阅读说明：本技术 有机发光器件 (Organic light emitting device ) 是由 徐尚德 郑珉祐 李征夏 韩修进 朴瑟灿 黄晟现 李东勋 于 2020-12-04 设计创作，主要内容包括：本公开内容提供了具有改善的驱动电压、效率和寿命的有机发光器件。(The present disclosure provides an organic light emitting device having improved driving voltage, efficiency, and lifetime.)

1. An organic light emitting device comprising:

an anode, a cathode, and a light emitting layer between the anode and the cathode,

wherein the light emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:

[ chemical formula 1]

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

a is a benzene ring condensed with two adjacent pentagonal rings respectively,

Ar₁to Ar₃Each independently is 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_5-60(ii) a heteroaryl group, wherein,

each R₁Independently is hydrogen; deuterium; halogen; a cyano group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_2-60An alkynyl group; substituted or unsubstituted C_3-60A cycloalkyl 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,

x is an integer of 1 to 10,

with the proviso that Ar₁To Ar₃And R₁Is substituted with at least one deuterium, or R₁At least one of which is deuterium, and said first compound comprises at least 5 deuterium,

[ chemical formula 2]

In the chemical formula 2,

b is a benzene ring condensed with two adjacent pentagonal rings respectively,

Ar₄is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

Ar₅is substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C containing a heteroatom selected from N, O and S_5-60(ii) a heteroaryl group, wherein,

each R₂Independently is hydrogen; deuterium; halogen; a cyano group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_2-60An alkynyl group; substituted or unsubstituted C_3-60A cycloalkyl 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_2-60Heteroaryl, and

y is an integer of 1 to 10.

2. The organic light emitting device according to claim 1, wherein the chemical formula 1 is represented by any one selected from the following chemical formulae 1-1 to 1-6:

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

In the chemical formulae 1-1 to 1-6, Ar₁To Ar₃、R₁And x is as defined in claim 1.

3. The organic light emitting device of claim 1, wherein Ar₁To Ar₃Each independently is phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

4. The organic light emitting device of claim 1, wherein Ar₁To Ar₃At least one of which is phenyl and the remainder are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

5. The organic light emitting device of claim 1, wherein Ar₁To Ar₃At least one of which is a phenyl group substituted with 5 deuterium groups, and the remainder being each unsubstituted phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

6. The organic light emitting device of claim 1, wherein the Ar is₁To Ar₃One of which is biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, each substituted with 5 or more deuterium groups, and

the remainder are independently unsubstituted phenyl or unsubstituted biphenyl.

7. The organic light emitting device of claim 1, wherein Ar₁To Ar₃One of phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, and

ar is₁To Ar₃Completely substituted with deuterium.

8. An organic light-emitting device according to claim 1 wherein all of the R' s₁Is hydrogen.

9. The organic light emitting device of claim 1, wherein R is₁At least 5 of which are deuterium, and the remainder being hydrogen.

10. The organic light-emitting device according to claim 1, wherein the first compound is any one selected from the group consisting of:

11. the organic light emitting device according to claim 1, wherein the chemical formula 2 is represented by any one selected from the following chemical formulae 2-1 to 2-6:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

In chemical formulae 2-1 to 2-6, Ar₄、Ar₅、R₂And y is as defined in claim 1.

12. The organic light emitting device of claim 1, wherein Ar₄And Ar₅Each independently is a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, or a 9, 9-diphenylfluorenyl group, each of which is unsubstituted.

13. The organic light emitting device of claim 1, wherein Ar₄Is in each case unsubstituted phenyl, biphenyl or terphenyl, and

Ar₅is respectively unsubstituted dibenzofuranyl, dibenzothienyl, carbazole-9-yl or 9-phenyl-9H-carbazolyl.

14. An organic light-emitting device according to claim 1 wherein all R' s₂Is hydrogen.

15. An organic light-emitting device according to claim 1, wherein the second compound is any one selected from the group consisting of:

Technical Field

Cross Reference to Related Applications

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

The present disclosure relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

Background

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted 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 enhance 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, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to a ground state again.

Among the above organic light emitting devices, there is a continuous need to develop organic light emitting devices having improved driving voltage, efficiency, and lifetime.

Disclosure of Invention

Technical problem

It is an object of the present disclosure to provide an organic light emitting device having improved driving voltage, efficiency and lifetime.

Technical scheme

Provided herein are the following organic light emitting devices:

an organic light emitting device, comprising: an anode, a cathode, and a light-emitting layer between the anode and the cathode,

wherein the light emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.

[ chemical formula 1]

In the chemical formula 1, the first and second,

a is a benzene ring condensed with two adjacent pentagonal rings respectively,

Ar₁to Ar₃Each independently is 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_5-60(ii) a heteroaryl group, wherein,

each R₁Independently is hydrogen; deuterium; halogen; a cyano group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_2-60An alkynyl group; substituted or unsubstituted C_3-60A cycloalkyl 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,

x is an integer of 1 to 10,

with the proviso that Ar₁To Ar₃And R₁Is substituted with at least one deuterium, or R₁At least one of which is deuterium, and the first compound comprises at least 5 deuterium,

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

b is a benzene ring condensed with two adjacent pentagonal rings respectively,

Ar₄is substituted or unsubstituted C_6-60An aryl group, a heteroaryl group,

Ar₅is substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C containing a heteroatom selected from N, O and S_5-60(ii) a heteroaryl group, wherein,

each R₂Independently is hydrogen; deuterium; halogen; a cyano group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_2-60An alkynyl group; substituted or unsubstituted C_3-60A cycloalkyl 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_2-60Heteroaryl, and

y is an integer of 1 to 10.

Advantageous effects

The organic light emitting device described above has excellent driving voltage, efficiency, and lifetime by including the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 in the light emitting layer.

Drawings

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

Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

Detailed Description

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

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

As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile 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 a heterocyclic group comprising at least one of N, O and the S atom, 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 attached" may be a biphenyl group. That is, biphenyl can be an aryl group, or it can 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) vinyl-1-yl, stilbenyl, 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, perylenyl,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 substituted fluorenyl radicals, may formAnd the like. However, the structure is not limited thereto.

In the present disclosure, the heterocyclic group is a heterocyclic group containing 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. Examples of heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,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, and arylamine 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 group may employ the foregoing description of the heterocyclic 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 heterocyclyl 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 the combination of two substituents. In the present disclosure, the foregoing description of heterocyclic groups may be applied, except that the heterocyclic group is not a monovalent group but is formed by combining two substituents.

The organic light emitting device according to the present disclosure may be a normal type organic light emitting device in which an anode, a light emitting layer, and a cathode are sequentially stacked on a substrate, or an inverted type organic light emitting device in which a cathode, a light emitting layer, and an anode are sequentially stacked on a substrate. In addition, the organic light emitting device may further optionally include at least one of a hole injection layer, a hole transport layer, and an electron blocking layer between the anode and the light emitting layer, and may further include at least one of a hole blocking layer, an electron injection layer, and an electron transport layer between the cathode and the light emitting layer. In addition, the electron injection layer and the electron transport layer may be included in the form of a single layer of the electron injection and transport layer, not a separate layer.

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

An anode and a cathode

The anode and the cathode used in the present disclosure mean electrodes used in an organic light emitting device.

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); of metals and oxidesCombinations, e.g. ZnO: Al or SnO₂Sb; conducting polymers, 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 may further include a hole injection layer on the anode, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has an ability to transport holes, and thus has an effect of injecting holes in the anode and an excellent hole injection effect to the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injecting layer or the electron injecting material, and is also excellent in an ability to form a thin film. Further, it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanenitrile-based hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.

Hole transport layer

If necessary, the organic light emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if present).

The hole transport layer is a layer that can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer, and the hole transport material is suitably a material having a large hole mobility that can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer.

Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers in which a conjugated portion and a non-conjugated portion coexist, and the like, but are not limited thereto.

Luminescent layer

The light-emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transported from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present disclosure, includes a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2 as hosts.

Preferably, the first compound represented by chemical formula 1 may be substituted with 5 or more deuterium. Specifically, Ar in chemical formula 1₁To Ar₃And R₁Is substituted with at least one deuterium, or R₁At least one of which is deuterium, whereby the first compound may contain 5 or more, or 6 or more, or 7 or more, or 8 or more, or 10 or more deuterium in the compound, or the first compound may be completely substituted with deuterium.

Preferably, chemical formula 1 may be represented by any one selected from the following chemical formulae 1-1 to 1-6:

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

In chemical formulae 1-1 to 1-6, Ar₁To Ar₃、R₁And x is as defined above.

In chemical formula 1, preferably, Ar₁To Ar₃May each independently be phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

In chemical formula 1, more preferably, Ar₁To Ar₃At least one of which may be phenyl, and the remainder may each independently be phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

Further, Ar₁To Ar₃At least one of which may be substituted with at least one deuterium. For example, Ar₁To Ar₃At least one of which may be selected from the following structures:

in the above formula, a is an integer of 1 to 5,

b is an integer of 0 to 4, c is an integer of 0 to 5, with the proviso that b and c are not simultaneously 0,

each d is independently an integer of 0 to 3, e is an integer of 0 to 5, provided that d and e are not both 0 at the same time,

f is an integer of 0 to 3, each g is independently an integer of 0 to 5, provided that f and g are not both 0 at the same time,

h is an integer of 0 to 3, i is an integer of 0 to 4, provided that h and i are not simultaneously 0,

j is an integer of 0 to 3, k is an integer of 0 to 4, each l is independently an integer of 0 to 5, provided that j, k and l are not simultaneously 0,

m is an integer from 0 to 4, n is an integer from 0 to 4, with the proviso that m and n are not both 0 at the same time, and

o is an integer of 0 to 3, p is an integer of 0 to 4, and q is an integer of 0 to 5, provided that o, p, and q are not simultaneously 0.

Further, preferably, Ar₁To Ar₃At least one of which may be substituted with 5 or more deuterium.

More preferably, in chemical formula 1, Ar₁To Ar₃At least one of which may be a phenyl group substituted with 5 deuterium groups, and the remainder may be a respective unsubstituted phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl group.

As an example, all Ar₁To Ar₃Is phenyl, provided that Ar₁To Ar₃At least one of, in particular, Ar₁To Ar₃Any one, two or all three of which may be substituted with 5 deuterium.

As another example, Ar₁To Ar₃One of which is a respective unsubstituted biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl group, and the remainder can be phenyl, provided that at least one of the remainder, i.e., one or both of the remainder can be substituted with 5 deuterium groups.

Further, preferably, Ar₁To Ar₃At least one of which may be a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a carbazol-9-yl group, or a 9-phenyl-9H-carbazolyl group, each of which is substituted with 5 or more deuterium groups, and the remaining of which may each independently be an unsubstituted phenyl group or an unsubstituted biphenyl group.

As an example, Ar₁To Ar₃One of which may be a biphenyl group substituted with 5 deuterium, and the remaining may each independently be an unsubstituted phenyl group or an unsubstituted biphenyl group. At this time, as an example, those in which biphenyl group is substituted with 5 deuterium may be represented by the following structure.

In the above formula, r is an integer of 0 to 4, more specifically 0.

As another example, Ar₁To Ar₃Two of which may be biphenyl substituted with 5 deuterium, and the remainder may be unsubstituted phenyl. At this time, those in which biphenyl group is substituted with 5 deuterium groups may be represented by the above structure.

As another example, Ar₁To Ar₃One of them may be biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, each of which is completely substituted with deuterium, and all of the remainder may be unsubstituted phenyl.

Further, preferably, Ar₁To Ar₃May each independently be phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothienyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, and all Ar₁To Ar₃May be completely substituted with deuterium.

Further, in chemical formula 1, it is preferredOptionally, all R₁May be hydrogen. At this time, in chemical formula 1, x is an integer of 10, and Ar₁To Ar₃At least one of which is substituted with 5 or more deuterium.

Further, in chemical formula 1, preferably, R₁At least 5 of which may be deuterium, and the remainder may be hydrogen. In this case, in chemical formula 1, x is an integer of 10. For example, in chemical formula 1, R₁5, or 6, or 7, or 8 of them are deuterium, and the remainder may be hydrogen, or all 10R₁May be deuterium.

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

the first compound represented by chemical formula 1 may be prepared, for example, by a preparation method as shown in the following reaction scheme 1.

[ reaction scheme 1]

In reaction scheme 1, Ar₁To Ar₃、R₁And X is as defined in chemical formula 1, and X is halogen, preferably chlorine or bromine.

Reaction scheme 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 used for the amine substitution reaction can be modified as known in the art. The above production method can be further illustrated in the production examples described below.

Meanwhile, chemical formula 2 may be preferably represented by any one selected from the following chemical formulae 2-1 to 2-6. More preferably, chemical formula 2 may be represented by any one selected from the following chemical formulae 2-1 to 2-3:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

In chemical formulae 2-1 to 2-6, Ar₄、Ar₅、R₂And y is as defined above.

In chemical formula 2, preferably, Ar₄And Ar₅May each independently be unsubstituted C_6-30Aryl, more preferably, Ar₄And Ar₅Each independently is a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a 9, 9-dimethylfluorenyl group, or a 9, 9-diphenylfluorenyl group, each of which is unsubstituted.

Further, in chemical formula 2, preferably, Ar₄Is unsubstituted C_6-30Aryl, and Ar₅May be unsubstituted C containing one heteroatom selected from N, O and S_5-60A heteroaryl group. More preferably, Ar₄May be phenyl, biphenyl or terphenyl, each unsubstituted, and Ar₅May be a dibenzofuranyl, dibenzothienyl, carbazol-9-yl or 9-phenyl-9H-carbazolyl group, each unsubstituted.

In chemical formula 2, preferably, all of R₂May be hydrogen, in which case y may be an integer of 10.

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

the compound represented by chemical formula 2 may be prepared, for example, by a preparation method as shown in the following reaction scheme 2.

[ reaction scheme 2]

In reaction scheme 2, Ar₄、Ar₅、R₂And Y is as defined in chemical formula 2, and Y is halogen, preferably chlorine or bromine. Ar is Ar such as Ar₄Or Ar₅As defined in (1).

Reaction scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction can be modified as known in the art. The above production method can be further illustrated in the production examples described below.

In reaction scheme 2, the reaction of compound (III) and compound (IV) is shown in one step, but in compound (2), when Ar is₄And Ar₅Are different from each otherWhen it is determined by changing Ar in the compound (IV) to correspond to Ar respectively₄And Ar₅The functional group of (a) is performed in two steps. At this time, the order of the reaction steps is not particularly limited.

Preferably, in the light emitting layer, a weight ratio of the first compound represented by chemical formula 1 to the second compound represented by chemical formula 2 is 10:90 to 90:10, more preferably, 20:80 to 80:20, 30:70 to 70:30, 30:70 to 50:50, or 30:70 to 40: 60.

Meanwhile, the light emitting layer may include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material for an organic light emitting device. As examples, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can be mentioned. Specific examples of the aromatic amine derivative include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, and examples thereof include pyrenes, anthracenes, anthracene, having an arylamino group,And diindenopyrene, and the like. The styrylamine compound is a compound in which at least one arylvinyl group is substituted 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, styrenediamine, styrenetriamine, styrenetetramine, and the like. Further, examples of the metal complex include iridium complexes, platinum complexes, and the like, but are 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, if necessary.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode and transports the electrons to the light-emitting layer, and suppresses transfer of holes from the light-emitting layer, and the electron transport material is suitably a material that: it can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility.

Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq₃The complex of (1); an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used according to conventional techniques. Suitable examples of cathode materials are, in particular, typical materials having a small work function, followed by an aluminum or silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum or silver layer.

Electron injection layer

The organic light emitting device according to the present disclosure may further include an electron injection layer on the light emitting layer (or on the electron transport layer if present).

The electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to a hole injection layer, and is also excellent in an ability to form a thin film.

Specific examples of the electron-injecting layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, fluorine-containing compound, and fluorine-containing compound,Azole,Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, 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

Fig. 1 and 2 illustrate the structure of an organic light emitting device according to the present disclosure. Fig. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3 and a cathode 4. Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

The organic light emitting device according to the present disclosure may be manufactured by sequentially stacking the above-described structures. In this case, the organic light emitting device may be manufactured by: the 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, forming the above-described layers on the anode, and then depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing on a substrate from a cathode material to an anode material in the reverse order of the above-described configuration (WO 2003/012890). In addition, the light emitting layer may be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. Herein, the solution coating method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

On the other hand, 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.

Hereinafter, preferred embodiments of the present disclosure will be provided to better understand the present invention. However, these embodiments are presented for illustrative purposes only, and the scope of the present disclosure is not limited thereto.

Synthesis example 1-1: synthesis of Compound 1-1

Step 1) preparation of intermediate A

Adding 11, 12-indolino [2,3-a ] into a three-neck flask]Carbazole (15.0g, 58.5mmol), 1-bromobenzene-2, 3,4,5,6-d5(10.4g, 64.4mmol), bis (tri-tert-butylphosphine) palladium (0) (Pd (P-t-Bu)₃)₂) (0.6g, 1.2mmol), sodium tert-butoxide (NaOtBu) (8.4g, 87.8mmol) and 500ml of toluene, and the mixture was stirred under argon atmosphere at reflux for 8 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and then H was added₂O, the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Dried and concentrated, and then the sample was purified by silica gel column chromatography to obtain 13.2g of intermediate a. (yield: 67%, MS: [ M + H ]]+＝337)

Step 2) Synthesis of Compound 1-1

To a three-necked flask were added intermediate A (13.0g, 38.5mmol), compound a (14.6g, 42.4mmol), bis (tri-tert-butylphosphine) palladium (0) (0.4g, 0.8mmol), sodium tert-butoxide (5.6g, 57.8mmol) and 400ml of xylene, and the mixture was stirred at room temperature under an argon atmosphere for 8 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and then H was added₂O, the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Dried and concentrated, and then the sample was purified by silica gel column chromatography and then by sublimation to obtain 7.9g of compound 1-1. (yield: 32%, MS: [ M + H ]]+＝644)

Synthesis examples 1 to 2: synthesis of Compound 1-2

Compound 1-2 was prepared in the same manner as in the preparation of Compound 1-1,except that in step 1 of Synthesis example 1-1, bromobenzene was used instead of 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate B and in step 2, compound B was used instead of compound a. (MS [ M + H)]⁺＝644)

Synthesis examples 1 to 3: synthesis of Compounds 1-3

Compound 1-3 was prepared in the same manner as in the preparation of Compound 1-1, except that in step 2 of Synthesis example 1-1, Compound c was used instead of Compound a. (MS [ M + H)]⁺＝649)

Synthesis examples 1 to 4: synthesis of Compounds 1-4

Compound 1-4 was prepared in the same manner as in the preparation of compound 1-1 except that in step 1 of synthesis example 1-1, bromo-1, 1' -biphenyl was used instead of 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate C, and in step 2, compound d was used instead of compound a. (MS [ M + H)]⁺＝649)

Synthesis examples 1 to 5: synthesis of Compounds 1-5

Step 1) Synthesis of intermediate 1-5-1

To a three-necked flask were added intermediate C (15.0g, 36.7mmol), compound e (13.9g, 40.4mmol), bis (tri-tert-butylphosphine) palladium (0) (0.4g, 0.7mmol), sodium tert-butoxide (5.3g, 55.1mmol) and 400ml of xylene, and the mixture was stirred at room temperature under an argon atmosphere for 8 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and then H was added₂O, the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Drying and concentrating, then passing the sample throughPurification by silica gel column chromatography gave 17.1g of Compound 1-5-1. (yield: 65%, MS: [ M + H ]]⁺＝715)

Step 2) Synthesis of Compounds 1-5

To a vibrating tube were added the compound 1-5-1(10.0g, 14.0mmol), PtO₂(1.0g, 4.2mmol) and 70ml D₂O, then the tube was sealed and heated at 250 ℃ and 600psi for 12 hours. After completion of the reaction, chloroform was added, and the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Dried and concentrated, and then the sample was purified by silica gel column chromatography and by sublimation to obtain 4.4g of the compounds 1 to 5. (yield: 42%, deuterium substitution rate: 82%, MS [ M + H ]]⁺＝749)。

Synthesis examples 1 to 6: synthesis of Compounds 1-6

Compound 1-6 was prepared in the same manner as in the preparation of Compound 1-1, except that in step 2 of Synthesis example 1-1, intermediate B was used instead of intermediate A, and Compound f was used instead of Compound a. (MS [ M + H)]⁺＝658)

Synthesis examples 1 to 7: synthesis of Compounds 1-7

Compounds 1 to 7 were prepared in the same manner as in the preparation of Compound 1-1, except that in step 1 of Synthesis example 1-1, 2-bromodibenzo [ b, d ] was used]Furan-1, 3,4,6,7,8,9-D7 instead of 1-bromobenzene-2, 3,4,5,6-D5 was used to prepare intermediate D and in step 2 compound g was used instead of compound a. (MS [ M + H)]⁺＝660)

Synthesis examples 1 to 8: synthesis of Compounds 1-8

Compound 1-8 was prepared in the same manner as in the preparation of Compound 1-1, except that in step 2 of Synthesis example 1-1, intermediate B was used instead of intermediate A and compound h was used instead of compound a. (MS [ M + H)]⁺＝733)

Synthesis examples 1 to 9: synthesis of Compounds 1-9

Compounds 1 to 9 were prepared in the same manner as in the preparation of Compound 1-1, except that in step 1 of Synthesis example 1-1, 5, 8-indolino [2,3-c ] was used]Carbazole instead of 11, 12-indolino [2,3-a ]]Carbazole. (MS [ M + H)]⁺＝644)

Synthesis examples 1 to 10: synthesis of Compounds 1-10

Compounds 1 to 10 were prepared in the same manner as in the preparation of Compound 1-1, except that in step 1 of Synthesis example 1-1, 5, 7-indolino [2,3-b ] was used]Carbazole instead of 11, 12-indolino [2,3-a ]]Carbazole and substituting bromobenzene for 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate F, and in step 2, compound c is used instead of compound a. (MS [ M + H)]⁺＝644)

Synthesis examples 1 to 11: synthesis of Compounds 1-11

Compound 1-11 is produced in the same manner as in the production of compound 1-1, except that in step 1 of Synthesis example 1-1, 5, 11-dihydroindolo [ 2]3,2-b]Carbazole instead of 11, 12-indolino [2,3-a ]]Carbazole to prepare intermediate G, and in step 2, compound i is used instead of compound a. (MS [ M + H)]⁺＝674)

Synthesis examples 1 to 12: synthesis of Compounds 1-12

Step 1) Synthesis of intermediate H

Adding 5, 12-indolino [3,2-a ] into a three-neck flask]Carbazole (10.0g, 39.0mmol), compound j (16.7g, 42.9mmol), bis (tri-tert-butylphosphino) palladium (0) (0.4g, 0.8mmol), sodium tert-butoxide (5.6g, 58.5mmol) and toluene 400ml, and the mixture was stirred at room temperature under an argon atmosphere for 8 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and then H was added₂O, the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Dried and concentrated, and then the sample was purified by silica gel column chromatography to obtain 16.9g of intermediate H. (yield: 71%, MS: [ M + H ]]⁺＝608)

Step 2) Synthesis of Compounds 1-12

To a three-necked flask were added intermediate H (15.0g, 24.6mmol), bromobenzene (4.3g, 27.1mmol), bis (tri-tert-butylphosphine) palladium (0) (0.3g, 0.5mmol), sodium tert-butoxide (3.6g, 37.0mmol) and 250ml of xylene, and the mixture was stirred at room temperature under an argon atmosphere for 8 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and then H was added₂O, the reaction solution was transferred to a separatory funnel and extracted. Extracting with MgSO 2₄Dried and concentrated, and then the sample was purified by silica gel column chromatography and purified by sublimation to obtain 5.4g of the compounds 1 to 12. (yield: 32%, MS: [ M + H ]]⁺＝684)

Synthesis examples 1 to 13: synthesis of Compounds 1-13

Compounds 1-13 were prepared in the same manner as in the preparation of compound 1-1 except that in step 1 of synthesis example 1-1, 5, 12-indolino [3,2-a ] carbazole was used instead of 11, 12-indolino [2,3-a ] carbazole and bromobenzene was used instead of 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate I, and in step 2, compound k was used instead of compound a. (MS [ M + H ] + ═ 657)

Synthesis examples 1 to 14: synthesis of Compounds 1-14

Compounds 1 to 14 were prepared in the same manner as in the preparation of Compound 1-1, except that in step 1 of Synthesis example 1-1, 11, 12-indolino [2,3-a ] was used]Carbazole-1, 3,5,6,8,10-d6 instead of 11, 12-indolino [2,3-a ]]Carbazole and using 3-bromo-1, 1':3',1 "-terphenyl instead of 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate J, and in step 2, using compound i instead of compound a. (MS [ M + H)]⁺＝723)

Synthesis examples 1 to 15: synthesis of Compounds 1-15

Compounds 1 to 15 were prepared in the same manner as in the preparation of Compound 1-1, except that in step 1 of Synthesis example 1-1, 11, 12-indolino [2,3-a ] was used]Carbazole-1, 2,3,4,5,6,7,8,9,10-d10 instead of 11, 12-indolino [2,3-a ]]Carbazole and using 3-bromo-1, 1':3',1 "-terphenyl instead of 1-bromobenzene-2, 3,4,5,6-d5 to prepare intermediate K, and in step 2, using compound m instead of compound a. (MS [ M + H)]⁺＝803)

Synthesis example 2-1: synthesis of Compound 2-1

Reacting 5, 8-indolino [2,3-c ] in nitrogen atmosphere]Carbazole (15.0g, 58.5mmol) and 4-bromo-1, 1' -biphenyl (30.0g, 128.8mmol) were added to 300ml of toluene, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (16.9g, 175.6mmol) and bis (tri-tert-butylphosphine) palladium (0) (0.9g, 1.8mmol) were added thereto. After reacting for 12 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was dissolved in chloroform again, washed with water twice, and then the organic layer was separated, to which anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography and then by sublimation to obtain 9.8g of compound 2-1. (yield: 30%, MS: [ M + H ]]⁺＝562)

Synthesis examples 2 to 2: synthesis of Compound 2-2

Step 1) Synthesis of intermediate 2-1-1

Reacting 5, 8-indolino [2,3-c ] in nitrogen atmosphere]Carbazole (15.0g, 58.5mmol) and 4-bromo-1, 1':4',1 "-terphenyl (19.9g, 64.4mmol) were added to 300ml of toluene, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (8.4g, 87.8mmol) and bis (tri-tert-butylphosphine) palladium (0) (0.9g, 1.8mmol) were added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was dissolved in chloroform again, washed with water twice, and then the organic layer was separated, to which anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 19.3g of intermediate 2-2-1. (yield: 68%, MS: [ M + H ]]⁺＝486)

Step 2) Synthesis of Compound 2-2

Intermediate 2-2-1(15.0g, 31.0mmol) and 3-bromo-1, 1' -biphenyl (7.9g, 34.0mmol) were added to 300ml of toluene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (4.5g, 46.4mmol) and bis (tri-tert-butylphosphine) palladium (0) (0.5g, 0.9mmol) were added thereto. After 7 hours of reaction, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was dissolved in chloroform again, washed with water twice, and then the organic layer was separated, to which anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography and then by sublimation to obtain 9.5g of compound 2-2. (yield: 48%, MS: [ M + H ]]⁺＝638)

Synthesis examples 2 to 3: synthesis of Compounds 2-3

Compound 2-3 was prepared in the same manner as in the preparation of Compound 2-2, except that in step 1 of Synthesis example 2-2, 5, 11-indolino [3,2-b ] was used]Carbazole instead of 5, 8-indolino [2,3-c]Carbazole and 4-bromo-1, 1 '-biphenyl instead of 4-bromo-1, 1':4',1 "-terphenyl, and in step 2 4-chloro-1, 1':3', 1" -terphenyl instead of 3-bromo-1, 1' -biphenyl. (MS [ M + H)]⁺638) synthesis examples 2 to 4: synthesis of Compounds 2-4

Compound 2-4 was prepared in the same manner as in the preparation of Compound 2-2, except that in step 1 of Synthesis example 2-2, 5, 12-indolino [3,2-a ] was used]Carbazole instead of 5, 8-indolino [2,3-c]Carbazole and use of 2-bromodibenzo [ b, d ]]Furan instead of 4-bromo-1, 1':4',1 '-terphenyl and in step 2, 4-bromo-1, 1' -biphenyl instead of3-bromo-1, 1' -biphenyl. (MS [ M + H)]⁺＝576)

Example 1

Is coated thereon with a thickness ofThe glass substrate of the thin film of ITO (indium tin oxide) of (1) was put in distilled water containing a detergent dissolved therein, and washed by ultrasonic waves. In this case, the cleaning agent used was a product commercially available from Fisher co, and the distilled water was distilled water filtered twice by using a filter commercially available from Millipore co. The ITO was washed for 30 minutes, and then the ultrasonic washing was repeated twice for 10 minutes by using distilled water. After the completion of the washing with distilled water, the substrate was ultrasonically washed with solvents of isopropyl alcohol, acetone and methanol and dried, after which it was transferred to a plasma cleaning machine. The substrate was then rinsed with oxygen plasma for 5 minutes and then transferred to a vacuum evaporator.

On the ITO transparent electrode thus prepared, the following HT-A and 5 wt% PD were thermally vacuum-deposited toTo form a hole injection layer and then depositing only the HT-a material to To form a hole transport layer. Thermal vacuum deposition of the following HT-B on hole transport layer toAs an electron blocking layer. Then, vacuum deposition was performed by using compound 1-1 and compound 2-1 in a weight ratio of 40:60 as a host of a light emitting layer, and GD of 8 wt% of the host as a dopant toIs thickAnd (4) degree. Then, the following ET-A was vacuum deposited toAs a hole blocking layer. Then, the following ET-B and Liq were thermally vacuum deposited on the hole blocking layer at a ratio of 2:1 toAnd then vacuum depositing LiF and magnesium to a ratio of 1:1To sequentially form an electron transport layer and an electron injection layer. Depositing magnesium and silver on the electron injection layer in a ratio of 1:4 toTo form a cathode, thereby completing the fabrication of the organic light emitting device.

Examples 2 to 23 and comparative examples 1 to 20

Organic light emitting devices of examples 2 to 23 and comparative examples 1 to 20 were respectively manufactured in the same manner as in example 1, except that the host materials were changed as shown in table 1 below. In this case, when a mixture of two compounds is used as a host, the parentheses mean the weight ratio between the host compounds.

Experimental example: evaluation of device characteristics

The voltage, efficiency and lifetime (T95) were measured by applying current to the organic light emitting devices manufactured in the examples and comparative examples, and the results are shown in table 1 below. At this time, at 10mA/cm²Measuring voltage and efficiency at a current density of (1), T95 means at 20mA/cm²The time (hours) required for the luminance to decrease to 95% of the initial luminance at the current density of (1).

[ Table 1]

In the present disclosure, both the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 have an indolocarbazole skeleton. Here, the first compound has a strong ability to transport electrons by including a triazine group, and the second compound has a strong ability to transport holes, and thus has characteristics suitable for using a mixture of two materials as a host. In particular, since both materials have an indolocarbazole structure, they are well mixed with each other and are advantageous in forming an exciplex, and in efficiently transferring energy to a dopant. At this time, the first compound becomes an anion, the second compound becomes a cation to form an exciplex, and the first compound which becomes an anionic state has a more unstable state. By substituting five or more deuterium therein, the first compound has reduced vibrational energy and more stable energy even in an anionic state.

Therefore, as can be seen from table 1, examples 1 to 23, in which the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 are simultaneously used as the light emitting layer of the organic electroluminescent device in the present disclosure, show significantly improved low voltage, high efficiency, and long lifetime characteristics.