0 deg.C. The reaction solution was stirred while gradually raising the temperature to room temperature. After 3 hours, diethyl ether (100mL) and saturated NH were added₄A Cl solution (400mL) was added to the reaction solution. The organic solvent was extracted with diethyl ether (200 mL. times.2) and MgSO₄The residual water was removed. The resultant was subjected to column chromatography with ethyl acetate: hexane ═ 1:9 (vol: vol) to give compound 3-2' (1.29g, yield: 26%).

Step 2) preparation of Compound 3-2 ″

Mg (95Mg, 3.92mmol), THF (10mL) and I₂(4mg) was placed in a 25mL round bottom flask and stirred. Compound 3-2' (1.0g, 3.92mmol) was added to the reaction solutionAnd stirred at room temperature. After 10 hours, complete dissolution of Mg was determined by solution darkening and diethyl ether (10mL) and BCl were added over 30 minutes₃(1.3mL, 1.3mmol, 1M in hexanes). After the reaction solution was stirred for one day, Na was added₂CO₃(30mL, 3.0mmol in H₂0.1M in O). The synthesized material was extracted with ethyl acetate (10mL x 3) and then with MgSO₄The residual water was removed. After removing all the solvent, water was completely removed with benzene using dean-Stark, and the solid was filtered to obtain compound 3-2 "(340 mg, yield: 28%).

Step 3) preparation of Compound 3-2

The compound 3-2' (200mg, 0.27mmol), 1- (4-vinylbenzyl) pyridine-1-Chloride (69mg, 0.30mmol), H₂O (10mL) and dichloromethane (10mL) were placed in a 25mL round bottom flask and stirred vigorously for 30 minutes. The organic solvent was extracted with ether (10 mL. times.3) and MgSO₄The residual water was removed. The solvent was removed and dried in vacuo to give compound 3-2(247mg, yield: 100%).

MS：[M-H]^-711 (negative mode)

MS：[M+H]⁺196 (positive mode)

Preparation examples 3 to 3: preparation of Compound 3-3

Step 1) preparation of Compound 3-3

1-bromo-2, 3,5, 6-tetrafluoro-4- (1,2, 2-trifluorovinyl) benzene (2g, 7.84mmol) was added to THF (20mL) in a 50mL round bottom flask and stirred at-78 ℃ for 30 min. n-BuLi (3.45mL, 8.63mmol, 2.5M in hexanes) was slowly added to the solutionIn solution and stirred at-78 ℃ for 30 minutes. The BCl was incubated at-78 deg.C for 15 minutes₃(2.6mL, 2.61mmol, 1M in hexanes) was added to the reaction solution and stirred. The reaction solution was stirred for one day while the temperature was slowly raised to room temperature, and then water (30mL) was added. The synthesized material was extracted with ethyl acetate (10mL x 3) and then all solvent was removed. Water was completely removed with benzene using dean-Stark, and the solid was filtered to obtain compound 3-3' (800mg, yield: 43%).

Step 2) preparation of Compound 3-3

Compound 3-3' (400mg, 0.56mmol), diphenyl iodideChloride (176mg, 0.56mmol), water (10mL) and acetone (10mL) were placed in a 25mL round bottom flask and stirred vigorously for 30 minutes. The resultant was extracted with dichloromethane (10mL × 3), and then dried after removing the solvent to obtain compound 3-3(552mg, yield: 100%).

MS：[M-H]^-711 (negative mode)

MS：[M+H]⁺281 (positive mode)

Preparation examples 3 to 4: preparation of Compounds 3-4

Step 1) preparation of Compound 3-4

Potassium carbonate (10.4g, 75.3mmol) was placed in a 500mL round-bottom flask, to which DMF (200mL) was added. 2,3,5, 6-tetrafluorophenol (10.0g, 60.22mmol) was added to the flask, and the mixture was stirred at 60 ℃ for 30 minutes. 4-vinylbenzyl chloride (7.66g, 50.18mmol) was slowly added to the reaction solution and stirred at 60 ℃ for 16 hours. Then, water (300mL) and ethyl acetate (200mL) were added. The organic layer was extracted with ethyl acetate (200 mL. times.2), andwith MgSO₄The residual water was removed. The resultant was subjected to column chromatography with ethyl acetate: hexane ═ 1:9 (v: v) to give compound 3-4' (11.2g, yield: 79%).

Step 2) preparation of Compounds 3-4 ″

Compound 3-4' (10g, 35.43mmol) was placed in a 250ml round-bottom flask, to which diethyl ether (130ml) was added, and the mixture was stirred. The reaction solution was cooled to-78 ℃ and stirred for 30 minutes. n-BuLi (17mL, 42.52mmol, 2.5M in hexanes) was injected slowly over 30 minutes. Then, the resultant was stirred for 1 hour. Slowly add BCl over 30 min₃(8.15ml, 8.15mmol, 1M in hexanes). The temperature of the reaction solution was slowly raised to room temperature. After the reaction solution was stirred for one day, water (200mL) was added thereto. The synthesized material was extracted with ether (100mL x 3) and all solvents were removed. Thereafter, water was completely removed with benzene using dean-Stark, and the solid was filtered to obtain Compound 3-4 "(6.2 g, yield: 66%).

Step 3) preparation of Compounds 3-4

Mixing compound 3-4 ″ (6.2g, 5.42mmol) and diphenyl iodideChloride (2.57g, 8.13mmol), water (50mL) and acetone (10mL) were placed in a 25mL round bottom flask and stirred vigorously for 30 minutes. The organic solvent was extracted with dichloromethane (20mL x 3) and the solvent was removed. The resultant was subjected to column chromatography with dichloromethane: acetone ═ 9:1 (v: v) to give compound 3-4(5.0g, yield: 65%).

MS：[M-H]^-1135 (negative mode)

MS：[M+H]⁺281 (positive mode)

Preparation example a: preparation of comparative Compound 1

Toluene was charged to a reactor containing 2-bromo-9, 9-diphenyl-9H-fluorene (1.49g, 3.74mmol), N4, N4 '-diphenyl- [1,1' -biphenyl]-4,4' -diamine (572mg, 1.7mmol) and sodium tert-butoxide (980mg, 10.2mmol) in a flask. The flask containing the reactants was immersed in an oil bath at 90 ℃ and then Pd (P (tBu)₃)₂(43mg, 0.085mmol) and stirred for 1 hour. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. The organic solvent was removed using a rotary vacuum concentrator, and the residue was subjected to column purification to give comparative compound 1(870mg, HPLC purity: 99.0%).

MS：[M+H]⁺＝969

Preparation example B: preparation of comparative Compound 2

Toluene was placed in a container containing bromonaphthalene (774mg, 3.74mmol), N4, N4 '-diphenyl- [1,1' -biphenyl]-4,4' -diamine (572mg, 1.7mmol) and sodium tert-butoxide (980mg, 10.2mmol) in a flask. The flask containing the reactants was immersed in an oil bath at 90 ℃ and then Pd (P (tBu)₃)₂(43mg, 0.085mmol) and stirred for 1 hour. The reaction was stopped by adding water, the mixture was extracted with dichloromethane and then MgSO₄The organic layer was dried. The organic solvent was removed using a rotary vacuum concentrator, and the residue was subjected to column purification to give comparative compound 2(830mg, HPLC purity: 99.0%).

MS：[M+H]⁺＝589

Preparation example C: preparation of comparative Polymer 1

Step 1) preparation of Compound d1

2,2 '-dibromo-9, 9' -spirobifluorene (50g, 105.4mmol, 1.0 equiv.) and 4-vinylphenylboronic acid (31.2g, 211mmol, 2.0 equiv.) were dissolved in 300g of Tetrahydrofuran (THF) and stirred in a water bath at 80 ℃ for 10 minutes. Will K₂CO₃(37.89g, 274mmol, 2.60 equiv.) was dissolved in 300mL of water and then added dropwise over 10 minutes. Pd catalyst (3.66g, 3.2mmol, 0.03 eq) was added at reflux. After stirring for 2 hours, with Ethyl Acetate (EA)/H₂The mixture was washed with O, the organic layer was separated, and the solvent was dried in vacuo. The resulting material was purified by column chromatography via n-hexane (n-Hex) and Ethyl Acetate (EA), followed by recrystallization from Tetrahydrofuran (THF) and ethanol to give compound d1' (22.8g) as a white solid.

MS：[M+H]⁺＝496

Step 2) preparation of monomer d1

Compound d1'(2.4g, 5.0mmol, 1.0 equiv.) and compound d2' (2.82g, 5.0mmol, 1.0 equiv.) were dissolved in 20mL of 1, 4-bisIn an alkane and stirred in a water bath at 120 ℃ for 30 minutes. Will K₂CO₃(5.10g, 37mmol, 1.75 equivalents) was dissolved in 40mL of water and the solution was added dropwise over 10 minutes while maintaining the internal temperature at 90 ℃. Pd catalyst (0.077g, 0.15mmol, 0.03 eq.) was added at reflux. After stirring for 1 hour, the mixture was stirred with Ethyl Acetate (EA)/H₂The mixture was washed with O, the organic layer was separated, and the solvent was dried in vacuo. The resulting material was purified by column chromatography via n-hexane (n-Hex) and Dichloromethane (DCM) and recrystallized from n-hexane (n-Hex) to give monomer d 1.

MS：[M+H]⁺＝854.5

Step 3) preparation of comparative Polymer 1

Monomer 1(500mg) and Azobisisobutyronitrile (AIBN) (1.2mg) were added to Ethyl Acetate (EA), and reacted at 25 ℃ for 12 hours under nitrogen substitution. The precipitate formed after the reaction was filtered to prepare comparative polymer 1.

Comparative Polymer 1 was prepared having a number average molecular weight of 37,100g/mol and a weight average molecular weight of 78,600 g/mol. At this time, the molecular weight was measured by GPC using PS standards and Agilent1200 series.

[ device examples ]

Example 1

Is coated thereon with a thickness ofITO (indium tin oxide) as a glass substrate of the thin film was ultrasonically cleaned with an acetone solvent for 10 minutes. Then, the substrate was put into distilled water in which a detergent was dissolved, ultrasonically cleaned for 10 minutes, and then ultrasonically cleaned twice for 10 minutes using distilled water. After the completion of the washing with distilled water, the substrate was ultrasonically washed with an isopropyl alcohol solvent for 10 minutes, and then dried. The substrate was then transferred to a glove box.

On the transparent ITO electrode prepared as above, a2 wt% cyclohexanone solution containing the previously prepared compounds 1-2 and 3-3 in a weight ratio of 8:2 was spin-coated and heat-treated at 230 ℃ for 30 minutes to form a film having a thickness ofThe hole injection layer of (1). A0.8 wt.% toluene solution containing the previously prepared polymer C2 was spin coated on the hole injection layer to form a thickness ofThe hole transport layer of (1).

Subsequently, the resultant was transferred to a vacuum depositor,the following compound A and the following compound B were then vacuum-deposited on the hole transport layer at a weight ratio of 9:1 to form a film having a thickness ofThe light emitting layer of (1). Vacuum depositing the following compound C on the light emitting layer to a thickness ofElectron injection and transport layers. On the electron injection and transport layers, sequentially deposited with thicknesses ofAndand aluminum, thereby forming a cathode.

In the above process, the deposition rate of the organic material is maintained atPer second toSecond, the deposition rates of LiF and Al are respectively maintained atSecond andsecond, and the vacuum during deposition was maintained at 2 x 10^-8To 5 x 10^-6And (4) supporting.

Examples 2 to 29

An organic light-emitting device was fabricated 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 fabricated 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.

Examples of the experiments

For the organic light emitting devices fabricated in the examples, at 10mA/cm²The driving voltage, current efficiency, power efficiency and lifetime were measured at the current density of (a), and the results are shown in table 1 below. In this case, LT90 means the time required for the luminance to decrease to 90% of the initial luminance.

[ Table 1]

As shown in the above table 1, it was determined that the organic light emitting device of the embodiment in which the cured product of the compound represented by chemical formula 1 was used as the host material of the hole injection layer and the cured product of the polymer including the repeating unit represented by chemical formula 2-1 and the repeating unit represented by chemical formula 2-2 was used as the hole transport layer material exhibited improved characteristics in terms of driving voltage, efficiency, and lifetime, particularly exhibited a significantly improved lifetime, as compared to the organic light emitting device in which the cured product of the polymer not including the repeating unit represented by chemical formula 2-1 and/or chemical formula 2-2 was used as the material of the hole transport layer.

It was also determined that the organic light emitting device of one embodiment of the present disclosure exhibits improved characteristics in terms of driving voltage, efficiency, and lifetime, particularly exhibits significantly improved lifetime, as compared to an organic light emitting device using a compound not including a curable group as a host material for a hole injection layer.

[ reference numerals ]

1: substrate 2: anode

3: hole injection layer 4: hole transport layer

5: light-emitting layer 6: cathode electrode

7: electron transport layer 8: electron injection layer