Compound for organic photoelectric device, composition for organic photoelectric device, organic photoelectric device and display device

Abstract

The present invention relates to a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device and a display device. Specifically, the present invention provides a compound for an organic optoelectronic device represented by Chemical Formula 1, a composition for an organic optoelectronic device containing the same, an organic optoelectronic device and a display device. The details of Chemical Formula 1 are as defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0088621 filed in the Korean Intellectual Property Office on July 6, 2021, Patent Application No. 10-2021-0064311 filed in the Korean Intellectual Property Office on May 18, 2021, Patent Application No. 10-2022-0059688 filed in the Korean Intellectual Property Office on May 16, 2022, and Patent Application No. 10-2022-0059689 filed in the Korean Intellectual Property Office on May 16, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed are a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device. Background Art

[0004] An organic photoelectric device (organic photodiode) is a device that can convert electrical energy and light energy into each other.

[0005] Organic optoelectronic devices can be categorized as follows based on their driving principles. One type is a photoelectric device that generates electrical energy by separating excitons formed from light energy into electrons and holes and transferring the electrons and holes to different electrodes. The other type is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0006] Examples of the organic optoelectronic device include an organic optoelectronic element, an organic light-emitting diode, an organic solar cell, and an organic photosensitive drum.

[0007] Among them, organic light emitting diodes (OLEDs) have recently attracted attention due to the increasing demand for flat panel displays. Organic light emitting diodes are devices that convert electrical energy into light, and their performance is greatly affected by the organic material between electrodes. Summary of the Invention

[0008] One embodiment provides a compound for an organic photoelectric device, which can realize an organic photoelectric device having high efficiency and a long lifespan.

[0009] Another embodiment provides a composition for an organic optoelectronic device, including the compound for an organic optoelectronic device.

[0010] Another embodiment provides an organic optoelectronic device including the compound for an organic optoelectronic device or the composition for an organic optoelectronic device.

[0011] Another embodiment provides a display device including an organic optoelectronic device.

[0012] According to one embodiment, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[0013] [Chemical Formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] R a and R 1 to R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0017] n1 is an integer from 1 to 3,

[0018] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0019] L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0020] R a and R 1 to R 18 At least one of them is deuterium;

[0021] R a and R 1 to R 18 at least one of which is a C1 to C30 alkyl group substituted with at least one deuterium, or a C6 to C30 aryl group substituted with at least one deuterium; or

[0022] Ar 1 and Ar 2 At least one of the groups is a C1 to C30 alkyl group substituted with at least one deuterium, a C6 to C30 aryl group substituted with at least one deuterium, or a C2 to C30 heterocyclic group substituted with at least one deuterium.

[0023] According to another embodiment, a composition for an organic photoelectric device includes a first compound and a second compound, wherein the first compound is the above-described compound for an organic photoelectric device, and the second compound is the compound for an organic photoelectric device represented by Chemical Formula 2.

[0024] [Chemical Formula 2]

[0025]

[0026] In Chemical Formula I,

[0027] Z 1 Is N or CL 3 -R 19 ,

[0028] Z 2 Is N or CL 4 -R 20 ,

[0029] Z 3 Is N or CL 5 -R 21 ,

[0030] Z 4 Is N or CL 6 -R 22 ,

[0031] Z 5 Is N or CL 7 -R 23 ,

[0032] Z 6 Is N or CL 8 -R 24 ,

[0033] Z 1 to Z 6 At least two of them are N,

[0034] L 3 To L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0035] R 19 to R 24 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0036] R 19 to R 24 are each independently present or adjacent groups are linked to each other to provide a substituted or unsubstituted aliphatic monocyclic ring, a substituted or unsubstituted aliphatic polycyclic ring, a substituted or unsubstituted aromatic monocyclic ring, a substituted or unsubstituted aromatic polycyclic ring, a substituted or unsubstituted heteroaromatic monocyclic ring, or a substituted or unsubstituted heteroaromatic polycyclic ring, and

[0037] When R 19 to R 24 When they exist independently, R 19 to R 24 At least one of them is a substituted or unsubstituted C10 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0038] According to another embodiment, an organic photoelectric device includes an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, wherein the organic layer includes a compound for an organic photoelectric device.

[0039] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0040] An organic photoelectric device with low driving force and long lifespan can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment. DETAILED DESCRIPTION

[0042] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary and the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0043] In one example of the present disclosure, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

[0044] In specific embodiments of the present disclosure, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, or cyano. In specific embodiments of the present disclosure, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl group, or cyano. In specific embodiments of the present disclosure, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl group, or cyano. In specific embodiments of the present disclosure, "substituted" means that at least one hydrogen in a substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0045] As used herein, "unsubstituted" means that a hydrogen atom is not replaced by another substituent, and hydrogen atoms remain.

[0046] As used herein, "hydrogen substitution (-H)" may include deuterium substitution (-D) or "tritium substitution (-T)."

[0047] As used herein, when no definition is otherwise provided, "hetero" means containing one to three heteroatoms selected from N, O, S, P and Si in one functional group and the remainder being carbon.

[0048] As used herein, "aryl" refers to a group containing at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic moieties may be connected by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic moieties may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl.

[0049] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0050] As used herein, "heterocyclic group" is a general concept of heteroaryl groups, and may contain at least one heteroatom selected from N, O, S, P and Si instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a condensed ring thereof or a combination thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms.

[0051] For example, "heteroaryl" may refer to an aryl group containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0052] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof, but is not limited thereto.

[0053] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted phenylthio group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzophenylthio group, a substituted or unsubstituted substituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, or a combination thereof, but not limited thereto.

[0054] In this specification, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, and due to the conductivity characteristics according to the highest occupied molecular orbital (HOMO) energy level, the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0055] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0056] Hereinafter, a compound for an organic photoelectric device according to one embodiment is described.

[0057] The compound for an organic photoelectric device according to one embodiment is represented by Chemical Formula 1.

[0058] [Chemical Formula 1]

[0059]

[0060] In Chemical Formula 1,

[0061] R a and R 1 to R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0062] n1 is an integer from 1 to 3,

[0063] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0064] L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and satisfy one or more of the conditions of the following Chemical Formula 1:

[0065] R a and R 1 to R 18 At least one of them is deuterium;

[0066] R a and R 1 to R 18 at least one of which is a C1 to C30 alkyl group substituted with at least one deuterium, or a C6 to C30 aryl group substituted with at least one deuterium; or

[0067] Ar 1 and Ar 2 At least one of the groups is a C1 to C30 alkyl group substituted with at least one deuterium, a C6 to C30 aryl group substituted with at least one deuterium, or a C2 to C30 heterocyclic group substituted with at least one deuterium.

[0068] Deuterium-substituted compounds are known to have lower ground-state energies than hydrogen-substituted compounds due to lower zero-point energy, lower vibrational energy, and reduced intermolecular interactions. This allows thin films to become amorphous, further improving heat resistance and effectively increasing the lifetime of organic light-emitting diodes fabricated using them. Therefore, the significantly improved lifetime achieved through deuterium substitution, combined with the improved hole injection and transport properties achieved through the direct bonding of carbazole to the nitrogen of the biscarbazole group, can effectively reduce the driving voltage of organic light-emitting diodes.

[0069] For example, Chemical Formula 1 may be represented by any one of Chemical Formula 1-I to Chemical Formula 1-IV.

[0070]

[0071]

[0072] In Chemical Formulas 1-I to 1-IV,

[0073] R 1 to R 18 、Ar 1 、Ar 2 , L 1 and L 2 Same as above, and R a1 to R a4 Independently with R a The definition is the same.

[0074] As a specific embodiment, Chemical Formula 1 can be represented by Chemical Formula 1-II or Chemical Formula 1-III.

[0075] In one embodiment, Chemical Formula 1 may be represented by Chemical Formula 1A.

[0076] [Chemical Formula 1A]

[0077]

[0078] In Chemical Formula 1A,

[0079] R a 、R 1 to R 7 , and R 15 to R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0080] n1 is an integer from 1 to 3,

[0081] Ar 1 and Ar 2are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and

[0082] L 1 and L 2 Each is independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group.

[0083] In a specific embodiment, Chemical Formula 1 can be represented by Chemical Formula 1B.

[0084] [Chemical Formula 1B]

[0085]

[0086] In Chemical Formula 1B,

[0087] R a 、R 1 to R 4 , and R 15 to R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0088] n1 is an integer from 1 to 3,

[0089] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and

[0090] L 1 and L 2 Each is independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group.

[0091] In a more specific embodiment, Chemical Formula 1 can be represented by Chemical Formula 1C.

[0092] [Chemical Formula 1C]

[0093]

[0094] In Chemical Formula 1C,

[0095] R a and R 15 to R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0096] n1 is an integer from 1 to 3,

[0097] Ar1 and Ar 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and

[0098] L 1 and L 2 Each is independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group.

[0099] For example, R a and R 1 to R 18 At least one of R a and R 1 to R 18 At least one of them may be a C1 to C10 alkyl group substituted by at least one deuterium, or a C6 to C20 aryl group substituted by at least one deuterium; or Ar 1 and Ar 2 At least one of may be a C1 to C10 alkyl group substituted with at least one deuterium, or a C6 to C20 aryl group substituted with at least one deuterium.

[0100] For example, the C1 to C10 alkyl group substituted by at least one deuterium may include a methyl group substituted by at least one deuterium, an ethyl group substituted by at least one deuterium, an n-propyl group substituted by at least one deuterium, an isopropyl group substituted by at least one deuterium, an n-butyl group substituted by at least one deuterium, an isobutyl group substituted by at least one deuterium, a neobutyl group substituted by at least one deuterium, a pentyl group substituted by at least one deuterium, a heptyl group substituted by at least one deuterium, an octyl group substituted by at least one deuterium, a nonyl group substituted by at least one deuterium, a decyl group substituted by at least one deuterium, and the like, but is not limited thereto.

[0101] For example, the C6 to C20 aryl group substituted by at least one deuterium may include a phenyl group substituted by at least one deuterium, a biphenyl group substituted by at least one deuterium, a terphenyl group substituted by at least one deuterium, a naphthyl group substituted by at least one deuterium, a phenanthrenyl group substituted by at least one deuterium, an anthracenyl group substituted by at least one deuterium, a triphenylene group substituted by at least one deuterium, a fluorenyl group substituted by at least one deuterium, and the like.

[0102] According to a more specific embodiment, the C6 to C20 aryl group substituted by at least one deuterium may be a phenyl group substituted by at least one deuterium, or a biphenyl group substituted by at least one deuterium, and

[0103] For example, it may be selected from the substituents of Group I.

[0104] [Group I]

[0105]

[0106] In Group I, * is the connection point.

[0107] The most specific examples of the compound for an organic photoelectric device represented by Chemical Formula 1 may include compounds of Group 1, but are not limited thereto.

[0108] [Group 1]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] A composition for an organic photoelectric device according to another embodiment includes a first compound and a second compound, wherein the first compound is the above-mentioned compound for an organic photoelectric device, and the second compound is an organic compound that may be a compound for a photoelectric device represented by Chemical Formula 2.

[0117] [Chemical Formula 2]

[0118]

[0119] In Chemical Formula 2,

[0120] Z 1 Is N or CL 3 -R 19 ,

[0121] Z 2 Is N or CL 4 -R 20 ,

[0122] Z 3 Is N or CL 5 -R 21 ,

[0123] Z 4 Is N or CL 6 -R 22 ,

[0124] Z 5 Is N or CL 7 -R 23 ,

[0125] Z6 Is N or CL 8 -R 24 ,

[0126] Z 1 to Z 6 At least two of them are N,

[0127] L 3 To L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0128] R 19 to R 24 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0129] R 19 to R 24 are each independently present or adjacent groups are linked to each other to provide a substituted or unsubstituted aliphatic monocyclic ring, a substituted or unsubstituted aliphatic polycyclic ring, a substituted or unsubstituted aromatic monocyclic ring, a substituted or unsubstituted aromatic polycyclic ring, a substituted or unsubstituted heteroaromatic monocyclic ring, or a substituted or unsubstituted heteroaromatic polycyclic ring, and

[0130] When R 19 to R 24 When they exist independently, R 19 to R 24 At least one of them is a substituted or unsubstituted C10 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0131] Depends on R 19 to R 24 Depending on whether adjacent groups are further fused, Chemical Formula 2 can be represented by any one of Chemical Formulas 2-I to 2-IV, for example.

[0132] For example, when R 19 to R 24 When each exists independently, it can be represented by Chemical Formula 2-1. In this case, at least one of R20, R22 and R24 is a substituted or unsubstituted C10 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0133] In another embodiment, R 20 and R 21to form a substituted or unsubstituted aromatic monocyclic ring or a substituted or unsubstituted aromatic polycyclic ring, and can be represented by Chemical Formula 2-II or Chemical Formula 2-III.

[0134] In another example, R 20 and R 21 may be linked to form a substituted or unsubstituted heteroaromatic polycyclic ring, which may be represented by Chemical Formula 2-IV.

[0135]

[0136]

[0137] [Chemical Formula 2-IV]

[0138]

[0139] In Chemical Formulae 2-I to 2-IV, Z 1 , Z 3 to Z 6 , L 4 , L 6 , L 8 、R 20 、R 22 and R 24 Same as above,

[0140] X 1 It is O or S,

[0141] Z in Chemical Formula 2-I 1 , Z 3 and Z 5 At least two of them are N,

[0142] Z in Chemical Formula 2-II 1 , Z 4 and Z 5 At least two of them are N,

[0143] Z in Chemical Formula 2-III and Chemical Formula 2-IV 1 , Z 4 to Z 6 At least two of them are N,

[0144] R b to R e are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0145] n2, n4 and n5 are each independently an integer from 1 to 4, and

[0146] n3 is an integer of 1 or 2.

[0147] In one embodiment, the second compound may be represented by Chemical Formula 2-I.

[0148] Specifically, in Chemical Formula 2-1, Z 1 , Z 3 and Z 5 can each independently be N or CH, and Z 1 , Z 3 and Z 5 At least two of can be N.

[0149] For example, Z 1 , Z 3 and Z 5 They can each be N.

[0150] For example, Z 1 and Z 3 Can be N, and Z 5 It can be CH.

[0151] In Chemical Formula 2-1, L 4 , L 6 and L 8 Each of them may independently be a single bond, a phenylene group, a biphenylene group, a carbazolylene group, a dibenzofuranylene group, a dibenzothiopheneylene group or a pyridylene group.

[0152] For example, L 4 , L 6 and L 8 Each independently may be a single bond, m-phenylene or p-phenylene.

[0153] In Chemical Formula 2-1, R 20 、R 22 and R 24 may be each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, R 20 、R 22 and R 24 At least one of them may be a substituted or unsubstituted C10 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0154] Specifically, R 20 、R 22 and R 24and each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fused carbazolyl group, a substituted or unsubstituted fused dibenzofuranyl group, a substituted or unsubstituted fused dibenzothiophenyl group, a substituted or unsubstituted fused indolocarbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted benzoquinazolinyl group, and

[0155] R 20 、R 22 and R 24 At least one of the may be a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fused carbazolyl group, a substituted or unsubstituted fused dibenzofuranyl group, a substituted or unsubstituted fused dibenzothiophenyl group, a substituted or unsubstituted fused indolocarbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted benzoquinazolinyl group.

[0156] For example, R 20 、R 22 and R 24 may be each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,

[0157] R 20 、R 22 , and R 24 At least one of the groups may be a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0158] For example, Chemical Formula 2-I may be represented by any one of Chemical Formulas 2-IA to 2-ID.

[0159]

[0160]

[0161] [Chemical Formula 2-ID]

[0162]

[0163] In Chemical Formulae 2-IA to 2-ID,

[0164] Z 1 , Z 3 , Z 5 , L 4 , L 6 , L 8 、R 22 and R 24 Same as described above,

[0165] X 2 Is O, S or NR i ,

[0166] Z 7 Is N or CL 9 -R 34 ,

[0167] Z 8 Is N or CL 10 -R 35 ,

[0168] Z 9 Is N or CL 11 -R 36 ,

[0169] Z 10 Is N or CL 12 -R 37 ,

[0170] Z 11 Is N or CL 13 -R 38 ,

[0171] Z 7 to Z 11 At least one of them is N,

[0172] L 9 To L 13 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0173] R i is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0174] R 25 to R 38 and R 42 to R 44 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0175] R 25 to R 38 are each independently present or adjacent groups are linked to each other to provide a substituted or unsubstituted aliphatic monocyclic ring, a substituted or unsubstituted aliphatic polycyclic ring, a substituted or unsubstituted aromatic monocyclic ring, a substituted or unsubstituted aromatic polycyclic ring, a substituted or unsubstituted heteroaromatic monocyclic ring, or a substituted or unsubstituted heteroaromatic polycyclic ring,

[0176] m is an integer from 0 to 3,

[0177] n6 to n8 are each independently an integer from 1 to 4,

[0178] n7 is an integer from 1 to 3, and

[0179] Ring A is represented by any one of Chemical Formulas A-1 to A-6,

[0180]

[0181] X 3 are each independently O or S,

[0182] R 45 to R 49 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0183] n10, n12 and n14 are each independently an integer from 1 to 4,

[0184] n11 and n13 are integers of 1 or 2, and

[0185] * is each fusion point.

[0186] In a specific embodiment, L 9 To L 13 may each independently be a single bond, a phenylene group or a biphenylene group,

[0187] R imay be a C6 to C12 aryl group, and

[0188] m can be one of integers from 0 to 2.

[0189] For example, the second compound may be represented by Chemical Formula 2-IB, and

[0190] For example, adjacent R 25 to R 28 The groups can be linked to form a series of chemical formula 2-IB-1 to chemical formula

[0191] A substituted or unsubstituted heteroaromatic polycyclic ring represented by any one of formula 2-IB-6.

[0192]

[0193]

[0194] In Chemical Formula 2-IB-1 to Chemical Formula 2-IB-6,

[0195] X 4 Yes O, S CR j R k or NL 14 -Ar 3 ,

[0196] L 4 , L 6 , L 8 and L 14 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0197] R j and R k are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

[0198] Ar 3 、R 22 and R 24 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0199] R 25 to R 32 and R 50 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen group, a cyano group, or a combination thereof, and

[0200] n15 is an integer from 1 to 4.

[0201] In a more specific embodiment, R j and R k Each may independently be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0202] In a more specific embodiment, Ar 3 It may be a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

[0203] In a more specific embodiment, R 22 and R 24 Each independently may be a substituted or unsubstituted C6 to C12 aryl group.

[0204] In a more specific embodiment, R 25 to R 32 and R 50 Each may independently represent hydrogen, deuterium, cyano, C1 to C10 alkyl, or C6 to C12 aryl.

[0205] For example, R j and R k Each of the groups may independently be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a combination thereof.

[0206] For example, Ar 3 It may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0207] For example, R 22 and R 24 Each independently may be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.

[0208] For example, R 25 to R 32 and R 50 Each may be independently hydrogen or deuterium, or at least one thereof may be a phenyl group, but is not limited thereto.

[0209] For example, R 42 to R 44 Each may be independently hydrogen or deuterium, or at least one thereof may be a phenyl group, but is not limited thereto.

[0210] In a most specific embodiment, the second compound can be represented by the above chemical formula 2-IB-2, wherein X 4 Can be NL 14 -Ar 3 , where n15 can be an integer from 1 to 4, where L 4 , L 6 , L 8 and L 14 Ar may be each independently a single bond, or a substituted or unsubstituted phenylene group, 3 It may be a substituted or unsubstituted C6 to C12 aryl group, R 22 and R 24 may each independently be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group, and R 25 to R 32 and R 50 may each independently be hydrogen or deuterium, or at least one thereof may be phenyl.

[0211] The most specific examples of the compound for an organic photoelectric device represented by Chemical Formula 2 may include, but are not limited to, compounds of Group 2.

[0212] [Group 2]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] For example, the first compound and the second compound can be included in a weight ratio of about 1:99 to about 99:1. Within the above range, the electron transport ability of the first compound and the hole transport ability of the second compound can be used to adjust the appropriate weight ratio to achieve bipolar characteristics and improve efficiency and lifespan. Within the above range, for example, they can be included in a weight ratio of about 10:90 to about 90:10, about 20:80 to about 80:20, such as about 20:80 to about 70:30, about 20:80 to about 60:40, and about 30:70 to about 60:40. As a specific embodiment, they can be included in a weight ratio of about 40:60, about 50:50, or about 60:40.

[0220] In addition to the above-mentioned compounds for an organic optoelectronic device, one or more compounds may be further included.

[0221] For example, the composition may further comprise a dopant.

[0222] The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, such as a red or green phosphorescent dopant.

[0223] A dopant is a material that emits light by mixing it in small amounts with a compound or composition used in an organic optoelectronic device. Typically, a dopant can be a material such as a metal complex that emits light by multiple excitations to a triplet state or more. The dopant can be, for example, an inorganic, organic, or organic-inorganic compound, and can contain one or more than one.

[0224] Examples of the dopant may include a phosphorescent dopant, and examples of the phosphorescent dopant may include an organometallic compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may use, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0225] [Chemical formula Z]

[0226] L 15 MX 5

[0227] In the chemical formula Z, M is a metal, and L 15 and X 5 are the same as or different from each other and are ligands that form a complex with M.

[0228] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L 15 and X 5 This may be, for example, a bidentate ligand.

[0229] By L 15 and X 5 Examples of the ligand represented by may be selected from the chemical formulae of Group A, but are not limited thereto.

[0230] [Group A]

[0231]

[0232] In Group A,

[0233] R 300 to R 302 are each independently hydrogen, deuterium, a C1 to C30 alkyl group which may be substituted by a halogen, a C6 to C30 aryl group which may be substituted by a C1 to C30 alkyl group, or a halogen, and

[0234] R 303 to R 324 Each is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroaryl, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C6 to C30 arylamino, SF5, a trialkylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group, a dialkylarylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group and a C6 to C30 aryl group, or a triarylsilyl group having a substituted or unsubstituted C6 to C30 aryl group.

[0235] As an example, a dopant represented by Chemical Formula V may be included.

[0236] [Chemical Formula V]

[0237]

[0238] In Chemical Formula V,

[0239] R 101 to R 116 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0240] R 132 to R 134 are each independently C1 to C6 alkyl,

[0241] R 101 to R 116 At least one of them is a functional group represented by Chemical Formula V-1,

[0242] L 100 is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone carbon pair or heteroatom, and

[0243] m15 and m16 are each independently any one of integers from 0 to 3, and m15+m16 is any one of integers from 1 to 3.

[0244] [Chemical Formula V-1]

[0245]

[0246] In Chemical Formula V-1,

[0247] R 135 to R 139 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0248] R 132 to R 134 are each independently C1 to C6 alkyl, and

[0249] * indicates a moiety attached to a carbon atom.

[0250] As an example, a dopant represented by Chemical Formula Z-1 may be included.

[0251] [Chemical Formula Z-1]

[0252]

[0253] In the chemical formula Z-1, rings A, B, C and D each independently represent a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0254] R A 、R B 、R C and R D each independently represents mono-, di-, tri-, or tetra-substituted or unsubstituted;

[0255] L B , L C , and L D Each is independently selected from a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', and combinations thereof;

[0256] When nA is 1, L E is selected from direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' and combinations thereof; when nA is 0, L E does not exist; and

[0257] R A 、R B 、R C 、R D R and R' are each independently selected from hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; any adjacent RA 、R B 、R C 、R D , R and R' are optionally linked to each other to provide a ring; X B 、X C 、X D and X E are each independently selected from carbon and nitrogen; and Q 1 , Q 2 , Q 3 and Q 4 Each represents oxygen or a direct bond.

[0258] The dopant according to an embodiment may be a platinum complex, and may be represented, for example, by Chemical Formula VI.

[0259] [Chemical Formula VI]

[0260]

[0261] In Chemical Formula VI,

[0262] X 100 Selected from O, S and NR 131 ,

[0263] R 117 to R 131 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0264] R 132 to R 134 are each independently C1 to C6 alkyl, and

[0265] R 117 to R 131 At least one of -SiR 132 R 133 R 134 or tert-butyl.

[0266] Hereinafter, an organic photoelectric device including the above-mentioned compound for an organic photoelectric device or the composition for an organic photoelectric device is described.

[0267] The organic photoelectric device may be any device that converts electrical energy into light energy, and vice versa, without particular limitation, and may be, for example, an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0268] Herein, an organic light emitting diode as one example of an organic photoelectric device is described with reference to the accompanying drawings.

[0269] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0270] Reference Figure 1 , an organic light emitting diode 100 according to one embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110 .

[0271] The anode 120 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; a metal oxide 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 and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0272] The cathode 110 may be made of a conductor with a small work function to facilitate electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, or an alloy thereof; or a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0273] The organic layer 105 may include the above-described compound for an organic photoelectric device or composition for an organic photoelectric device.

[0274] The organic layer 105 may include, for example, a light-emitting layer 130 , and the light-emitting layer 130 may include, for example, the above-described compound for an organic photoelectric device or composition for an organic photoelectric device.

[0275] For example, the composition for an organic optoelectronic device further including a dopant may be a green light-emitting composition.

[0276] The light emitting layer 130 may include, for example, the above-described composition for an organic optoelectronic device as a phosphorescent host.

[0277] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0278] The charge transport region may be, for example, a hole transport region 140 .

[0279] The hole transport region 140 can further increase the hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons. Specifically, the hole transport region 140 may include a hole transport layer between the anode 120 and the light emitting layer 130, and a hole transport auxiliary layer between the light emitting layer 130 and the hole transport layer, and

[0280] The compound for an organic photoelectric device or the composition for an organic photoelectric device may be included in at least one layer of a hole transport layer and a hole transport auxiliary layer.

[0281] For example, it may be contained in a hole transport auxiliary layer.

[0282] As another example, at least one of the compounds of Group B may be included in at least one of the hole transport layer and the hole transport auxiliary layer.

[0283] [Group B]

[0284]

[0285]

[0286]

[0287]

[0288] In the hole transport region 140 , in addition to these compounds, known compounds disclosed in US Pat. No. 5,061,569 A , JP 1993-009471 A , WO 1995-009147 A1 , JP 1995-126615 A ​​, JP 1998-095973 A , and the like, and compounds similar thereto can be used.

[0289] Also, the charge transport region may be, for example, the electron transport region 150 .

[0290] The electron transport region 150 may further increase electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0291] Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light emitting layer 130, and an electron transport auxiliary layer between the light emitting layer 130 and the electron transport layer, and at least one of the compounds of Group C may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[0292] [Group C]

[0293]

[0294]

[0295]

[0296]

[0297] One embodiment may provide an organic light emitting diode including a light emitting layer as an organic layer.

[0298] The light-emitting layer may include the above-mentioned composition for an organic optoelectronic device.

[0299] Another embodiment may provide an organic light emitting diode including a light emitting layer and a hole transport region as organic layers.

[0300] The hole transport region may include the above-mentioned compound for an organic optoelectronic device.

[0301] For example, the hole transport auxiliary layer may include the above-mentioned compound for an organic optoelectronic device.

[0302] Another embodiment may provide an organic light emitting diode including a light emitting layer and an electron transport region as organic layers.

[0303] In addition to the light emitting layer 130 as the organic layer 105, the organic light emitting diode according to one embodiment of the present invention may include a hole transport region 140 and an electron transport region 150, such as Figure 1 As shown in .

[0304] On the other hand, the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), and the like in addition to the light emitting layer as the above-mentioned organic layer.

[0305] The organic light emitting diode 100 may be manufactured by forming an anode or cathode on a substrate, forming an organic layer using a dry film forming method such as vacuum deposition (evaporation), sputtering, plasma plating, and ion plating, and forming the cathode or anode thereon.

[0306] Organic light emitting diodes can be applied to organic light emitting display devices.

[0307] Hereinafter, the embodiment is described in more detail with reference to Examples. However, these Examples are exemplary, and the present scope is not limited thereto.

[0308] Hereinafter, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., or Tokyo chemical industry unless specifically commented or synthesized by known methods.

[0309] (Preparation of Compounds for Organic Photoelectric Devices)

[0310] Synthesis Example 1: Synthesis of Compound 1-32

[0311] [Reaction Scheme 1]

[0312]

[0313] Step 1: Synthesis of intermediate Int-1

[0314] Under nitrogen conditions, 9-phenyl-3,3'-di-9H-carbazole (20 g, 49.0 mmol), 2-bromo-9-phenylcarbazole (15.8 g, 49.0 mmol), NaOtBu (7.1 g, 73.5 mmol), Pd2(dba)3 (2.2 g, 2.5 mmol), and P(t-Bu)3 (1.5 g, 7.4 mmol) were placed in a round-bottom flask and dissolved in xylene (245 ml), and then stirred at 120°C under reflux for 12 hours. When the reaction was complete, excess distilled water was poured into it, and then stirred for 1 hour. The solid therein was filtered and dissolved in toluene at high temperature. After removing moisture with MgSO4 and filtering the organic solvent with a silica gel pad, the filtrate therefrom was stirred. When a solid was formed, the solid was filtered and vacuum dried to obtain 21.6 g (68%) of intermediate Int-1.

[0315] Step 2: Synthesis of Compound 1-32

[0316] Under nitrogen conditions, intermediate Int-1 (21.6g, 33.27mmol), trifluoromethanesulfonic acid (24.96g, 166.35mmol) and benzene-D6 (174.97g, 2079.32mmol) are placed in a round-bottom flask and then stirred at 50°C under reflux for 20 hours. When the reaction is complete, D2O (124.82ml) is slowly poured therein for quenching and then fully stirred. A saturated solution of K3PO4 (aq) is titrated to neutralize the resulting product. After completing the reaction and removing the water layer with a separatory funnel, the organic solvent is removed therefrom under reduced pressure to obtain a solid. The obtained solid is dissolved in toluene at high temperature. After removing moisture with MgSO4 and filtering the organic solvent with a silica gel pad, the filtrate therefrom is stirred. When a solid is formed, the solid is filtered and vacuum dried to obtain 16.73g (75%) of compound 1-32.

[0317] Synthesis Example 2: Synthesis of Compound 1-62

[0318] [Reaction Scheme 2]

[0319]

[0320] Step 1: Synthesis of intermediate Int-2

[0321] Intermediate Int-2 (22.6 g, 71%) was obtained in the same manner as in the first step of Synthesis Example 1, except that the reactant was changed from 2-bromo-9-phenylcarbazole to 3-bromo-9-phenylcarbazole.

[0322] Step 2: Synthesis of Compound 1-62

[0323] Compound 1-62 (16.6 g, 71%) was obtained in the same manner as in the second step of Synthesis Example 1, except that Intermediate Int-2 was used instead of Intermediate Int-1.

[0324] Synthesis Example 3: Synthesis of Compound 1-76 [Reaction Scheme 3]

[0325]

[0326] Step 1: Synthesis of intermediate Int-3

[0327] Under nitrogen conditions, 3,3'biscarbazole (20 g, 60.2 mmol), 3-bromobiphenyl (7 g, 30.1 mmol), NaOtBu (8.7 g, 90.3 mmol), Pd2(dba)3 (2.8 g, 3.0 mmol) and P(t-Bu)3 (1.8 g, 9.0 mmol) were placed in a round-bottom flask and dissolved in 300 ml of xylene, followed by stirring at 120 ° C. under reflux for 12 hours. When the reaction was complete, an excess of distilled water was poured therein, and after stirring the mixture for 1 hour, the aqueous layer was removed therefrom. Subsequently, 11.1 g (38%) of the intermediate Int-3 was obtained by column chromatography (hexane:DCM (20%)).

[0328] Step 2: Synthesis of intermediate Int-4

[0329] Intermediate Int-4 (6.5 g, 59%) was obtained in the same manner as the first step of Synthesis Example 1, except that the reactant was changed from 9-phenyl-3,3′-di-9H-carbazole to Intermediate Int-3 and from 2-bromo-9-phenylcarbazole to 3-bromo-9-phenylcarbazole.

[0330] Step 3: Synthesis of Compound 1-76

[0331] Compound 1-76 (3.5 g, 52%) was obtained in the same manner as in the second step of Synthesis Example 1, except that Intermediate Int-4 was used instead of Intermediate Int-1.

[0332] Synthesis Example 4: Synthesis of Compound 1-33

[0333] [Reaction Scheme 4]

[0334]

[0335]

[0336] Step 1: Synthesis of intermediate Int-5

[0337] Under nitrogen conditions, 9-phenyl-3,3'-di-9H-carbazole (25g, 61.2mmol), trifluoromethanesulfonic acid (45.9g, 306.01mmol) and benzene-D6 (321.88g, 3825.06mmol) were placed in a round-bottom flask and stirred at 50°C under reflux for 20 hours. When the reaction was complete, D2O (229.61ml) was slowly poured therein for quenching and then stirred thoroughly. A saturated solution of K3PO4 (aq) was titrated to neutralize the resultant. After completing the reaction and removing the water layer with a separatory funnel, the organic solvent was treated by column chromatography (hexane: DCM (20%)) to obtain 15.5g (60%) of intermediate Int-5.

[0338] Step 2: Synthesis of intermediate Int-6

[0339] Under nitrogen conditions, iodobenzene-d5 (15 g, 71.8 mmol), 2-bromo-9H-carbazole (17.7 g, 71.8 mmol), NaOtBu (10.3 g, 107.6 mmol), Pd2(dba)3 (3.3 g, 3.6 mmol), and P(t-Bu)3 (2.2 g, 10.8 mmol) were placed in a round-bottom flask and dissolved in 360 ml of xylene, followed by stirring at 120° C. for 12 hours under reflux. When the reaction was complete, an excess of distilled water was poured into the mixture, and after stirring the mixture for 1 hour, the aqueous layer was removed therefrom. Subsequently, 16.4 g (70%) of intermediate Int-6 was obtained by column chromatography (hexane:DCM (20%)).

[0340] Step 3: Synthesis of Compound 1-33

[0341] Compound 1-33 (17.4 g, 71%) was obtained in the same manner as in the first step of Synthesis Example 1, except that Intermediate Int-5 was used instead of 9-phenyl-3,3′-di-9H-carbazole and Intermediate Int-6 was used instead of 2-bromo-9H-carbazole.

[0342] Synthesis Example 5: Synthesis of Compound 2-69

[0343] [Reaction Scheme 5]

[0344]

[0345] Under nitrogen conditions, 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (15 g, 43.6 mmol), 11,12-dihydro-11-phenylindole [2,3-a] carbazole (11.6 g, 34.9 mmol), and NaH (1.6 g, 65.4 mmol) were placed in a round-bottom flask and dissolved in 220 ml of DMF, and then stirred at room temperature for 12 hours. When the reaction was complete, excess distilled water was poured into it and then stirred for 1 hour. The solid was filtered and dissolved in MCB at high temperature. After removing moisture with MgSO4 and filtering the organic solvent with a silica gel pad, the filtrate therefrom was stirred. When a solid was formed, the solid was filtered and dried in vacuo to obtain 20.4 g (73%) of compound 2-69.

[0346] Synthesis Example 6: Synthesis of Compound 3

[0347] [Reaction Scheme 6]

[0348]

[0349] 7.6 g (42%) of Compound 3 was synthesized in the same manner as in the first step of Synthesis Example 1 except that 4-bromo-1,1′-biphenyl was used instead of 2-bromo-9H-carbazole, and then purified by column chromatography (hexane:DCM (20%)).

[0350] Comparative Synthesis Example 1: Synthesis of Compound C-1

[0351] [Reaction Scheme 7]

[0352]

[0353] Step 1: Synthesis of intermediate Int-7

[0354] Under nitrogen conditions, 9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (20 g, 40.4 mmol), 3-bromo-9-phenylcarbazole (32.5 g, 101 mmol), K2CO3 (16.7 g, 121.2 mmol), and Pd(PPh3)4 (2.3 g, 2 mmol) were placed in a round-bottom flask and dissolved in 135 ml of THF and 70 ml of distilled water, followed by stirring at 60°C under reflux for 12 hours. When the reaction was complete, after removing the aqueous layer, the organic solvent was removed under reduced pressure to obtain a solid. This solid was dissolved in MCB at high temperature.

[0355] After removing moisture with MgSO4 and filtering the organic solvent with a silica gel pad, the filtrate therefrom was stirred. When a solid was formed, the solid was filtered and dried in vacuo to obtain 18.2 g (62%) of Intermediate Int-7.

[0356] Step 2: Synthesis of Compound C-1

[0357] Compound C-1 (13.3 g, 71%) was obtained in the same manner as in the second step of Synthesis Example 1, except that Intermediate Int-7 was used instead of Intermediate Int-1.

[0358] Comparative Synthesis Example 2: Synthesis of Compound C-2

[0359] [Reaction Scheme 8]

[0360]

[0361] Step 1: Synthesis of intermediate Int-8

[0362] Intermediate Int-8 (11.6 g, 54%) was obtained in the same manner as in the first step of Comparative Synthesis Example 1, except that 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole was used instead of 9-phenyl-3,6-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole and 1-bromo-4-iodobenzene was used instead of 3-bromo-9-phenylcarbazole.

[0363] Step 2: Synthesis of intermediate Int-9

[0364] Intermediate Int-9 (26.6 g, 73%) was obtained in the same manner as in the first step of Synthesis Example 1, except that Intermediate Int-8 was used instead of 2-bromo-9H-carbazole.

[0365] Step 3: Synthesis of Compound C-2

[0366] Compound C-2 (20 g, 73%) was obtained in the same manner as in the second step of Synthesis Example 1, except that Intermediate Int-9 was used instead of Intermediate Int-1.

[0367] (Manufacturing of organic light-emitting diodes)

[0368] Example 1

[0369] A glass substrate coated with ITO (indium tin oxide) was ultrasonically cleaned with distilled water. After cleaning with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, then moved to a plasma cleaner, cleaned for 10 minutes using oxygen plasma, and moved to a vacuum depositor. The prepared ITO transparent electrode was used as an anode, and Compound A (Novaled GmbH) doped with 1% NDP-9 was vacuum deposited on the ITO substrate to form A hole injection layer is formed, and compound A is deposited on the hole injection layer. The thickness of the hole transport layer is 0.0447mm to form the hole transport layer. The compound 1-32 of Synthesis Example 1 is deposited on the hole transport layer. On the hole transport auxiliary layer, a mixture of compound 2-69 obtained in Synthesis Example 5 and compound 3 obtained in Synthesis Example 6 was used as a host in a weight ratio of 3:7 and doped with 10 wt% of PhGD as a dopant to form a hole transport auxiliary layer by vacuum deposition. Then, compound C is deposited on the light-emitting layer to form A thick electron transport auxiliary layer was formed, and compound D and LiQ were vacuum deposited at a weight ratio of 1:1 to form On the electron transport layer, LiQ and Al are vacuum deposited sequentially to Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0370] The structure is ITO / compound A (1% NDP-9 doping, ) / Compound A / Compound 1-32 / EML [90 wt% host (Compound 2-69:Compound 3 = 3:7 w / w): 10 wt% PhGD] Compound C / Compound D:LiQ / LiQ / Al

[0371] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0372] Compound B: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluoren)-2-amine

[0373] Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-biphenyl-1,3,5-triazine

[0374] Compound D: 2-(biphenyl-4-yl)-4-(9,9-biphenyl-9H-fluoren-4-yl)-6-phenyl-1,3,5-triazine

[0375] [PhGD]

[0376]

[0377] Example 2

[0378] An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 1-62 of Synthesis Example 2 was used instead of Compound 1-32.

[0379] Comparative Example 1

[0380] An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound C-1 of Comparative Synthesis Example 1 was used instead of Compound 1-32.

[0381] Example 3

[0382] A glass substrate coated with ITO (indium tin oxide) was ultrasonically cleaned with distilled water. After cleaning with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, then moved to a plasma cleaner, cleaned for 10 minutes using oxygen plasma, and moved to a vacuum depositor. The prepared ITO transparent electrode was used as an anode, and Compound A (Novaled GmbH) doped with 1% NDP-9 was vacuum deposited on the ITO substrate to form A hole injection layer is formed, and compound A is deposited on the hole injection layer. The hole transport layer is formed by depositing a thickness of Compound B was added to form a hole transport auxiliary layer. On the hole transport auxiliary layer, a mixture of Compound 1-32 obtained in Synthesis Example 1 and Compound 2-69 obtained in Synthesis Example 5 was used as a host in a weight ratio of 7:3, and 10 wt% of PhGD was doped as a dopant to form a hole transport auxiliary layer by vacuum deposition. Subsequently, compound C is deposited to form a thick light-emitting layer on the light-emitting layer. A thick electron transport auxiliary layer was formed, and compound D and LiQ were vacuum deposited at a weight ratio of 1:1 to form On the electron transport layer, LiQ and Al are vacuum deposited sequentially to Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0383] The structure is ITO / Compound A (1% NDP-9 doping, ) / Compound A / Compound B / EML [90 wt% host (Compound 1-32:Compound 2-69=7:3 w / w):10 wt% PhGD] Compound C / Compound D:LiQ / LiQ / Al

[0384] Example 4

[0385] An organic light emitting diode was manufactured in the same manner as in Example 3, except that Compound 1-62 of Synthesis Example 2 was used instead of Compound 1-32.

[0386] Comparative Example 2

[0387] An organic light emitting diode was manufactured in the same manner as in Example 3, except that Compound C-1 of Comparative Synthesis Example 1 was used instead of Compound 1-32.

[0388] Comparative Example 3

[0389] An organic light emitting diode was manufactured in the same manner as in Example 3, except that Compound C-2 of Comparative Synthesis Example 2 was used instead of Compound 1-32.

[0390] Comparative Example 4

[0391] An organic light emitting diode was manufactured in the same manner as in Example 3, except that Compound Int-1 of Synthesis Example 1 was used instead of Compound 1-32.

[0392] Comparative Example 5

[0393] An organic light emitting diode was manufactured in the same manner as in Example 3, except that Compound Int-2 of Synthesis Example 2 was used instead of Compound 1-32.

[0394] evaluate

[0395] The driving voltage and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 4 and Comparative Examples 1 to 5 were evaluated.

[0396] The specific measurement method is as follows, and the results are shown in Tables 1 and 2.

[0397] (1) Measurement of current density changes according to voltage changes

[0398] The obtained organic light emitting diode was measured with respect to a current value flowing in a unit device while increasing a voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by an area to provide a result.

[0399] (2) Measurement of brightness changes according to voltage changes

[0400] While the voltage of the organic light emitting diode was increased from 0V to 10V, the luminance was measured by using a luminance meter (Minolta Cs-1000A).

[0401] (3) Measurement of current efficiency

[0402] By using the luminance and current density and voltage from items (1) and (2) to calculate the current density at the same current density (10 mA / cm 2 ) under the current efficiency (cd / A).

[0403] (4) Driving voltage

[0404] The ampere-voltmeter (Keithley 2400) was used to measure the 2 Measure the driving voltage of each diode.

[0405] (5) Power efficiency

[0406] The power efficiency value was calculated by Equation 1 and was calculated based on the relative value of the power efficiency of Comparative Example 1 and is shown in Table 1.

[0407] [Equation 1]

[0408] Power efficiency (lm / W) = [current efficiency (cd / A) / driving voltage (V)] * Π

[0409] (π represents the ratio of circumference)

[0410] (6) Lifespan measurement

[0411] The brightness (cd / m 2 ) maintained at 24000cd / m 2 , and measured the time it took for the current efficiency (cd / A) to drop to 97% to obtain the results.

[0412] Table 2 shows relative values ​​obtained by converting the life of T97 in Example 4 to 100%.

[0413] (Table 1)

[0414] serial number Hole transport auxiliary layer Power efficiency ratio (%) Example 1 1-32 114％ Example 2 1-62 110％ Comparative Example 1 C-1 100％

[0415] Referring to Table 1, the organic light emitting diode manufactured by using the compound represented by the above Chemical Formula 1 as a hole transport auxiliary layer material particularly achieves high efficiency characteristics.

[0416] (Table 2)

[0417] serial number First subject Second subject T97 lifespan ratio (%) Example 3 1-32 2-69 117％ Example 4 1-62 2-69 100％ Comparative Example 2 C-1 2-69 13％ Comparative Example 3 C-2 2-69 71％ Comparative Example 4 Int-1 2-69 90％ Comparative Example 5 Int-2 2-69 76％

[0418] Referring to Table 2, an organic light-emitting diode manufactured by using the compound represented by Chemical Formula 1 as a host material of a light-emitting layer particularly achieves long life characteristics. In particular, the organic light-emitting diode using the compound represented by Chemical Formula 1 exhibits a significant increase in lifespan compared to a diode using a different compound having a skeleton identical to or similar to that of Chemical Formula 1 but with different carbazole and deuterium substituted bonding positions.

[0419] While the invention has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0420] <Description of label>

[0421] 100: Organic Light-Emitting Diode

[0422] 105: Organic layer

[0423] 110: cathode

[0424] 120: Anode

[0425] 130: Luminous layer

[0426] 140: Hole transport zone

[0427] 150: Electron transport region.

Claims

1. A compound for an organic optoelectronic device, represented by chemical formula 1C: [Chemical formula 1C] In Chemical Formula 1C, R a and R 15 To R 18 It's deuterium. n1 is 3, Ar 1 and Ar 2 are each independently a C6 to C30 aryl group, and L 1 and L 2 are each independently a single bond.

2. The compound for an organic optoelectronic device according to claim 1, wherein The compound is one of the compounds of Group 1: [Group 1] [1-2] [1-11] [1-16] [1-21] [1-28] [1-32] [1-41] [1-46] [1-51] [1-58] [1-62] [1-71] [1-76] [1-81] [1-88] [1-92] [1-101] [1-106] [1-111] [1-118] 3. A composition for an organic optoelectronic device, comprising a first compound and a second compound, in, The first compound is the compound for an organic photoelectric device according to claim 1, and The second compound is a compound represented by Chemical Formula 2: [Chemical formula 2] Wherein, in Chemical Formula 2, Z 1 N or CL 3 -R 19 , Z 2 N or CL 4 -R 20 , Z 3 N or CL 5 -R 21 , Z 4 N or CL 6 -R 22 , Z 5 N or CL 7 -R 23 , Z 6 N or CL 8 -R 24 , Z 1 To Z 6 At least two of them are N, L 3 To L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, R 19 To R 24 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof, R 19 To R 24 Each independently is present or adjacent groups thereof are linked to each other to provide a substituted or unsubstituted aliphatic monocyclic ring, a substituted or unsubstituted aliphatic polycyclic ring, a substituted or unsubstituted aromatic monocyclic ring, a substituted or unsubstituted aromatic polycyclic ring, a substituted or unsubstituted heteroaromatic monocyclic ring, or a substituted or unsubstituted heteroaromatic polycyclic ring, and When R 19 To R 24 When they exist independently, R 19 To R 24 At least one of them is a substituted or unsubstituted C10 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

4. The composition for an organic optoelectronic device according to claim 3, wherein: The second compound is represented by chemical formula 2-IB: [Chemical formula 2-IB] Wherein, in chemical formula 2-IB, Z 1 , Z 3 and Z 5 are each independently N or CH, Z 1 , Z 3 and Z 5 At least two of them are N, L 4 , L 6 and L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, R 22 and R 24 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, R 25 To R 32 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano, or a combination thereof, and R 25 To R 32 Each is independently present or adjacent groups are linked to each other to provide a substituted or unsubstituted aliphatic monocyclic ring, a substituted or unsubstituted aliphatic polycyclic ring, a substituted or unsubstituted aromatic monocyclic ring, a substituted or unsubstituted aromatic polycyclic ring, a substituted or unsubstituted heteroaromatic monocyclic ring, or a substituted or unsubstituted heteroaromatic polycyclic ring.

5. The composition for an organic optoelectronic device according to claim 4, wherein: The second compound is represented by any one of Chemical Formula 2-IB-1 to Chemical Formula 2-IB-6: In the chemical formula 2-IB-1 to the chemical formula 2-IB-6, X 4 Yes O, S CR j R k or NL 14 -Ar 3 , n15 is an integer from 1 to 4, L 4 , L 6 , L 8 and L 14 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, R j and R k are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, Ar 3 , R 22 , and R 24 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, and R 25 To R 32 and R 50 Each is independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof.

6. An organic optoelectronic device comprising The anode and cathode face each other, at least one organic layer between the anode and the cathode, in, The organic layer comprises the compound for an organic photoelectric device according to any one of claims 1 to 2 or the composition for an organic photoelectric device according to any one of claims 3 to 5 .

7. The organic optoelectronic device according to claim 6, wherein: The organic layer includes a light-emitting layer, and The light-emitting layer includes the composition for an organic photoelectric device.

8. The organic optoelectronic device according to claim 6, wherein: The organic layer includes a light-emitting layer, a hole transport layer between the anode and the cathode, and a hole transport auxiliary layer between the light-emitting layer and the hole transport layer, and The hole transport auxiliary layer includes the compound for an organic photoelectric device. 9 . A display device comprising the organic optoelectronic device according to claim 6 .

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