WO2017018795A2 - Heterocyclic compound and organic light emitting diode using same - Google Patents

Abstract

The present application provides: a heterocyclic compound capable of greatly improving the lifespan, efficiency, electrochemical stability, and thermal stability of an organic light emitting diode; and an organic light emitting diode having the heterocyclic compound contained in an organic compound layer.

Description

Heterocyclic compound and organic light emitting device using the same

This application is filed with the Korean Patent Application No. 10-2015-0106063, filed with the Korean Patent Office on July 27, 2015, and the Korean Patent Application No. 10-2016-0057665 and 2016, filed with the Korean Patent Office on May 11, 2016. Claims the benefit of the filing date of Korean Patent Application No. 10-2016-0059084 filed with the Korea Intellectual Property Office on May 13, 2013, the entire contents of which are incorporated herein.

The present application relates to a heterocyclic compound and an organic light emitting device using the same.

The electroluminescent device is a kind of self-luminous display device, and has an advantage of having a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting element has a structure in which an organic thin film is arranged between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from two electrodes are combined in the organic thin film to form a pair, then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers as necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound which may itself constitute a light emitting layer may be used, or a compound that may serve as a host or a dopant of a host-dopant-based light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, or the like may be used.

In order to improve the performance, lifespan, or efficiency of an organic light emitting element, development of the material of an organic thin film is continuously required.

Compounds having a chemical structure capable of satisfying the conditions required for materials usable in the organic light emitting device, such as appropriate energy level, electrochemical stability and thermal stability, and can play various roles required in the organic light emitting device according to substituents. There is a need for a study on an organic light emitting device comprising a.

An exemplary embodiment of the present application provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

L1 and L2 are the same as or different from each other, and each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group,

Ar1 is a substituted or unsubstituted, C _{2 Through} C ₆₀ Heteroaryl group containing at least one,

Ar2 is represented by any one of the following Chemical Formulas 3 and 4,

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

Y1 to Y4 are the same as or different from each other, and each independently a substituted or unsubstituted C ₆ to C ₆₀ aromatic hydrocarbon ring; Or substituted or unsubstituted C ₂ to C ₆₀ aromatic heterocycle,

R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

In addition, another exemplary embodiment of the present application is an organic light emitting device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, and at least one of the organic material layers is a heterocyclic compound represented by Formula 1 above. It provides an organic light emitting device comprising a.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, comprising a heterocyclic compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 at the same time.

[Formula 2]

In Chemical Formula 2,

R1 'to R4' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

L 1 ′ is a C ₆ to C ₆₀ arylene group which is directly bonded or substituted or unsubstituted,

Ar1 'is a substituted or unsubstituted C _{6 Through} C ₆₀ aryl group; Or a substituted or unsubstituted, C _{2 Through} C ₆₀ A heteroaryl group containing at least one of S and O,

Ar2 'is a substituted or unsubstituted C _{6 Through} C ₆₀ Aryl group; Or a substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

m ', p' and q 'are each independently an integer from 0 to 4,

n 'is an integer of 0-2.

The heterocyclic compound according to the exemplary embodiment of the present application may be used as an organic material layer material of the organic light emitting device. The heterocyclic compound may be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a charge generating layer, etc. in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 may be used as a material of an electron transporting layer, a hole transporting layer or a light emitting layer of the organic light emitting device. In addition, when used in the heterocyclic compound organic light emitting device represented by the formula (1) can reduce the drive voltage of the device, improve the light efficiency, and can improve the life characteristics of the device by the thermal stability of the compound.

In addition, the heterocyclic compound represented by Formula 1, and the compound represented by Formula 2 may be used as a material of the light emitting layer of the organic light emitting device at the same time. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are simultaneously used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the compound is thermally stabilized. Lifespan characteristics can be improved.

1 to 3 are diagrams schematically showing a laminated structure of an organic light emitting device according to an exemplary embodiment of the present application.

4 shows a graph of LTPL measurements at 363 nm wavelength of Compound 1-2.

5 shows a PL measurement graph at 238 nm wavelength of Compound 1-2.

6 shows the UV absorption spectrum of Compound 1-2.

FIG. 7 shows a graph of LTPL measurements at 339 nm wavelength of compound 1-11.

8 shows a PL measurement graph at 234 nm wavelength of Compound 1-11.

9 shows the UV absorption spectrum of Compound 1-11.

10 shows a graph of LTPL measurements at 241 nm wavelength of Compound 1-23.

11 shows a PL measurement graph at 241 nm wavelength of Compound 1-23.

12 shows the UV absorption spectrum of Compound 1-23.

FIG. 13 shows a graph of LTPL measurements at 340 nm wavelength of Compound 1-27. FIG.

14 shows a PL measurement graph at 241 nm wavelength of Compound 1-27.

15 shows the UV absorption spectrum of Compound 1-27.

16 shows a graph of LTPL measurements at 291 nm wavelength of Compound 1-33.

FIG. 17 shows a PL measurement graph of 239 nm wavelength of Compound 1-33. FIG.

18 shows the UV absorption spectrum of Compound 1-33.

19 shows a graph of LTPL measurements at 259 nm wavelength of Compound 1-39.

FIG. 20 shows a PL measurement graph at 259 nm wavelength of Compound 1-39. FIG.

21 shows the UV absorption spectra of Compounds 1-39.

22 shows a graph of LTPL measurements at 260 nm wavelength of Compound 1-41.

FIG. 23 shows a PL measurement graph at 260 nm wavelength of Compound 1-41.

24 shows the UV absorption spectrum of Compound 1-41.

25 shows a graph of LTPL measurements at 361 nm wavelength of Compound 1-65.

FIG. 26 shows a PL measurement graph of 235 nm wavelength of Compound 1-65. FIG.

27 shows the UV absorption spectrum of Compound 1-65.

28 is a graph of LTPL measurements at 360 nm wavelength of Compound 1-66.

29 shows a PL measurement graph at 307 nm wavelength of Compound 1-66.

30 shows the UV absorption spectrum of Compound 1-66.

FIG. 31 is a graph of LTPL measurements at 361 nm wavelength of Compound 1-67. FIG.

32 shows a PL measurement graph of 266 nm wavelength of Compound 1-67.

33 shows the UV absorption spectrum of Compound 1-67.

34 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-69.

35 shows a PL measurement graph of 308 nm wavelength of Compound 1-69.

36 shows the UV absorption spectrum of Compound 1-69.

37 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-70.

FIG. 38 shows a PL measurement graph of 267 nm wavelength of Compound 1-70. FIG.

39 shows the UV absorption spectrum of Compound 1-70.

40 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-71.

FIG. 41 is a graph of PL measurement at 241 nm wavelength of Compound 1-71.

42 shows the UV absorption spectrum of Compound 1-71.

43 is a graph of LTPL measurements at 361 nm wavelength of Compound 1-78.

44 shows a PL measurement graph at 263 nm wavelength of Compound 1-78.

45 shows the UV absorption spectrum of Compound 1-78.

FIG. 46 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-82.

FIG. 47 shows a PL measurement graph at 307 nm wavelength of Compound 1-82.

48 shows the UV absorption spectra of Compounds 1-82.

FIG. 49 is a graph of LTPL measurements at 363 nm wavelength of Compound 1-84.

50 shows a PL measurement graph at 298 nm wavelength of Compound 1-84.

51 shows the UV absorption spectra of Compounds 1-84.

FIG. 52 is a graph of LTPL measurements at 355 nm wavelength of Compound 1-99.

53 shows a PL measurement graph at 355 nm wavelength of Compound 1-99.

54 shows the UV absorption spectrum of Compound 1-99.

<Description of Major Codes in Drawings>

100: substrate

200: anode

300: organic material layer

301: hole injection layer

302: hole transport layer

303: light emitting layer

304: hole blocking layer

305: electron transport layer

306: electron injection layer

400: cathode

Hereinafter, the present application will be described in detail.

Heterocyclic compound according to an exemplary embodiment of the present application is characterized in that represented by the formula (1). More specifically, the heterocyclic compound represented by Formula 1 may be used as an organic material layer material of the organic light emitting device by the structural features of the core structure and the substituents as described above.

In Formulas 3 and 4, * represents a position connected to L2 of the formula (1).

According to an exemplary embodiment of the present application, Chemical Formula 3 may be represented by any one of the following structural formulas.

X 1 to X 6 in the structural formulas are the same as or different from each other, and each independently NR, S, O, or CR′R ″,

R8 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

m is an integer of 0-8, n, o, p, q, r, and s are each independently the integer of 0-6.

According to the exemplary embodiment of the present application, Chemical Formula 4 may be represented by any one of the following structural formulas.

X7 and X8 in the above structural formula is the same as or different from each other, and each independently NR, S, O or CR'R ",

R15 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

t is an integer of 0-7.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 5 to 10.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 5 to 10, R1 to R6, R8, R9, R12, R13, R16, L1, Ar1, X1, X4, X5, m, n, q, r, and t are defined in Formula 1 and Structural Formula Is the same as the definition of

In one embodiment of the present application, R1 to R6 of Formula 1 may be each independently hydrogen or deuterium.

In one embodiment of the present application, R8 to R18 of the structural formulas are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Or a substituted or unsubstituted C _{2 Through} C _{60 It} may be a heteroaryl group.

In one embodiment of the present application, R, R 'and R "of the general formula (1) are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C ₁ to C ₆₀ alkyl group; or a substituted or unsubstituted C ₆ to C ₆₀ aryl group.

In addition, the composition for an organic material layer of the organic light emitting device according to an exemplary embodiment of the present application is characterized in that it comprises a heterocyclic compound represented by the formula (1), and a compound represented by the formula (2) at the same time.

According to an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of the following Chemical Formulas 11 to 22.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

In Chemical Formulas 11 to 22, the definitions of L1, Ar1, Ar2, R1 to R4, m, n, p, and q are the same as the definitions in Chemical Formula 2.

In an exemplary embodiment of the present application, when m ', n', p 'and q' of the general formula (2) are each independently 2 or more, two or more R1 'to R4' may be the same or different from each other.

In one embodiment of the present application, R1 'to R4' of Chemical Formula 2 may be each independently hydrogen or deuterium.

In an exemplary embodiment of the present application, Ar1 'of Chemical Formula 2 is a substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted, C ₂ to C ₆₀ heteroaryl group containing S; Or a substituted or unsubstituted, C ₂ to C ₆₀ heteroaryl group containing O.

In an exemplary embodiment of the present application, Ar1 ′ of Formula 2 may be a phenyl group, a biphenyl group, a naphthyl group, an fluorene group substituted with an alkyl group, a dibenzothiophene group, or a dibenzofuran group.

In an exemplary embodiment of the present application, Ar 2 ′ of Formula 2 may be a substituted or unsubstituted C ₆ to C ₆₀ aryl group.

In one embodiment of the present application, Ar2 'of Formula 2 may be a phenyl group.

In the present application, the substituents of Chemical Formulas 1 and 2 will be described in more detail below.

In the present specification, "substituted or unsubstituted" is deuterium; Halogen group; -CN; C ₁ to C ₆₀ alkyl group; C _{2 Through} C ₆₀ Alkenyl group; C _{2 Through} C ₆₀ Alkynyl group; A C ₃ to C ₆₀ cycloalkyl group; C _{2 Through} C ₆₀ Heterocycloalkyl group; C _{6 Through} C ₆₀ An aryl group; C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= 0) RR '; C ₁ to C ₂₀ alkylamine group; C _{6 Through} C ₆₀ An arylamine group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of C ₂ to C ₆₀ heteroarylamine group, substituted or unsubstituted with a substituent to which two or more of the substituents are bonded, or two or more substituents selected from the substituents Mean substituted or unsubstituted by a substituent. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked. Said additional substituents may be further substituted further. R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cyclo An alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, a halogen group, -CN, SiRR'R ", P (= O) RR ', C ₁ to C ₂₀ linear or branched alkyl group , Unsubstituted or substituted with one or more substituents selected from the group consisting of C ₆ to C ₆₀ aryl groups, and C ₂ to C ₆₀ heteroaryl groups,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ to C ₆₀ substituted heteroaryl or unsubstituted alkyl group of C ₁ to C _60; an aryl group of deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ a, and C ₂ A C ₃ to C ₆₀ cycloalkyl group unsubstituted or substituted with a C ₆ to C ₆₀ heteroaryl group; deuterium, halogen, —CN, an alkyl group of C ₁ to C ₂₀ , an aryl group of C ₆ to C ₆₀ , and C ₂ to C ₆₀ substituted or unsubstituted group heteroaryl C ₆ to C ₆₀ aryl group; or an alkyl group of deuterium, halogen, -CN, C ₁ to C _20, C ₆ to C ₆₀ aryl, and C ₂ to C ₆₀ Or a C ₂ to C ₆₀ heteroaryl group unsubstituted or substituted with a heteroaryl group.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. Carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically, 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group and the like, but is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. Carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples thereof include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, and 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(Naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. Carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, or the like. Carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group and the like, but is not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, or the like. Carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other ring group may be an aryl group, but may be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, or the like. The aryl group includes a spiro group. Carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenenyl group, pyre Neyl group, tetrasenyl group, pentaxenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof Etc., but is not limited thereto.

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro groups may include any of the groups of the following structural formula.

In the present specification, the heteroaryl group includes S, O, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. Carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 25. Specific examples of the heteroaryl group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl and thiazolyl Group, isothiazolyl group, triazolyl group, furazanyl group, oxdiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, deoxyyl group, triazinyl group, tetragenyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyl group, naphthyridyl group, acridinyl group, phenanthtridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triaza indene group, indolyl group, indolinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, Dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo [ 2,3-a] carbazolyl group, indolo [2,3-b] carbazolyl group, indolinyl group, 10,11-dihydro-dibenzo [b, f] azepine group, 9,10-dihydro Acridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, benzo [c] [1,2,5] thiadiazolyl group, 5,10-di Hydrodibenzo [b, e] [1,4] azasilinyl, pyrazolo [1,5-c] quinazolinyl group, pyrido [1,2-b] indazolyl group, pyrido [1,2- a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b] carbazolyl group, and the like, but are not limited thereto.

In the present specification, the amine group is a monoalkylamine group; Monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine groups; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkyl heteroaryl amine group; And it may be selected from the group consisting of arylheteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluore And a phenylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, an arylene group means one having two bonding positions, that is, a divalent group. The description of the aforementioned aryl group can be applied except that they are each divalent. In addition, a heteroarylene group means a thing which has two bonding positions, ie, a bivalent group, in a heteroaryl group. The description of the aforementioned heteroaryl group can be applied except that they are each divalent.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structures of Formulas (1) and (2), compounds having the inherent properties of the introduced substituents can be synthesized. For example, by introducing a substituent mainly used in the hole injection layer material, the hole transporting material, the light emitting layer material, the electron transporting material and the charge generating layer material used in the manufacture of the organic light emitting device to meet the requirements required for each organic material layer The substance to make can be synthesize | combined.

In addition, it is possible to finely control the energy bandgap by introducing a variety of substituents in the structure of Formulas (1) and (2), on the other hand to improve the properties at the interface between the organic material and to vary the use of the material .

On the other hand, the heterocyclic compound has a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

The heterocyclic compound according to one embodiment of the present application may be prepared by a multistage chemical reaction. Some intermediate compounds may be prepared first, and compounds of formula 1 or 2 may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application may be prepared based on the preparation examples described below.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, comprising a heterocyclic compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2.

The details of the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 are the same as described above.

 The weight ratio of the heterocyclic compound represented by Formula 1 in the composition: the compound represented by Formula 2 may be 1:10 to 10: 1, 1: 8 to 8: 1, and 1: 5 to 5 : 1, and 1: 2 to 2: 1, but is not limited thereto.

The composition may be used when forming the organic material of the organic light emitting device, and particularly preferably used when forming the host of the light emitting layer.

The composition may be a form in which two or more compounds are simply mixed, and may be mixed with a powder material before forming an organic material layer of the organic light emitting device, or may be mixed with a compound that is in a liquid state at an appropriate temperature or more. The composition is in a solid state below the melting point of each material, and can be maintained in the liquid phase by adjusting the temperature.

Another embodiment of the present application provides an organic light emitting device including the heterocyclic compound represented by Formula 1.

In addition, the organic light emitting device according to the exemplary embodiment of the present application includes an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, and at least one of the organic material layers is a hetero ring represented by Chemical Formula 1 It characterized in that it comprises a compound, and a compound represented by the formula (2).

An organic light emitting device according to an exemplary embodiment of the present application is a conventional organic light emitting device, except that one or more organic material layers are formed using the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2. It can be produced by a method and a material for manufacturing a light emitting device.

The compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.

Specifically, the organic light emitting device according to the exemplary embodiment of the present application includes an anode, a cathode and at least one organic material layer provided between the anode and the cathode, one or more of the organic material layer is a hetero ring represented by the formula (1) Compound.

In addition, the organic light emitting device according to the exemplary embodiment of the present application includes an anode, a cathode and at least one organic layer provided between the anode and the cathode, one or more of the organic layer is a heterocyclic compound represented by the formula (1) And it includes a heterocyclic compound represented by the formula (2).

1 to 3 illustrate a lamination order of an electrode and an organic material layer of an organic light emitting diode according to an exemplary embodiment of the present application. However, these drawings are not intended to limit the scope of the present application, the structure of the organic light emitting device known in the art can be applied to the present application.

Referring to FIG. 1, an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is illustrated. However, the present invention is not limited thereto, and as illustrated in FIG. 2, an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case where the organic material layer is a multilayer. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and other layers except for the light emitting layer may be omitted, and other functional layers may be added as needed.

The organic light emitting device according to the present specification includes a heterocyclic compound represented by Chemical Formula 1 above at least one layer of an organic material layer, or includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2 at the same time. Except that it can be prepared by materials and methods known in the art.

The heterocyclic compound represented by Chemical Formula 1 may constitute one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the organic material layer may be mixed with other materials.

The heterocyclic compound represented by Chemical Formula 1 may be used as an electron transport layer, a hole blocking layer, a light emitting layer, or the like in an organic light emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material of an electron transporting layer, a hole transporting layer, or a light emitting layer of an organic light emitting device.

In addition, the heterocyclic compound represented by Formula 1 may be used as a material of the light emitting layer in the organic light emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material of the phosphorescent host of the light emitting layer in the organic light emitting device.

In addition, the organic compound layer containing the heterocyclic compound represented by Formula 1, and the heterocyclic compound represented by Formula 2 may further include other materials as necessary.

The heterocyclic compound represented by Formula 1, and the heterocyclic compound represented by Formula 2 may be used as a material of the charge generating layer in the organic light emitting device.

The heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as an electron transport layer, a hole blocking layer, or a light emitting layer in an organic light emitting device. As an example, the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material of an electron transporting layer, a hole transporting layer, or a light emitting layer of an organic light emitting device.

In addition, the heterocyclic compound represented by Formula 1, and the compound represented by Formula 2 may be used as a material of the light emitting layer in the organic light emitting device. As an example, the heterocyclic compound represented by Formula 1, and the compound represented by Formula 2 may be used as a material of the phosphorescent host of the light emitting layer in the organic light emitting device.

In the organic light emitting device according to the exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 are exemplified below, but these are for illustrative purposes only and the scope of the present application It is not intended to be limiting and may be substituted with materials known in the art.

As the anode material, materials having a relatively large work function may be used, and a transparent conductive oxide, a metal, or a conductive polymer may be used. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

As the cathode material, materials having a relatively low work function may be used, and a metal, a metal oxide, or a conductive polymer may be used. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

As the hole injection material, a well-known hole injection material may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). Starburst amine derivatives such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA), 4,4 ', 4 "-tri [phenyl (m-tolyl) amino] triphenylamine (m- MTDATA), 1,3,5-tris [4- (3-methylphenylphenylamino) phenyl] benzene (m-MTDAPB), polyaniline / dodecylbenzenesulfonic acid, or poly (line) 3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate)), polyaniline / Camphor sulfonic acid or polyaniline / Poly (4-styrenesulfonate) (Polyaniline / Poly (4-styrene-sulfonate)) etc. can be used.

As the hole transporting material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular or polymer materials may be used.

Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthhraquinomethane and derivatives thereof, and fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like can be used, as well as high molecular weight materials as well as high molecular materials.

As the electron injection material, for example, LiF is representatively used in the art, but the present application is not limited thereto.

As the light emitting material, a red, green or blue light emitting material may be used, and if necessary, two or more light emitting materials may be mixed. In this case, two or more light emitting materials may be deposited and used as separate sources, or premixed and deposited as one source. In addition, although a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material. As the light emitting material, a material which combines holes and electrons injected from the anode and the cathode, respectively, to emit light may be used, but materials in which both the host material and the dopant material are involved in light emission may be used.

In the case of mixing and using a host of luminescent materials, the host of the same series may be mixed and used, or the host of another series may be mixed and used. For example, any two or more kinds of materials of n-type host material or P-type host material can be selected and used as the host material of the light emitting layer.

The organic light emitting device according to the exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a double-sided emission type according to a material used.

The heterocyclic compound according to the exemplary embodiment of the present application may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

Hereinafter, the present specification will be described in more detail with reference to Examples, but these are merely to illustrate the present application and are not intended to limit the scope of the present application.

< Example >

< Production Example  1> Preparation of Compound 1-11-2

1) Preparation of Compound 1-11-2

5.0 g (19.0 mM) of 2-bromodibenzo [b, d] thiophene, 2.6 g (15.8 mM) of 9H-carbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL of trans-1,2-diaminocyclohexane (15.8 mM) and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized with methanol to obtain 4.7 g (85%) of the title compound 1-11-2.

2) Preparation of Compound 1-11-1

5 g (14.3 mM) of Compound 1-11-2 and 100 mL of THF were added dropwise at 7.78 mL (18.6 mM) of 2.5 M n-BuLi at -78 ° C, and the mixture was stirred at room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethylborate (B (OMe) ₃ ) was added dropwise to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: MeOH = 100: 3) and recrystallized with DCM to obtain 3.9 g (70%) of the title compound 1-11-1.

3) Preparation of Compound 1-11

1-11-1 7.5 g (19.0 mM), 2-chloro-4,6-diphenyl-1,3,5-triazine 5.1 g (19.0 mM), Pd (PPh ₃ ) ₄ 1.1 g (0.95 mM) 5.2 g (38.0 mM) of K ₂ CO ₃ was dissolved in toluene / EtOH / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized with methanol to obtain 7.7 g (70%) of the title compound 1-11.

Except for using Intermediate A of Table 1 below instead of 9H-carbazole in Preparation Example 1 and using Intermediate B of Table 1 below instead of 2-chloro-4,6-diphenyl-1,3,5-triazine The target compound A was synthesized in the same manner as in Preparation of Preparation Example 1.

TABLE 1

< Production Example  2> Preparation of Compound 1-64

1) Preparation of Compound 1-64-2

2-bromodibenzo [b, d] thiophene 5.0 g (19.0 mM), (9-phenyl-9H-carbazol-3-yl) boronic acid 5.5 g (19.0 mM), Pd (PPh ₃ ) ₄ 1.1 g (0.95 mM) and 5.2 g (38.0 mM) of K ₂ CO ₃ were dissolved in toluene / EtOH / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from hexane to give the title compound 1-64-2. 5.7 g (70%) was obtained.

2) Preparation of Compound 1-64-1

6.1 g (14.3 mM) of Compound 1-64-2 and 100 mL of THF were added dropwise at 7.78 mL of 2.5M n-BuLi at -78 ° C and stirred at room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethylborate (B (OMe) ₃ ) was added dropwise to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: MeOH = 100: 3) and recrystallized with DCM to obtain 4.7 g (70%) of the title compound 1-64-1.

3) Preparation of Compound 1-64

8.9 g (19.0 mM) of compound 1-64-1, 5.1 g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of Pd (PPh ₃ ) ₄ ), 5.2 g (38.0 mM) of K ₂ CO ₃ was dissolved in toluene / EtOH / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized with methanol to give 8.7 g (70%) of the title compound 1-64.

Intermediate C of Table 2 was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid in Preparation Example 2, and 2-chloro-4,6-diphenyl-1,3,5-triazine was used. Instead, except for using the intermediate D in Table 2 was prepared in the same manner as in Preparation Example 2 to synthesize the target compound B.

TABLE 2

< Production Example  3> Compound 2-2 Synthesis

1) Preparation of Compound 2-2-2 (Ref 1)

2-bromodibenzo [b, d] thiophene 4.2 g (15.8 mM), 9-phenyl-9H, 9'H-3,3'-bicarbazole 6.5 g (15.8 mM), CuI 3.0 g (15.8 mM) ), 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane, followed by reflux for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to obtain 7.9 g (85%) of the title compound 2-2-2.

2) Preparation of Compound 2-2-1

8.4 g (14.3 mmol) of Compound 2-2-1 and 100 mL of THF were added dropwise at 7.78 mL (18.6 mmol) of 2.5M n-BuLi at -78 ° C, and the mixture was stirred at room temperature for 1 hour. 4.8 mL (42.9 mmol) of trimethyl borate was added dropwise to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: MeOH = 100: 3) and recrystallized with DCM to obtain 3.9 g (70%) of the title compound 2-2-1.

3) Preparation of Compound 2-2

Compound 2-2-1 6.7 g (10.5 mM), iodobenzene 2.1 g (10.5 mM), Pd (PPh ₃ ) ₄ 606 mg (0.52 mM), K ₂ CO ₃ 2.9 g (21.0 mM) was added to toluene / EtOH / H ₂ O was dissolved in 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give the title compound 2-2. 4.9 g (70%) was obtained.

< Production Example  4> Compound 2-3 Synthesis

Except for using 4-iodo-1,1'-biphenyl instead of iodobenzene in the preparation of the compound 2-2 and the target compound 2-3 (83%) was prepared in the same manner as in the preparation of the compound 2-2 Got it.

< Production Example  5> Compound ref 2 synthesis

1) Preparation of Compound ref 2-2

A mixed solution containing 30.0 g (121.4 mM) of 2-bromodibenzofuran and 300 mL of THF was added dropwise at 878 mL (157.8 mM) at -78 ° C and stirred for 1 hour. 11.0 g (42.9 mmol) of iodine was added to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction product was purified by column chromatography (DCM) and recrystallized with MeOH to obtain 23.1 g (51%) of the title compound ref 2-2.

2) Preparation of Compound ref 2-1

Compound ref 2-2 3.9 g (10.5 mM), phenylboronic acid 1.3 g (10.5 mM), Pd (PPh ₃ ) ₄ 606 mg (0.52 mM), K ₂ CO ₃ 2.9 g (21.0 mM) toluene / EtOH / H _It was dissolved in 2O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give the title compound ref 2-1. 2.4 g (70%) was obtained.

3) Preparation of Compound Ref 2

Compound ref 2-1 5.1 g (15.8 mM), 9-phenyl-9H, 9'H-3,3'-bicarbazole 6.5 g (15.8 mM), CuI 3.0 g (15.8 mM), trans-1,2 1.9 mL (15.8 mM) of diaminocyclohexane and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized with methanol to obtain the title compound ref 2 8.7g (85%).

< Production Example  6> Manufacture of ref 3

5.5 g (19.0 mmol) of (3- (9H-carbazole-9-yl) phenyl) boronic acid, 5.1 g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of Pd (PPh ₃ ) _{4 and} 5.2 g (38.0 mM) of K ₂ CO ₃ were dissolved in toluene / ethanol / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give the desired compound ref 3 6.3 g (70%) was obtained.

< Production Example  7> Compound 2-7 Synthesis

Compound 2-7 using 2-bromo-9,9-dimethyl-9 hydrogen-fluorene (2-bromo-9,9-dimethyl-9H-fluorene) instead of iodobenzene in the preparation of compound 2-2 Was obtained (yield 69%).

< Production Example  8> Synthesis of Compound 2-9

In the preparation of Compound 2-2, 2-bromodibenzo [b, d] thiophene was used instead of iodobenzene to obtain Compound 2-9 (yield 72%).

< Production Example  9> Compound 2-11 Synthesis

Compound 2-11 was obtained using 2-bromodibenzo [b, d] furan instead of iodobenzene in the preparation of compound 2-2 (yield 68%).

< Production Example  10> Preparation of Compound ref 4

5.5 g (19.0 mmol) of (3- (9H-carbazole-9-yl) phenyl) boronic acid, 5.1 g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of Pd (PPh ₃ ) _{4 and} 5.2 g (38.0 mM) of K ₂ CO ₃ were dissolved in toluene / ethanol / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give compound ref 4 6.3 g (70%) was obtained.

< Production Example  11> Preparation of Compound ref 5

5.8 g (19.0 mM) of (3- (dibenzo [b, d] thiophen-4-yl) phenyl) boronic acid, 5.1 g of 2-chloro-4,6-diphenyl-1,3,5-triazine (19.0 mM), 1.1 g (0.95 mM) of Pd (PPh ₃ ) _{4 and} 5.2 g (38.0 mM) of K ₂ CO ₃ were dissolved in toluene / ethanol / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give compound ref 5 6.5 g (70%) was obtained.

< Production Example  12> Synthesis of Compound ref 6

1) Preparation of Compound ref 6-2

11.4 mL (22.8 mM) of 2.0 M lithium diisopropyl amine was added dropwise at −78 ° C. to a mixed solution containing 4.7 g (19.0 mM) of 2-bromodienzozo [b, d] furan and 100 mL of THF. Stirred for time. 4.8 mL (42.9 mM) of trimethyl borate was added dropwise to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: MeOH = 100: 3) and recrystallized with DCM to obtain 3.9 g (70%) of compound ref 6-2.

2) Preparation of Compound ref 6-1

Compound ref 6-2 5.5 g (19.0 mM), 2-bromo-4,6-diphenylpyrimidine 5.9 g (19.0 mM), Pd (PPh ₃ ) ₄ 1.1 g (0.95 mM), K ₂ CO ₃ 5.2 g (38.0 mM) was dissolved in toluene / ethanol / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from hexane to give compound ref 6-1 6.3 g (70%) was obtained.

3) Preparation of Compound ref 6

Compound ref 6-1 9.1 g (19.0 mM), 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole 4.5 g (15.8 mM), CuI 3.0 g (15.8 mM), 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane and then refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give 9.1 g (85%) of compound ref 6.

< Production Example  13> Synthesis of Compound ref 7

1) Preparation of Compound ref 7-2

5.0 g (19.0 mM) of 4-bromodibenzo [b, d] thiophene, 2.6 g (15.8 mM) of 9H-carbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL of trans-1,2-diaminocyclohexane (15.8 mM) and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give 4.7 g (85%) of compound ref 7-2.

2) Preparation of Compound ref 7-1

5.0 g (14.3 mM) of compound ref 7-2 and 100 mL of THF were added dropwise at 7.78 mL (18.6 mM) of 2.5 M n-BuLi at -78 ° C, and the mixture was stirred at room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethyl borate was added dropwise to the reaction mixture, which was stirred for 2 hours at room temperature. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: MeOH = 100: 3) and recrystallized with DCM to obtain 3.9 g (70%) of the title compound ref 7-1.

3) Preparation of Compound ref 7

Compound ref 7-1 7.5 g (19.0 mM), 2-chloro-4,6-diphenyl-1,3,5-triazine 5.1 g (19.0 mM), Pd (PPh ₃ ) ₄ 1.1 g (0.95 mM) 5.2 g (38.0 mM) of K ₂ CO ₃ was dissolved in toluene / ethanol / H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give 7.7 g (70%) of compound ref 7.

< Production Example  14> Synthesis of Compound ref 8

5.0 g (19.0 mM) of 2-bromodibenzo [b, d] thiophene, 4.5 g (15.8 mM) of 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole, CuI 3.0 g (15.8 mM), 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give 7.3 g (85%) of compound ref 8.

< Production Example  15> Synthesis of Compound ref 9

2-bromodibenzo [b, d] thiophene 4.2 g (15.8 mM), 9-phenyl-9H, 9'H-3,3'-bicarbazole 6.5 g (15.8 mM), CuI 3.0 g (15.8 mM) ), 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-oxane, followed by reflux for 24 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to give 7.9 g (85%) of compound ref 9.

Compounds were prepared in the same manner as in Preparation Examples, and the synthesis results thereof are shown in Tables 3 to 23 below.

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

TABLE 15

TABLE 16

TABLE 17

TABLE 18

TABLE 19

TABLE 20

TABLE 21

Table 22

TABLE 23

Table 21 shows NMR values, and Tables 22 and 23 show measured values of a field desorption mass spectrometry (FD-MS).

4 shows a graph of LTPL measurements at 363 nm wavelength of Compound 1-2.

5 shows a PL measurement graph at 238 nm wavelength of Compound 1-2.

6 shows the UV absorption spectrum of Compound 1-2.

FIG. 7 shows a graph of LTPL measurements at 339 nm wavelength of compound 1-11.

8 shows a PL measurement graph at 234 nm wavelength of Compound 1-11.

9 shows the UV absorption spectrum of Compound 1-11.

10 shows a graph of LTPL measurements at 241 nm wavelength of Compound 1-23.

11 shows a PL measurement graph at 241 nm wavelength of Compound 1-23.

12 shows the UV absorption spectrum of Compound 1-23.

FIG. 13 shows a graph of LTPL measurements at 340 nm wavelength of Compound 1-27. FIG.

14 shows a PL measurement graph at 241 nm wavelength of Compound 1-27.

15 shows the UV absorption spectrum of Compound 1-27.

16 shows a graph of LTPL measurements at 291 nm wavelength of Compound 1-33.

FIG. 17 shows a PL measurement graph of 239 nm wavelength of Compound 1-33. FIG.

18 shows the UV absorption spectrum of Compound 1-33.

19 shows a graph of LTPL measurements at 259 nm wavelength of Compound 1-39.

FIG. 20 shows a PL measurement graph at 259 nm wavelength of Compound 1-39. FIG.

21 shows the UV absorption spectra of Compounds 1-39.

22 shows a graph of LTPL measurements at 260 nm wavelength of Compound 1-41.

FIG. 23 shows a PL measurement graph at 260 nm wavelength of Compound 1-41.

24 shows the UV absorption spectrum of Compound 1-41.

25 shows a graph of LTPL measurements at 361 nm wavelength of Compound 1-65.

FIG. 26 shows a PL measurement graph of 235 nm wavelength of Compound 1-65. FIG.

27 shows the UV absorption spectrum of Compound 1-65.

28 is a graph of LTPL measurements at 360 nm wavelength of Compound 1-66.

29 shows a PL measurement graph at 307 nm wavelength of Compound 1-66.

30 shows the UV absorption spectrum of Compound 1-66.

FIG. 31 is a graph of LTPL measurements at 361 nm wavelength of Compound 1-67. FIG.

32 shows a PL measurement graph of 266 nm wavelength of Compound 1-67.

33 shows the UV absorption spectrum of Compound 1-67.

34 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-69.

35 shows a PL measurement graph of 308 nm wavelength of Compound 1-69.

36 shows the UV absorption spectrum of Compound 1-69.

37 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-70.

FIG. 38 shows a PL measurement graph of 267 nm wavelength of Compound 1-70. FIG.

39 shows the UV absorption spectrum of Compound 1-70.

40 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-71.

FIG. 41 is a graph of PL measurement at 241 nm wavelength of Compound 1-71.

42 shows the UV absorption spectrum of Compound 1-71.

43 is a graph of LTPL measurements at 361 nm wavelength of Compound 1-78.

44 shows a PL measurement graph at 263 nm wavelength of Compound 1-78.

45 shows the UV absorption spectrum of Compound 1-78.

FIG. 46 is a graph of LTPL measurements at 344 nm wavelength of Compound 1-82.

FIG. 47 shows a PL measurement graph at 307 nm wavelength of Compound 1-82.

48 shows the UV absorption spectra of Compounds 1-82.

FIG. 49 is a graph of LTPL measurements at 363 nm wavelength of Compound 1-84.

50 shows a PL measurement graph at 298 nm wavelength of Compound 1-84.

51 shows the UV absorption spectra of Compounds 1-84.

FIG. 52 is a graph of LTPL measurements at 355 nm wavelength of Compound 1-99.

53 shows a PL measurement graph at 355 nm wavelength of Compound 1-99.

54 shows the UV absorption spectrum of Compound 1-99.

Experimental Example

Experimental Example 1

1) Fabrication of organic light emitting device

A glass substrate coated with a thin film of ITO to a thickness of 1,500 kPa was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic washing with a solvent such as acetone, methanol, isopropyl alcohol and the like was dried and then UVO treated for 5 minutes using UV in a UV cleaner. Subsequently, the substrate was transferred to a plasma cleaner (PT), and then plasma-treated to remove ITO work function and residual film in a vacuum state, and then transferred to an organic deposition thermal deposition apparatus.

The hole injection layer 2-TNATA (4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine) which is a common layer on the ITO transparent electrode (anode) and the hole transport layer NPB (N, N'-Di ( 1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine) was formed.

The light emitting layer was thermally vacuum deposited on it as follows. The light emitting layer was deposited at 400 Å with 7% doping of Ir (ppy) ₃ to the host using Ir (ppy) ₃ (tris (2-phenylpyridine) iridium) as a host, the compound shown in Table 24 below, as a green phosphorescent dopant. Thereafter, 60 B of BCP was deposited as the hole blocking layer, and 200 Å of Alq ₃ was deposited as the electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to form a electron injecting layer by depositing 10 Å thick. Then, an aluminum (Al) cathode is deposited to a thickness of 1,200 위에 on the electron injecting layer to form a cathode. An electroluminescent device was manufactured.

On the other hand, all of the organic compounds required for the OLED device fabrication is 10 ^-6 to 10 respectively, for each material ^- and vacuum sublimation purification under 8torr was used in OLED production.

2) Driving voltage and luminous efficiency of organic EL device

The electroluminescent (EL) characteristics of the organic electroluminescent device manufactured as described above were measured by Maxiers M7000, and the reference luminance was 6,000 through the life equipment measuring equipment (M6000) manufactured by McScience Inc. with the measurement results. T ₉₀ was measured at cd / m ² . The characteristics of the organic EL device of the present invention are shown in Table 24 below.

TABLE 24

As can be seen from the results of Table 24, the organic electroluminescent device using the organic electroluminescent device light emitting layer material of the present invention has a lower driving voltage, improved luminous efficiency and a markedly improved lifetime as compared with Comparative Examples 1 to 7. .

On the other hand, when phenylene is positioned between carbazole and triazine as in Comparative Example 2, the electrons in the LUMO region cannot be stabilized and the service life is reduced. In addition, when there is no carbazole as in Comparative Example 3, the hole mobility is lowered and the balance between the holes and the electrons in the light emitting layer is broken, and the lifespan is reduced. In addition, in the case of a compound containing dibenzofuran as in Comparative Example 4, the electrons in the LUMO region cannot be stabilized and the lifespan is reduced. In addition, when a substituent is bonded to positions 2 and 6 of dibenzothiophene as in Comparative Example 5, the balance of holes and electrons is broken in the light emitting layer, and the life is reduced. Also, as in Comparative Examples 6 and 7, when the heteroaryl group including at least one N is not bonded to the Ar 1 position of Formula 1 of the present invention, there is no substituent to stabilize the electrons, so that the balance of holes and electrons in the light emitting layer is not good. It broke, resulting in the fall of efficiency and lifetime.

Experimental Example 2 Fabrication of Organic Light-Emitting Element

A glass substrate coated with a thin film of ITO to a thickness of 1,500 kPa was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic washing with a solvent such as acetone, methanol, isopropyl alcohol and the like was dried and then UVO treated for 5 minutes using UV in a UV cleaner. Subsequently, the substrate was transferred to a plasma cleaner (PT), and then plasma-treated to remove ITO work function and residual film in a vacuum state, and then transferred to an organic deposition thermal deposition apparatus.

The hole injection layer 2-TNATA (4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine) which is a common layer on the ITO transparent electrode (anode) and the hole transport layer NPB (N, N'-Di ( 1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine) was formed.

The light emitting layer was thermally vacuum deposited on it as follows. The light emitting layer was deposited with a compound of Formula 1 and a compound of Formula 2 at 400 kV from each individual source as a host and the green phosphorescent dopant was deposited by 7% doping of Ir (ppy) ₃ . Subsequently, 60 Å of BCP was deposited as the hole blocking layer, and Alq ₃ Was deposited at 200 Hz. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to form a electron injecting layer by depositing 10 Å thick. Then, an aluminum (Al) cathode is deposited to a thickness of 1,200 위에 on the electron injecting layer to form a cathode. An electroluminescent device was manufactured.

On the other hand, all of the organic compounds required for the OLED device fabrication is 10 ^-6 to 10 respectively, for each material ^- and vacuum sublimation purification under 8torr was used in OLED production.

Experimental Example 3 Fabrication of Organic Light-Emitting Element

A glass substrate coated with a thin film of ITO to a thickness of 1,500 kPa was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic washing with a solvent such as acetone, methanol, isopropyl alcohol and the like was dried and then UVO treated for 5 minutes using UV in a UV cleaner. Subsequently, the substrate was transferred to a plasma cleaner (PT), and then plasma-treated to remove ITO work function and residual film in a vacuum state, and then transferred to an organic deposition thermal deposition apparatus.

The hole injection layer 2-TNATA (4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine) which is a common layer on the ITO transparent electrode (anode) and the hole transport layer NPB (N, N'-Di ( 1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine) was formed.

The light emitting layer was thermally vacuum deposited on it as follows. The light emitting layer was pre-mixed with a compound of Formula 1 and a compound of Formula 2 as a host, and deposited 400 kPa in one park, and a green phosphorescent dopant was deposited by doping Ir (ppy) ₃ with 7%. Thereafter, 60 B of BCP was deposited as the hole blocking layer, and 200 Å of Alq ₃ was deposited as the electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to form a electron injecting layer by depositing 10 Å thick. Then, an aluminum (Al) cathode is deposited to a thickness of 1,200 위에 on the electron injecting layer to form a cathode. An electroluminescent device was manufactured.

On the other hand, all of the organic compounds required for the OLED device fabrication is 10 ^-6 to 10 respectively, for each material ^- and vacuum sublimation purification under 8torr was used in OLED production.

Driving voltage and luminous efficiency of the organic EL device according to Experimental Example 2 and Experimental Example 3 are as follows.

The electroluminescent (EL) characteristics of the organic electroluminescent device manufactured as described above were measured by Maxiers M7000, and the reference luminance was 6,000 through the life equipment measuring equipment (M6000) manufactured by McScience Inc. with the measurement results. T ₉₀ was measured at cd / m ² .

Properties of the organic electroluminescent device of the present invention are as shown in Tables 25 to 27. For reference, Table 25 is an example of simultaneously depositing two host compounds of Experimental Example 2 as a separate source, Table 26 is an example of depositing two light emitting layer compounds of Experimental Example 3 as a source after premixing, Table 27 In Experimental Example 2, a single host material is applied.

[Ref 1]

[Ref 2]

[Ref 3]

TABLE 25

TABLE 26

TABLE 27

The organic light emitting device of the present invention includes a light emitting layer using a host and a phosphorescent dopant, and the host includes a host compound composed of a conventional single compound by being composed of a host compound (pn type) in which two or more compounds are mixed. There is an effect that has a lifespan characteristics superior to the organic light emitting device.

In particular, the pn type host of the present invention has the advantage of increasing the emission characteristics by adjusting the ratio of the host, which can be achieved by a suitable combination of P host with good hole mobility and n host with good electron mobility to be.

In the present invention, the light emitting host consisting of a plurality of compounds was pre-mixed with the compound, and then formed by depositing with one deposition source. In this case, since the deposition is not performed several times, the uniformity and the thin film characteristics of the thin film may be improved, and the process may be simplified, the cost may be reduced, and the efficiency and the lifetime of the device may be improved.

Claims (17)

Heterocyclic compounds represented by the formula (1): [Formula 1]

In Chemical Formula 1, L1 and L2 are the same as or different from each other, and each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group, Ar1 is a substituted or unsubstituted, C _{2 Through} C ₆₀ Heteroaryl group containing at least one, Ar2 is represented by any one of the following Chemical Formulas 3 and 4, [Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4, Y1 to Y4 are the same as or different from each other, and each independently a substituted or unsubstituted C ₆ to C ₆₀ aromatic hydrocarbon ring; Or substituted or unsubstituted C ₂ to C ₆₀ aromatic heterocycle, R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. The heterocyclic compound according to claim 1, wherein Chemical Formula 3 is represented by any one of the following structural formulas:

X 1 to X 6 in the structural formulas are the same as or different from each other, and each independently NR, S, O, or CR′R ″, R8 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, m is an integer of 0-8, n, o, p, q, r, and s are each independently the integer of 0-6. The heterocyclic compound according to claim 1, wherein Formula 4 is represented by any one of the following structural formulas:

X7 and X8 in the above structural formula is the same as or different from each other, and each independently NR, S, O or CR'R ", R15 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, t is an integer of 0-7. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 5 to 10: [Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formulas 5 to 10, Definitions of R1 to R6, L1, and Ar1 is the same as the definition in Formula 1, X1, X4 and X5 are the same as or different from each other, and each independently NR, S, O or CR'R ", R8, R9, R12, R13 and R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, m is an integer of 0-8, n, q, and r are each independently the integer of 0-6, t is an integer of 0-7. The heterocyclic compound according to claim 1, wherein R1 to R6 of Formula 1 are each independently hydrogen or deuterium. The method according to claim 2, R8 to R14 of the structural formula are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. The method according to claim 3, wherein R5 to R18 of the structural formula are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. The organic light emitting device of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

An organic light emitting device comprising an anode, a cathode and at least one organic material layer provided between the anode and the cathode, at least one of the organic material layer comprises a heterocyclic compound according to any one of claims 1 to 8. The method according to claim 9, wherein the organic layer comprises at least one layer of a hole blocking layer, an electron injection layer and an electron transport layer, wherein at least one of the hole blocking layer, an electron injection layer and the electron transport layer comprises the heterocyclic compound. An organic light emitting device characterized in that. The organic light emitting device of claim 9, wherein the organic material layer comprises a light emitting layer, and the light emitting layer comprises the heterocyclic compound. The method according to claim 9, wherein the organic layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, wherein one of the layers comprises the heterocyclic compound An organic light emitting element. The organic light emitting device of claim 9, wherein the organic material layer including the heterocyclic compound further includes a compound represented by Formula 2 below: [Formula 2]

In Chemical Formula 2, R1 'to R4' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, L 1 ′ is a C ₆ to C ₆₀ arylene group which is directly bonded or substituted or unsubstituted, Ar1 'is a substituted or unsubstituted C _{6 Through} C ₆₀ aryl group; Or a substituted or unsubstituted, C _{2 Through} C ₆₀ A heteroaryl group containing at least one of S and O, Ar2 'is a substituted or unsubstituted C _{6 Through} C ₆₀ Aryl group; Or a substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, m ', p' and q 'are each independently an integer from 0 to 4, n 'is an integer of 0-2. The organic light emitting diode of claim 13, wherein Chemical Formula 2 is represented by one of Chemical Formulas 11 to 22: [Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

In Chemical Formulas 11 to 22, the definitions of L1, Ar1, Ar2, R1 to R4, m, n, p, and q are the same as the definitions in Chemical Formula 2. The organic light emitting device of claim 13, wherein Chemical Formula 2 is represented by any one of the following compounds:

A composition for an organic material layer of an organic light emitting device, comprising a heterocyclic compound represented by the following Chemical Formula 1, and a compound represented by the following Chemical Formula 2 simultaneously: [Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, L1 and L2 are the same as or different from each other, and each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group, Ar1 is a substituted or unsubstituted, C _{2 Through} C ₆₀ Heteroaryl group containing at least one, Ar2 is represented by any one of the following Chemical Formulas 3 and 4, [Formula 3]

[Formula 4]

Y1 to Y4 are the same as or different from each other, and each independently a substituted or unsubstituted C ₆ to C ₆₀ aromatic hydrocarbon ring; Or substituted or unsubstituted C ₂ to C ₆₀ aromatic heterocycle, R1 to R7 and R1 'to R4' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkenyl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group; Substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group; -SiRR'R "; -P (= O) RR '; and substituted by C ₁ to C ₂₀ alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, L 1 ′ is a C ₆ to C ₆₀ arylene group which is directly bonded or substituted or unsubstituted, Ar1 'is a substituted or unsubstituted C _{6 Through} C ₆₀ aryl group; Or a substituted or unsubstituted, C _{2 Through} C ₆₀ A heteroaryl group containing at least one of S and O, Ar2 'is a substituted or unsubstituted C _{6 Through} C ₆₀ Aryl group; Or a substituted or unsubstituted C _{2 Through} C ₆₀ Heteroaryl group, R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, m ', p' and q 'are each independently an integer from 0 to 4, n 'is an integer of 0-2. The composition of claim 16, wherein the weight ratio of the heterocyclic compound represented by Chemical Formula 1 in the composition to the compound represented by Chemical Formula 2 is 1:10 to 10: 1.

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