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

Abstract

The present invention relates to: a compound for an organic optoelectronic device represented by chemical formula 1; a composition comprising the compound for an organic optoelectronic device; an organic optoelectronic device; and a display device. The details of the chemical formula 1 are as defined in the specification.

Description

Technical Field

[0001] 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

[0002] Organic optoelectronic devices (organic optoelectronic diodes) are devices that can convert electrical energy into light energy and vice versa.

[0003] Organic optoelectronic devices can be roughly divided into two categories based on their working principles: one is a photoelectric device that generates electrical energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively; the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0004] Examples of the organic optoelectronic device include an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0005] Among them, organic light emitting diodes (OLEDs) have attracted much attention in recent years due to the increasing demand for flat panel display devices. Organic light emitting diodes are devices that convert electrical energy into light, and the performance of organic light emitting diodes is greatly affected by organic materials between electrodes. Summary of the invention

[0006] Technical issues

[0007] One embodiment provides a compound for an organic optoelectronic device capable of realizing a high-efficiency and low-driving organic optoelectronic device.

[0008] Another embodiment provides a composition for an organic optoelectronic device including the compound for an organic optoelectronic device.

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

[0010] Another embodiment provides a display device including the organic optoelectronic device.

[0011] Technical Solution

[0012] According to one embodiment, a compound represented by Chemical Formula 1 is provided.

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] R 1is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C6 to C20 heterocyclic group,

[0017] Z 1 To Z 3 Each independently is N or CR a ,

[0018] Z 1 To Z 3 At least two of them are N,

[0019] Z 4 To Z 6 Each independently is N or CR b ,

[0020] Z 4 To Z 6 At least two of them are N,

[0021] R a , R b , R 2 and R 3 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0022] L 1 To L 4 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group,

[0023] Ar 1 To Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0024] m1 and m2 are each independently one of integers from 1 to 4, and

[0025] m3 is one of integers from 1 to 3.

[0026] According to another embodiment, a composition for an organic optoelectronic device includes a first compound and a second compound.

[0027] The first compound may be the above-described compound for an organic optoelectronic device, and the second compound may be represented by Chemical Formula 2, a combination of Chemical Formula 3 and Chemical Formula 4, or Chemical Formula 5.

[0028] [Chemical formula 2]

[0029]

[0030] In chemical formula 2,

[0031] R 4 To R 8 and Ar 7 To Ar 10 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0032] Ar 5 and Ar 6 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0033] L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0034] m4, m7 and m8 are each independently one of integers from 1 to 4,

[0035] m5 and m6 are each independently one of integers from 1 to 3, and

[0036] n is an integer from 0 to 2;

[0037] [Chemical formula 3] [Chemical formula 4]

[0038]

[0039] In Chemical Formula 3 and Chemical Formula 4,

[0040] a1* to a4* in Chemical Formula 3 are each independently a connecting carbon (C) or CL a -R c ,

[0041] Among a1* to a4* in Chemical Formula 3, two adjacent ones are each connected to * in Chemical Formula 4, L a , L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0042] R c ,Ar 13 ,Ar 14 , R 9 and R 10are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0043] Ar 11 and Ar 12 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0044] m9 and m10 are each independently one of integers from 1 to 4;

[0045] [Chemical formula 5]

[0046]

[0047] In Chemical Formula 5,

[0048] L 10 is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0049] R 16 To R 28 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0050] Ar 13 is a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0051] m16 is an integer between 1 and 3.

[0052] According to another embodiment, an organic optoelectronic 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 the compound for an organic optoelectronic device or the composition for an organic optoelectronic device.

[0053] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0054] Beneficial Effects

[0055] Low-drive and high-efficiency organic optoelectronic devices can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0057] <Description of Reference Numerals>

[0058] 100: Organic Light Emitting Diode

[0059] 105: Organic layer

[0060] 110: cathode

[0061] 120: Anode

[0062] 130: Luminous layer

[0063] 140: Hole transport region

[0064] 150: Electron transport region DETAILED DESCRIPTION

[0065] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

[0066] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of a substituent or a 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.

[0067] In one example of the present invention, "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 a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl or cyano. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl or cyano. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl or naphthyl.

[0068] In the present specification, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0069] In the present specification, "hydrogen substitution (-H)" may include "deuterium substitution (-D)" or "tritium substitution (-T)".

[0070] In the present specification, when a definition is not otherwise provided, "hetero" means containing one to three hetero atoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0071] In the present specification, "aryl" refers to a group including at least one hydrocarbon aromatic portion, and all elements of the hydrocarbon aromatic portion have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic portions may be connected by a σ bond, and may be, for example, a biphenyl group, a terphenyl group, a quaterphenyl group, etc., and two or more hydrocarbon aromatic portions are directly or indirectly fused to provide a non-aromatic fused ring, such as a fluorenyl group.

[0072] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0073] As used herein, "heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si in place of carbon (C) in a cyclic compound such as an aryl, a cycloalkyl, 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 include one or more heteroatoms.

[0074] For example, "heteroaryl" may refer to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.

[0075] 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 tetraphenyl group, a substituted or unsubstituted pyrene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted para-terphenyl group, a substituted or unsubstituted meta-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted peryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

[0076] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted The invention may include, but is not limited to, a substituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted naphthyridinyl, a substituted or unsubstituted benzoxazinyl, a substituted or unsubstituted benzothiazinyl, a substituted or unsubstituted acridinyl, a substituted or unsubstituted phenazinyl, a substituted or unsubstituted phenothiazinyl, a substituted or unsubstituted phenoxazinyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzofuranyl or a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted benzonaphthofuranyl, a substituted or unsubstituted benzonaphthothiophenyl, a substituted or unsubstituted benzofuranofluorenyl, a substituted or unsubstituted benzothiophenefluorenyl, or a combination thereof, but is not limited thereto.

[0077] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductive 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.

[0078] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level.

[0079] Hereinafter, a compound for an organic optoelectronic device according to one embodiment is described.

[0080] The compound for an organic optoelectronic device according to one embodiment is represented by Chemical Formula 1.

[0081] [Chemical formula 1]

[0082]

[0083] In Chemical Formula 1,

[0084] R 1is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C6 to C20 heterocyclic group,

[0085] Z 1 To Z 3 Each independently is N or CR a ,

[0086] Z 1 To Z 3 At least two of them are N,

[0087] Z 4 To Z 6 Each independently is N or CR b ,

[0088] Z 4 To Z 6 At least two of them are N,

[0089] R a , R b , R 2 and R 3 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0090] L 1 To L 4 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group,

[0091] Ar 1 To Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0092] m1 and m2 are each independently one of integers from 1 to 4, and

[0093] m3 is one of integers from 1 to 3.

[0094] The compound for an organic optoelectronic device represented by Chemical Formula 1 has a structure in which the carbazole is substituted with a nitrogen-containing 6-membered ring in both the N direction (9-direction) and the phenyl direction (1-direction to 8-direction) of the carbazole relative to the center.

[0095] The N-direction (9-direction) substituent of carbazole is linked via an o-phenylene group, and the luminescence efficiency of a device applied thereto can be improved by shallowly controlling the LUMO energy level.

[0096] Furthermore, since the nitrogen-containing 6-membered ring is additionally substituted in the phenyl direction (1-direction to 8-direction) of carbazole, electron mobility can be increased, and thus the operating voltage of a device applied thereto can be reduced.

[0097] That is, a device to which the compound for an organic optoelectronic device represented by Chemical Formula 1 is applied may simultaneously achieve low driving and high efficiency characteristics.

[0098] For example, R 1 A substituent other than an electron withdrawing group may be provided.

[0099] For example, R 1 It may be hydrogen, deuterium, a substituted or unsubstituted C1 to C6 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0100] The electron withdrawing group may be, for example, a halogen atom (such as F, Cl, I, Br), a halogenated alkyl compound composed of these atoms, a cyano group, and the like.

[0101] When R 1 When it is an electron withdrawing group, the LUMO level cannot be shallowly controlled, and in this case, the desired effect cannot be obtained.

[0102] In one embodiment, R 1 It may be hydrogen, deuterium or a substituted or unsubstituted C1 to C5 alkyl group.

[0103] For example, R 2 and R 3 Each may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

[0104] As a specific example, R 2 and R 3 They may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0105] For example, R 2 and R 3 and may each independently be hydrogen, deuterium, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl or substituted or unsubstituted naphthyl.

[0106] For example, L 1 To L 4 Each may independently be a single bond or a substituted or unsubstituted C6 to C12 arylene group.

[0107] As a specific example, L 1 To L4 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0108] For example, Ar 1 To Ar 4 Each of them may independently 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 anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group or a substituted or unsubstituted dibenzosilyl group.

[0109] As a specific example, Ar 1 To Ar 4 Each of them independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothienyl group.

[0110] For example, Chemical Formula 1 may be represented by any one of Chemical Formulas 1A to 1D according to a specific substitution position of the nitrogen-containing 6-membered ring on the phenyl group of carbazole.

[0111]

[0112] In Chemical Formulae 1A to 1D,

[0113] Z 1 To Z 6 , R 1 To R 3 , L 1 To L 4 ,Ar 1 To Ar 4 And m1 to m3 are the same as above.

[0114] As a specific example, Chemical Formula 1 may be represented by any one of Chemical Formula 1B or Chemical Formula 1D.

[0115] For example, Chemical Formula 1 may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-9.

[0116]

[0117]

[0118] In Chemical Formula 1-1 to Chemical Formula 1-9,

[0119] R 1 To R 3 , L1 To L 4 ,Ar 1 To Ar 4 And m1 to m3 are the same as above.

[0120] As a specific example, Chemical Formula 1 can be represented by Chemical Formula 1-1.

[0121] As a more specific example, Chemical Formula 1 may be represented by Chemical Formula 1-B-1 or Chemical Formula 1-D-1.

[0122]

[0123] In Chemical Formula 1-B-1 and Chemical Formula 1-D-1,

[0124] R 1 To R 3 , L 1 To L 4 ,Ar 1 To Ar 4 And m1 to m3 are the same as above.

[0125] For example, the compound for an organic optoelectronic device represented by Chemical Formula 1 may be one selected from the compounds listed in Group 1, but is not limited thereto.

[0126] [Group 1]

[0127]

[0128]

[0129] A composition for an organic optoelectronic device according to another embodiment includes a first compound and a second compound, wherein the first compound may be the above-mentioned compound for an organic optoelectronic device, and the second compound may be represented by Chemical Formula 2, a combination of Chemical Formula 3 and Chemical Formula 4, or Chemical Formula 5.

[0130] [Chemical formula 2]

[0131]

[0132] In chemical formula 2,

[0133] R 4 To R 8 and Ar 7 To Ar 10 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0134] Ar 5 and Ar 6 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0135] L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0136] m4, m7 and m8 are each independently one of integers from 1 to 4,

[0137] m5 and m6 are each independently one of integers from 1 to 3, and

[0138] n is an integer from 0 to 2.

[0139]

[0140] In Chemical Formula 3 and Chemical Formula 4,

[0141] a1* to a4* in Chemical Formula 3 are each independently a connecting carbon (C) or CL a -R c ,

[0142] Among a1* to a4* in Chemical Formula 3, two adjacent ones are each connected to * in Chemical Formula 4, L a , L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0143] R c ,Ar 13 ,Ar 14 , R 9 and R 10 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0144] Ar 11 and Ar 12 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0145] m9 and m10 are each independently one of integers from 1 to 4.

[0146] [Chemical formula 5]

[0147]

[0148] In Chemical Formula 5,

[0149] L 10 is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0150] R 16 To R 28 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0151] Ar 13 is a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0152] m16 is an integer between 1 and 3.

[0153] The second compound may be used together with the first compound in the light emitting layer to improve light emitting efficiency and lifespan characteristics by increasing charge mobility and stability.

[0154] For example, in Formula 2, Ar 5 and Ar 6 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 naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted fluorenyl group,

[0155] In chemical formula 2, L 5 and L 6 may each independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,

[0156] In chemical formula 2, R 4 To R 8 and Ar 7 To Ar 10 may each independently be hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, and

[0157] n can be 0 or 1.

[0158] As an example, in Chemical Formula 2, "substituted" means that at least one hydrogen is replaced by deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.

[0159] For example, in Formula 2, Ar 5 and Ar6 Each of them independently may be a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted fluorenyl group.

[0160] In one embodiment of the present invention, Chemical Formula 2 may be represented by one of Chemical Formulas 2-1 to 2-15.

[0161]

[0162]

[0163] In Chemical Formulae 2-1 to 2-15, R 4 To R 8 and Ar 7 To Ar 10 may each independently be hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, and *-L 5 -Ar 5 and *-L 6 -Ar 6 Each may independently be one of the substituents listed in Group I.

[0164] [Group I]

[0165]

[0166] In Group I,

[0167] R 11 To R 15 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl,

[0168] m11 is an integer from 1 to 5,

[0169] m12 is an integer from 1 to 4,

[0170] m13 is an integer from 1 to 3,

[0171] m14 is an integer of 1 or 2.

[0172] m15 is an integer from 1 to 7, and

[0173] * is the connection point.

[0174] In a specific embodiment of the present invention, the combination of Chemical Formula 3 and Chemical Formula 4 can be represented by any one of Chemical Formula 3A, Chemical Formula 3B, Chemical Formula 3C, Chemical Formula 3D, and Chemical Formula 3E, for example.

[0175]

[0176] In Chemical Formulae 3A to 3E, Ar 11 ,Ar 12 , L 7 , L 8 ,Ar 13 ,Ar 14 , R 9 and R 10 Same as above,

[0177] L a1 To L a4 Definition and above L 7 and L 8 The same, and

[0178] R c1 To R c4 Definition and Ar 13 ,Ar 14 , R 9 and R 10 same.

[0179] For example, in Formulas 3 and 4, Ar 11 and Ar 12 may each independently 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 anthracenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted fluorenyl group, and

[0180] R c1 To R c4 ,Ar 13 ,Ar 14 , R 9 and R 10 Each of them may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

[0181] In a specific embodiment of the present invention, in Chemical Formulas 3 and 4, *-L 7 -Ar 11 and *-L 8 -Ar 12 The substituents listed in Group I may be each independently selected.

[0182] In one embodiment, R c1 To R c4 ,Ar 13 ,Ar 14 , R9 and R 10 Each of them may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

[0183] For example, R c1 To R c4 ,Ar 13 ,Ar 14 , R 9 and R 10 may each independently be hydrogen, deuterium, cyano or substituted or unsubstituted phenyl, and

[0184] In one embodiment, R c1 To R c4 ,Ar 13 ,Ar 14 , R 9 and R 10 and may each independently be hydrogen, deuterium, or substituted or unsubstituted phenyl.

[0185] In a specific embodiment of the present invention, Chemical Formula 5 may be represented by, for example, any one of Chemical Formula 5-1 to Chemical Formula 5-4.

[0186]

[0187]

[0188] In Chemical Formula 5-1 to Chemical Formula 5-4,

[0189] L 10 , R 16 To R 28 ,Ar 13 and m16 are the same as above.

[0190] For example, in Formula 5, Ar 13 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 anthracenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted fluorenyl group, and

[0191] R 16 To R 28Each of them may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

[0192] In a specific embodiment of the present invention, the second compound can be represented by Chemical Formula 2-8, in which Ar 5 and Ar 6 may be each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group, L 5 and L 6 may each independently be a single bond or a substituted or unsubstituted C6 to C20 arylene group, and Ar 7 To Ar 10 and R 4 To R 7 Each of them may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

[0193] For example, in Chemical Formula 2-8, Ar 7 To Ar 10 and R 4 To R 7 may each independently be hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, and *-L 5 -Ar 5 and *-L 6 -Ar 6 The substituents listed in Group I may be each independently selected.

[0194] In a specific embodiment of the present invention, the second compound can be represented by Chemical Formula 3C, in which L a3 and L a4 Can be a single bond, L 7 and L 8 may be each independently a single bond or a substituted or unsubstituted C6 to C12 arylene group, Ar 13 ,Ar 14 , R 9 , R 10 , R c3 and R c4 may each independently be hydrogen, deuterium or phenyl, and Ar 11 and Ar 12Each of them may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.

[0195] For example, in Formula 3C, L c3 and L c4 Can be a single bond, Ar 13 ,Ar 14 , R 9 , R 10 , R c3 and R c4 may each independently be hydrogen, deuterium or C6 to C12 aryl, and *-L 7 -Ar 11 and *-L 8 -Ar 12 Each may independently be one of the substituents listed in Group I.

[0196] In another embodiment of the present invention, the second compound can be represented by Chemical Formula 5-2 or Chemical Formula 5-3, and L 10 -Ar 13 The substituents listed in Group I may be selected.

[0197] For example, R 16 To R 28 They may each independently be hydrogen, deuterium, cyano or substituted or unsubstituted phenyl.

[0198] For example, the second compound for an organic optoelectronic device may be one selected from the compounds listed in Group 2, but is not limited thereto.

[0199] [Group 2]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] In addition, examples are given below in which at least one hydrogen in Compound B-1 to Compound B-152 listed in Group 2 is replaced by deuterium, but are not limited thereto.

[0208]

[0209]

[0210] (Dn refers to the number of deuterium substitution and represents a structure substituted with one or more deuterium)

[0211] For compounds B-153 to B-197 of Group 2, the most specific structures are provided below according to deuterium substitution positions and substitution ratios only as examples, and are not intended to limit the scope of rights to compounds not provided below.

[0212] The scope of the present invention is determined by the claims, and if substituted with deuterium, the present invention is not limited to the compounds exemplified below, but can include all variable ranges within the range of Compound B-1 to Compound B-197 according to the deuterium substitution position and deuterium substitution rate, etc.

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] In addition, examples are given below in which at least one hydrogen in Compound C-1 to Compound C-57 listed in Group 2 is replaced by deuterium, but are not limited thereto.

[0220]

[0221] (Dn refers to the number of deuterium substitution and represents a structure substituted with one or more deuterium)

[0222]

[0223]

[0224]

[0225] In addition, examples are given below in which at least one hydrogen in Compound D-1 to Compound D-60 listed in Group 2 is replaced by deuterium, but are not limited thereto.

[0226]

[0227]

[0228]

[0229] (Dn refers to the number of deuterium substitution and represents a structure substituted with one or more deuteriums)

[0230] The first compound and the second compound may be included in a weight ratio of, for example, 1:99 to 99:1. Within the above range, bipolar characteristics may be achieved by matching the appropriate weight ratio using the electron transport capability of the first compound and the hole transport capability of the second compound, thereby improving efficiency and lifespan. Within this range, for example, they may be included in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20 (e.g., 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 example, they may be included in a weight ratio of 40:60, 50:50, or 60:40.

[0231] In addition to the above-mentioned first compound and second compound, one or more additional compounds may be contained.

[0232] The above-mentioned compound for an organic optoelectronic device or the composition for an organic optoelectronic device may be a composition further including a dopant.

[0233] The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a red or green phosphorescent dopant.

[0234] A dopant is a material mixed in a small amount with a compound or composition for an organic optoelectronic device to cause light emission, and may generally be a material such as a metal complex that emits light by multiple excitations to a triplet state or more. The dopant may be, for example, an inorganic, organic, or organic / inorganic compound, and one or more types thereof may be used.

[0235] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal 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 be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0236] [Chemical formula Z]

[0237] L 9 MX

[0238] In the chemical formula Z, M is a metal and L 9 and X are the same or different and are ligands that form a complex with M.

[0239] 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 9 and X may be, for example, a bidentate ligand.

[0240] By L 9 Examples of the ligand represented by and X may be selected from the chemical formulae listed in Group A, but are not limited thereto.

[0241] [Group A]

[0242]

[0243] In Group A,

[0244] R 300 To R 302 are each independently hydrogen, deuterium, C1 to C30 alkyl which may be substituted by halogen, C6 to C30 aryl which may be substituted by C1 to C30 alkyl, or halogen, and

[0245] 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.

[0246] The dopant according to one embodiment may be an iridium complex, and may be represented, for example, by Chemical Formula 6-1 or Chemical Formula 6-2.

[0247] [Chemical formula 6-1]

[0248]

[0249] In chemical formula 6-1,

[0250] 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 R134 ,

[0251] R 132 To R 134 are each independently C1 to C6 alkyl,

[0252] R 101 To R 116 At least one of them is a functional group represented by the chemical formula V-1,

[0253] L 100 is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone electron pair of a carbon or heteroatom, and

[0254] m19 and m20 are each independently any one of integers from 0 to 3 and m19+m20 is any one of integers from 1 to 3,

[0255] [Chemical formula V-1]

[0256]

[0257] In chemical formula V-1,

[0258] 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 ,and

[0259] * indicates a moiety attached to a carbon atom.

[0260] [Chemical formula 6-2]

[0261]

[0262] In chemical formula 6-2,

[0263] R 101 To R 117 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 133 R 134 R 135 ,

[0264] R 133 To R 135 are each independently a substituted or unsubstituted C1 to C6 alkyl group,

[0265] L 100is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone electron pair of a carbon or heteroatom, and

[0266] n1 and n2 are each independently any one of integers from 0 to 3 and n1+n2 is any one of integers from 1 to 3.

[0267] As an example, a dopant represented by Chemical Formula Z-1 may be included.

[0268] [Chemical formula Z-1]

[0269]

[0270] In the chemical formula Z-1, rings A, B, C and D independently represent a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0271] R A , R B , R C and R D independently represents mono-, di-, tri- or tetra-substituted or unsubstituted;

[0272] 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;

[0273] When nA is 1, L E is selected from the group consisting of 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

[0274] R A , R B , R C , R D R, 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 R A , 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 Eare each independently selected from carbon and nitrogen; and Q 1 , Q 2 , Q 3 and Q 4 Each represents oxygen or a direct bond.

[0275] The platinum complex may be represented by, for example, Chemical Formula 7-1 or Chemical Formula 7-2.

[0276] [Chemical formula 7-1]

[0277]

[0278] [Chemical formula 7-2]

[0279]

[0280] In Chemical Formula 7-1 and Chemical Formula 7-2,

[0281] X 100 Selected from O, S and NR 132 ,

[0282] R 118 To R 132 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 133 R 134 R 135 ,

[0283] R 133 To R 135 are each independently a substituted or unsubstituted C1 to C6 alkyl group,

[0284] R 118 To R 132 At least one of them is -SiR 133 R 134 R 135 or tert-butyl, and

[0285] R 133 To R 135 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0286] Hereinafter, an organic optoelectronic device using the above-mentioned compound for an organic optoelectronic device or the composition for an organic optoelectronic device is described.

[0287] The organic optoelectronic device may be a suitable device that converts electrical energy into light energy, and vice versa, such as an organic photovoltaic device, an organic light emitting diode, an organic solar cell, or an organic photosensitive drum.

[0288] Here, an organic light emitting diode as an example of an organic optoelectronic device is described with reference to the accompanying drawings.

[0289] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0290] 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 .

[0291] 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 the like, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; 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.

[0292] The cathode 110 may be made of a conductor having 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 include a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca, but is not limited thereto.

[0293] The organic layer 105 may include the above-described compound for an organic optoelectronic device or the composition for an organic optoelectronic device.

[0294] The organic layer 105 may include a light emitting layer 130 , and the light emitting layer 130 may include the above-described compound for an organic optoelectronic device or composition for an organic optoelectronic device.

[0295] The composition for an organic optoelectronic device further including a dopant may be, for example, a green light emitting composition.

[0296] The light emitting layer 130 may include, for example, the above-described compound for an organic optoelectronic device or the composition for an organic optoelectronic device as a phosphorescent host.

[0297] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0298] The charge transport region may be, for example, a hole transport region 140 .

[0299] The hole transport region 140 may further increase hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.

[0300] 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 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.

[0301] [Group B]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308] (Dn refers to the number of deuterium substitution and represents a structure substituted with one or more deuteriums)

[0309] In the hole transport region 140, in addition to the above-mentioned compounds, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds having similar structures can be used.

[0310] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0311] 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.

[0312] 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.

[0313] [Group C]

[0314]

[0315]

[0316]

[0317] One embodiment may be an organic light emitting diode including a light emitting layer as an organic layer.

[0318] Another embodiment may be an organic light emitting diode including a light emitting layer and a hole transporting region as organic layers.

[0319] Another embodiment may be an organic light emitting diode including a light emitting layer and an electron transport region as organic layers.

[0320] Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region 140 and an electron transport region 150 as the organic layer 105 in addition to the light emitting layer 130, such as Figure 1 as shown in .

[0321] On the other hand, the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), etc. as organic layers in addition to the light emitting layer.

[0322] The organic light emitting diode 100 may be manufactured by forming an anode or a cathode on a substrate, then forming an organic layer by a dry film method such as vacuum deposition, sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0323] The organic light emitting diode may be applied to an organic light emitting display device.

[0324] Invention Mode

[0325] Hereinafter, the embodiments are described in more detail with reference to examples. However, these examples are exemplary, and the scope of claims is not limited thereto.

[0326] Hereinafter, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo Chemical Industry or P&H Tech, or synthesized by known methods unless otherwise specified.

[0327] (Preparation of Compounds for Organic Optoelectronic Devices)

[0328] Synthesis Example 1: Synthesis of Compound A-1

[0329] [Reaction 1]

[0330]

[0331] Step 1: Synthesis of Compound A-1-3

[0332] 23.4 g (87.3 mmol, A-1-1) of 1 equivalent of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to 200 mL of toluene and 100 mL of distilled water, and 1 equivalent of 9H-carbazole-4-pinacol borate (A-1-2, cas: 1255309-13-7), 0.03 equivalent of Pd(PPh3)4 and 2 equivalents of K2CO3 were added thereto, and then stirred at 80°C for 6 hours under a nitrogen atmosphere. After removing the water layer, the organic layer obtained therefrom was dried under reduced pressure. The solid obtained therefrom was washed with water and hexane, and recrystallized with 300 mL of toluene to obtain compound A-1-3 with a yield of 60%.

[0333] Step 2: Synthesis of Compound A-1

[0334] 12 g (30.1 mmol) of 1 equivalent of compound A-1-3 was added to 100 mL of DMF, and 1 equivalent of intermediate A-1-4 (cas: 1818371-42-4) and 3 equivalents of K3PO4 were added thereto, and then stirred at 140° C. for 6 hours under a nitrogen atmosphere. After the organic layer was dried under reduced pressure, the solid obtained therefrom was washed with water and hexane, and recrystallized with 150 mL of toluene to obtain a white solid of compound A-1 with a yield of 70%.

[0335] (LC / MS: theoretical value 705.26 g / mol, measured value: 706.37 g / mol)

[0336] Synthesis Example 2: Synthesis of Compound A-15

[0337] [Reaction 2]

[0338]

[0339] Step 1: Synthesis of Compound A-15-2

[0340] 23.4 g (87.3 mmol, A-1-1) of 1 equivalent of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to 200 mL of toluene and 100 mL of distilled water, and 1 equivalent of 9H-carbazole-2-pinacol borate (A-15-1, cas: 1242412-60-7), 0.03 equivalent of Pd(PPh3)4 and 2 equivalents of K2CO3 were added thereto, and then stirred at 80°C for 6 hours under a nitrogen atmosphere. After removing the water layer, the organic layer obtained therefrom was dried under reduced pressure. The solid obtained therefrom was washed with water and hexane, and recrystallized with 300 mL of toluene to obtain intermediate A-15-2 with a yield of 60%.

[0341] Step 2: Synthesis of Compound A-15

[0342] Compound A-15 was synthesized with a yield of 75% in the same manner as in the second step of Synthesis Example 1, except that 1 equivalent of compound A-15-2 and 1 equivalent of compound A-1-4 were used.

[0343] (LC / MS: theoretical value 705.26 g / mol, measured value: 706.35 g / mol)

[0344] Synthesis Example 3: Synthesis of Compound A-27

[0345] [Reaction 3]

[0346]

[0347] Step 1: Synthesis of Compound A-27-1

[0348] Under nitrogen conditions, 4-bromo-9H-carbazole (16.4g, 66.5mmol), trifluoromethanesulfonic acid (29.9g, 199.5mmol) and benzene-D6 (78.4g, 931.0mmol) were added to a round-bottom flask, and then stirred and refluxed at 50°C for 20 hours. When the reaction was complete, D2O (10ml) was slowly poured thereinto, then quenched and stirred thoroughly. The product was neutralized by titration with a saturated solution of K3PO4 (aq). When the reaction was complete, after removing the water layer with a separatory funnel, the organic solvent was removed therefrom under reduced pressure to obtain a solid. The obtained solid was dissolved in toluene and treated with MgSO4 to remove moisture, and after filtering the organic solvent using a silica gel pad, the filtrate obtained therefrom was vacuum dried to obtain 14.2g of compound A-27-1 (84%).

[0349] Step 2: Synthesis of Compound A-27-2

[0350] 14.2g (56.1mmol) of compound A-27-1 is added to 200mL of toluene in a 500mL round-bottom flask, and 0.05 equivalent of dichlorodiphenylphosphine ferrocene palladium, 1.2 equivalents of bis-pinacolato diboron and 2 equivalents of potassium acetate are added thereto, then heated to reflux for 4 hours under a nitrogen atmosphere. After 200mL of heated toluene (80°C) is added to the reaction solution and the mixture is filtered through silica gel, the filtrate obtained therefrom is concentrated. The concentrated solid (A-27-2) is dried and then used in subsequent reactions without additional purification processes.

[0351] Step 3: Synthesis of Compound A-27-3

[0352] In the same manner as in the first step of Synthesis Example 1, Compound A-27-3 was synthesized in a yield of 60% by using 1 equivalent of Compound A-27-2.

[0353] Step 4: Synthesis of Compound A-27

[0354] In the same manner as in the second step of Synthesis Example 1, by using 1 equivalent of Compound A-27-3 and 1 equivalent of Compound A-1-4, Compound A-27 was synthesized with a yield of 70%.

[0355] (LC / MS: theoretical value 712.31 g / mol, measured value: 713.29 g / mol)

[0356] Comparative Synthesis Example 1: Synthesis of Compound C1

[0357]

[0358] Compound C1 was synthesized with reference to patent EP 3315581.

[0359] Comparative Synthesis Example 2: Synthesis of Compound C2

[0360] [Reaction 4]

[0361]

[0362] Compound C2 was synthesized by referring to the synthesis method of EP 3315581 using compound A-15-2 and compound C2-1 (refer to EP3315581).

[0363] Comparative Synthesis Example 3: Synthesis of Compound C3

[0364] [Reaction 5]

[0365]

[0366] 8 g (30 mmol) of 1 equivalent of intermediate A-1-1, 12.0 g (30 mmol) of 1 equivalent of compound A-1-3, 1.5 equivalents of NaOtBu, 0.03 equivalents of Pd2(dba)3 and 0.12 equivalents of P(t-Bu)3 were added to 150 mL of xylene, and then stirred and refluxed for 12 hours under a nitrogen stream. After removing xylene, 200 mL of methanol was added to the obtained mixture to crystallize the solid, which was filtered and dissolved in MCB, then filtered, and compound C3 was obtained by condensing an appropriate amount of organic solvent with a yield of 60%.

[0367] (LC / MS theoretical value: 629.23 g / mol, measured value: M+1=630.32 g / mol)

[0368] Comparative Synthesis Example 4: Synthesis of Compound C4

[0369] [Reaction 6]

[0370]

[0371] Compound C4 was synthesized with a yield of 80% in the same manner as in Comparative Synthesis Example 3, except that 1 equivalent of Intermediate C4-1 and 1 equivalent of Compound A-1-3 were used.

[0372] (LC / MS theoretical value: 705.26 g / mol, measured value: M+1=706.31 g / mol)

[0373] Comparative Synthesis Example 5: Synthesis of Compound C5

[0374] [Reaction 7]

[0375]

[0376] Compound C5 was synthesized with a yield of 75% in the same manner as in Comparative Synthesis Example 3, except that 1 equivalent of Intermediate C5-1 and 1 equivalent of Compound A-1-3 were used.

[0377] (LC / MS theoretical value: 705.26 g / mol, measured value: M+1=706.30 g / mol)

[0378] (Preparation of Second Compound)

[0379] Compound B-99 synthesized using the same method disclosed in US 2017-0317293 A1.

[0380] Synthesis Example 4: Synthesis of Compound B-186

[0381] [Reaction formula 8]

[0382]

[0383] Step 1: Synthesis of compound Int 5

[0384] Compound Int 1 was synthesized according to the method disclosed in Korean Publication No. 2016-0049842.

[0385] Step 2: Synthesis of Compound B-186

[0386] 30 g (0.0535 mol) of compound Int 5, 40 g (0.267 mol) of trifluoromethanesulfonic acid and 282 g (3.35 mol) of D6-benzene were added thereto, and then stirred at 10°C for 24 hours. After adding pure water thereto, the mixture was neutralized with a saturated K3PO4 solution. The organic layer obtained therefrom was concentrated and column purified to obtain 18 g of compound B-186 (white solid, LC-Mass Mz578.79, C 42 H 10 D 18 N2).

[0387] Synthesis Example 5: Synthesis of Compound C-5

[0388] [Reaction formula 9]

[0389]

[0390] Step 1: Synthesis of intermediate C-5-1

[0391] In a round-bottom flask, 10.44 g (42.41 mmol) of 4-bromo-9H-carbazole, 11.88 g (42.41 mmol) of 4-iodo-1,1'-biphenyl (Aldrich Sigma Co., Ltd.), 0.388 g (0.424 mmol) of Pd2(dba)3, 0.206 g (0.848 mmol) of P(t-Bu)3 and 6.11 g (63.61 mmol) of NaO(t-Bu) were suspended in 420 ml of toluene, and then stirred at 60°C for 12 hours. When the reaction was completed, distilled water was added thereto, followed by stirring for 30 minutes for extraction, and the organic layer obtained therefrom was treated by silica gel (hexane / dichloromethane = 9:1 (v / v)) column only, thereby obtaining 14.70 g of intermediate C-5-1 (yield: 87%).

[0392] Step 2: Synthesis of intermediate C-5-2

[0393] In a round-bottom flask, 15.50 g (38.92 mmol) of intermediate C-5-1, 7.15 g (42.81 mmol) of (2-nitrophenyl) boronic acid, 16.14 g (116.75 mmol) of potassium carbonate and 1.35 g (1.17 mmol) of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh 3) 4) were suspended in 150 ml of toluene and 70 ml of distilled water, and then stirred and refluxed for 12 hours. The organic layer was then extracted therefrom with dichloromethane and distilled water, and then filtered with silica gel. After removing the organic solution, the product solid obtained therefrom was recrystallized with dichloromethane and n-hexane to obtain 13.72 g of intermediate C-5-2 (yield: 80%).

[0394] Step 3: Synthesis of intermediate C-5-3

[0395] 22.46g (51.00mmol) of intermediate product C-5-2 and 52.8ml of triethyl phosphite are added in a round-bottomed flask and after replacing with nitrogen, stirred at 160°C for 12 hours. When the reaction is complete, 3L of MeOH is added thereto, then stirred and filtered, and the filtrate obtained therefrom is volatilized. 10.42g of intermediate C-5-3 (yield 50%) is obtained by purification via column chromatography.

[0396] Step 4: Synthesis of compound C-5

[0397] Compound C-5 was synthesized in the same manner as in the first step of Synthesis Example 5 (yield: 60%), except that intermediate C-5-3 and 1-iodo-3-phenylbenzene were used.

[0398] (LC / MS: theoretical value 560.23 g / mol, measured value: 561.57 g / mol)

[0399] (Manufacturing of organic light-emitting diodes)

[0400] Example 1

[0401] A glass substrate coated with an ITO (indium tin oxide) thin film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus prepared was used as an anode, and Compound A (Novaled GmbH) doped with 3% NDP-9 was vacuum deposited on the ITO substrate to form A hole injection layer is formed on the hole injection layer to a thickness of Compound B is deposited on the hole transport layer to a thickness of On the hole transport auxiliary layer, the compound A-1 obtained in Synthesis Example 1 was used as a host and doped with 7 wt % of PhGD as a dopant to form a hole transport auxiliary layer by vacuum deposition. Subsequently, compound C is deposited on the light-emitting layer to The thickness of the electron transport auxiliary layer is formed, and the compound D and LiQ are simultaneously vacuum deposited at a weight ratio of 1:1 to form a layer with a thickness of The electron transport layer is formed by vacuum depositing LiQ and Al is used to form a cathode to manufacture an organic light emitting diode.

[0402] ITO / Compound A (3% NDP-9 doping, ) / compound / Compound / EML[93wt% of host (Compound A-1):7wt% of PhGD](400

[0403] / Compound / Compound D:

[0404] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0405] Compound B: N-[4-(4-dibenzofuranyl)phenyl]-N-[4-(9-phenyl-9H-fluoren-9-yl)phenyl][1,1'-biphenyl]-4-amine

[0406] Compound C: 2,4-diphenyl-6-(4',5',6'-triphenyl[1,1':2',1":3",1"':3"',1""-pentaphenyl]-3""-yl)-1,3,5-triazine

[0407] Compound D: 2-(1,1'-biphenyl-4-yl)-4-(9,9-diphenylfluoren-4-yl)-6-phenyl-1,3,5-triazine

[0408] [PhGD]

[0409]

[0410] Example 2

[0411] A glass substrate coated with an ITO (indium tin oxide) thin film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus prepared was used as an anode, and Compound A (Novaled GmbH) doped with 3% NDP-9 was vacuum deposited on the ITO substrate to form A hole injection layer is formed on the hole injection layer to a thickness of Compound E is deposited on the hole transport layer to a thickness of On the hole transport auxiliary layer, the compound A-1 obtained in Synthesis Example 1 and the compound B-186 obtained in Synthesis Example 4 were used as hosts at the same time and doped with 10 wt % of PhGD as a dopant to form a hole transport auxiliary layer by vacuum deposition. Subsequently, compound F is deposited on the light-emitting layer to The electron transport auxiliary layer is formed by vacuum depositing compound G and LiQ at a weight ratio of 1:1 to form a layer having a thickness of The electron transport layer is formed by vacuum depositing LiQ and Al is used to form a cathode to manufacture an organic light emitting diode.

[0412] ITO / Compound A (3% NDP-9 doping, ) / compound / Compound / EML[90wt% host (Compound A-1:Compound B-186=4:6w / w):10wt% PhGD] / Compound / Compound G:

[0413] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0414] Compound E: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluoren)-2-amine

[0415] Compound F: 2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine

[0416] Compound G: 2-[4-[4-(4'-cyano-1,1'-biphenyl-4-yl)-1-naphthyl]phenyl]-4,6-diphenyl-1,3,5-triazine

[0417] Examples 3 to 8 and Comparative Examples 1 to 11

[0418] The diodes of Examples 3 to 8 and Comparative Examples 1 to 11 were manufactured in the same manner as in Example 1 or 2, except that the host and composition were changed as described in Tables 1 and 2.

[0419] evaluate

[0420] (1) Measuring the change in current density due to voltage change

[0421] While increasing the voltage from 0 V to 10 V, the current value flowing through the unit device in the obtained organic light emitting diode was measured using a current-voltage meter (Keithley 2400), and the measured current value was divided by the area to provide a result.

[0422] (2) Measuring the change in brightness due to voltage changes

[0423] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured using a luminance meter (Minolta Cs-1000A).

[0424] (3) Measurement of luminous efficiency

[0425] By using the luminance and current density of (1) and (2) above, the luminance at the same current density (10 mA / cm 2 ) under luminous efficiency (cd / A).

[0426] Table 1 shows the relative values ​​of the luminous efficiency based on Comparative Example 1.

[0427] Table 2 shows the relative values ​​of the luminous efficiency based on Comparative Example 6.

[0428] (4) Measurement life

[0429] In use 24,000cd / m 2 As the initial brightness (cd / m 2 ) after emitting light and measuring the decrease in brightness of the organic light emitting diodes over time using a Polanonix lifetime measurement system, the T95 lifetime of the organic light emitting diodes is measured as the time when their brightness decreases to 95% relative to the initial brightness.

[0430] Table 1 shows the relative values ​​of T95 life based on Comparative Example 1.

[0431] Table 2 shows the relative values ​​of T95 life based on Comparative Example 6.

[0432] [Table 1]

[0433]

[0434] [Table 2]

[0435]

[0436] Referring to Table 1, the organic light-emitting diode to which the compound according to the embodiment of the present invention is applied has significantly improved efficiency and lifespan characteristics compared with the organic light-emitting diode according to the comparative example, and in particular, referring to Table 2, the organic light-emitting diode to which the composition containing the compound according to the embodiment of the present invention is applied also has improved efficiency and lifespan characteristics.

[0437] While the invention has been described in connection 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 is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic optoelectronic device, the compound being represented by Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R 1 is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C6 to C20 heterocyclic group, Z 1 To Z 3 Each independently is N or CR a , Z 1 To Z 3 At least two of them are N, Z 4 To Z 6 Each independently is N or CR b , Z 4 To Z 6 At least two of them are N, R a , R b , R 2 and R 3 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, L 1 To L 4 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group, Ar 1 To Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, m1 and m2 are each independently one of integers from 1 to 4, and m3 is one of integers from 1 to 3.

2. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1A to Chemical Formula 1D: In Chemical Formulae 1A to 1D, Z 1 To Z 6 , R 1 To R 3 , L 1 To L 4 ,Ar 1 To Ar 4 and m1 to m3 are the same as defined in claim 1.

3. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-9: In Chemical Formula 1-1 to Chemical Formula 1-9, R 1 To R 3 , L 1 To L 4 ,Ar 1 To Ar 4 and m1 to m3 are the same as defined in claim 1.

4. The compound for an organic optoelectronic device according to claim 1, wherein Chemical formula 1 is represented by Chemical formula 1-B-1 or Chemical formula 1-D-1: In Chemical Formula 1-B-1 and Chemical Formula 1-D-1, R 1 To R 3 , L 1 To L 4 ,Ar 1 To Ar 4 and m1 to m3 are the same as defined in claim 1.

5. The compound for an organic optoelectronic device according to claim 1, wherein Ar 1 To Ar 4 Each is independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothienyl group.

6. A compound for an organic optoelectronic device, the compound being selected from the compounds listed in Group 1: [Group 1] 7. 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 optoelectronic device according to claim 1, and The second compound is represented by Chemical Formula 2, a combination of Chemical Formula 3 and Chemical Formula 4, or Chemical Formula 5: In chemical formula 2, R 4 To R 8 and Ar 7 To Ar 10 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, Ar 5 and Ar 6 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, m4, m7 and m8 are each independently one of integers from 1 to 4, m5 and m6 are each independently one of integers from 1 to 3, and n is an integer from 0 to 2; In Chemical Formula 3 and Chemical Formula 4, a1* to a4* in Chemical Formula 3 are each independently a connecting carbon (C) or CL a -R c , Among a1* to a4* in Chemical Formula 3, two adjacent ones are each connected to * in Chemical Formula 4, L a , L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, R c ,Ar 13 ,Ar 14 , R 9 and R 10 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, Ar 11 and Ar 12 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and m9 and m10 are each independently one of integers from 1 to 4; In Chemical Formula 5, L 10 is a single bond or a substituted or unsubstituted C6 to C20 arylene group, R 16 To R 28 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, Ar 13 is a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and m16 is an integer between 1 and 3.

8. The composition for an organic optoelectronic device according to claim 7, wherein: Chemical formula 2 is represented by Chemical formula 2-8: In Chemical Formula 2-8, Ar 7 To Ar 10 and R 4 To R 7 are each independently hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, m4 and m7 are each independently an integer from 1 to 4, m5 and m6 are each independently one of integers from 1 to 3, and *-L 5 -Ar 5 and *-L 6 -Ar 6 Each is independently one of the substituents listed in Group I, [Group I] In Group I, R 11 To R 15 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, m11 is an integer from 1 to 5, m12 is an integer from 1 to 4, m13 is an integer from 1 to 3, m14 is an integer of 1 or 2. m15 is an integer from 1 to 7, and * is the connection point.

9. The composition for an organic optoelectronic device according to claim 7, wherein: The combination of Chemical Formula 3 and Chemical Formula 4 is represented by Chemical Formula 3C: In chemical formula 3C, L c3 and L c4 is a single key, Ar 13 ,Ar 14 , R 9 , R 10 , R c3 and R c4 are each independently hydrogen, deuterium or C6 to C12 aryl, m9 and m10 are each independently one of integers from 1 to 4, and *-L 7 -Ar 11 and *-L 8 -Ar 12 Each is independently one of the substituents listed in Group I, [Group I] In Group I, R 11 To R 15 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, m11 is an integer from 1 to 5, m12 is an integer from 1 to 4, m13 is an integer from 1 to 3, m14 is an integer of 1 or 2. m15 is an integer from 1 to 7, and * is the connection point.

10. The composition for an organic optoelectronic device according to claim 7, wherein: Chemical formula 5 is represented by Chemical formula 5-2 or Chemical formula 5-3: In Chemical Formula 5-2 and Chemical Formula 5-3, L 10 , R 16 To R 28 ,Ar 13 and m16 are the same as defined in claim 7.

11. An organic optoelectronic device, comprising: an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, Wherein, the organic layer comprises: The compound for an organic optoelectronic device according to any one of claims 1 to 6; or The composition for an organic optoelectronic device according to any one of claims 7 to 10.

12. The organic optoelectronic device according to claim 11, wherein: The organic layer includes a light-emitting layer, and The light-emitting layer includes the compound for an organic optoelectronic device or the composition for an organic optoelectronic device. 13 . A display device comprising the organic optoelectronic device according to claim 11 .

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