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

Abstract

The present invention relates to a compound for an organic optoelectronic element represented by a combination of Chemical Formula 1 and Chemical Formula 2, a composition for an organic optoelectronic element comprising the same, an organic optoelectronic element, and a display device. Details of the chemical formula 1 and the chemical formula 2 are 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] An organic optoelectronic device (organic optoelectronic diode) is a device that can convert electrical energy into light energy and vice versa.

[0003] Organic optoelectronic devices can be broadly divided into two categories based on their operating principles: photovoltaic devices that generate electrical energy by separating excitons formed from light energy into electrons and holes and transferring these electrons and holes to different electrodes; and light-emitting devices that generate light energy from electrical energy by applying 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 the organic material between electrodes. Summary of the Invention

[0006] Technical issues

[0007] One embodiment provides a compound for an organic optoelectronic device having low driving force, high efficiency, and long lifespan.

[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 an organic optoelectronic device.

[0011] Technical Solution

[0012] According to one embodiment, a compound represented by a combination of Chemical Formula 1 and Chemical Formula 2 is provided.

[0013]

[0014] In Chemical Formula 1 and Chemical Formula 2,

[0015] X 1 and X 2 are each independently O or S,

[0016] * Each is a connecting carbon (C),

[0017] * in Chemical Formula 1 is connected to * in Chemical Formula 2, respectively,

[0018] R 1 to R 6 are each independently hydrogen, deuterium, 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] R 7 to R 11 are each independently hydrogen, deuterium or substituted or unsubstituted phenyl,

[0020] m1, m3 and m5 are each independently an integer from 1 to 3,

[0021] m2 is an integer of 1 or 2, and

[0022] m4 and m6 are each independently one of integers from 1 to 4.

[0023] According to another embodiment, provided is a composition for an organic optoelectronic device including a first compound and a second compound.

[0024] The first compound may be the above-described compound for an organic optoelectronic device and the second compound may be represented by Chemical Formula 3.

[0025] [Chemical Formula 3]

[0026]

[0027] In Chemical Formula 3,

[0028] Z 1 to Z 6 Each independently is N or CL a -R a ,

[0029] Z 1 to Z 6 At least two of them are N,

[0030] L a 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,

[0031] R aare 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

[0032] R a Each exists independently, or adjacent groups are linked to form a substituted or unsubstituted aliphatic, aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aliphatic, aromatic or heteroaromatic polycyclic ring.

[0033] 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 a compound for an organic optoelectronic device or a composition for an organic optoelectronic device.

[0034] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0035] Beneficial effects

[0036] An organic optoelectronic device with low driving force, high efficiency and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0038] <Description of Reference Numerals>

[0039] 100: Organic Light-Emitting Diode

[0040] 105: Organic layer

[0041] 110: cathode

[0042] 120: Anode

[0043] 130: Luminous layer

[0044] 140: Hole transport zone

[0045] 150: Electron transport region. DETAILED DESCRIPTION

[0046] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

[0047] In the present specification, when no definition is otherwise provided, "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.

[0048] In one embodiment of the present invention, "substituted" means that at least one hydrogen atom 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 one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl, or cyano. In one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. In one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0049] In the present specification, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0050] In the present specification, "hydrogen (—H)" may include "deuterium substitution (—D)" or "tritium substitution (—T)".

[0051] 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.

[0052] In this specification, "aryl" refers to a group including 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.

[0053] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0054] In this specification, "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 group, a cycloalkyl group, a fused ring thereof or a combination thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.

[0055] For example, "heteroaryl" may refer to an aryl group comprising 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 comprises two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0056] 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 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 chrysene 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, or a combination thereof, but is not limited thereto.

[0057] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furyl, 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 present invention also includes, but is not limited to, a substituted or unsubstituted quinolinyl, a substituted or unsubstituted isoquinolinyl, 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, a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted benzonaphthofuranyl, a substituted or unsubstituted benzonaphthothiophenyl, a substituted or unsubstituted benzofuranofluorenyl, a substituted or unsubstituted benzothienofluorenyl, or a combination thereof, but is not limited thereto.

[0058] 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.

[0059] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the 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.

[0060] Hereinafter, a compound for an organic optoelectronic device according to one embodiment is described.

[0061] The compound for an organic optoelectronic device according to one embodiment is represented by a combination of Chemical Formula 1 and Chemical Formula 2.

[0062]

[0063] In Chemical Formula 1 and Chemical Formula 2,

[0064] X 1 and X 2 are each independently O or S,

[0065] * Each is a connecting carbon (C),

[0066] * in Chemical Formula 1 is connected to * in Chemical Formula 2, respectively,

[0067] R 1 to R 6 are each independently hydrogen, deuterium, 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,

[0068] R 7 to R 11 are each independently hydrogen, deuterium or substituted or unsubstituted phenyl,

[0069] m1, m3 and m5 are each independently an integer from 1 to 3,

[0070] m2 is an integer of 1 or 2, and

[0071] m4 and m6 are each independently one of integers from 1 to 4.

[0072] The first compound has a structure in which oxazole or thiazole is fused to dibenzofuran (dibenzothiophene), and has the advantages of high charge mobility, large current on / off ratio, extremely low driving voltage, and excellent efficiency and lifespan characteristics by including the dibenzofuran (dibenzothiophene) portion.

[0073] Furthermore, the oxazole or thiazole moiety is structurally characterized by a low dielectric constant and has a low dipole moment value, which enables excellent image quality when applied to the final device.

[0074] In particular, the hole mobility of the structure fused at the 1-position and the 2-position of dibenzothiophene is optimal, and thus, an organic light emitting diode including it has low voltage / high efficiency / long life characteristics.

[0075] Furthermore, the bicarbazole substituent with excellent hole injection / transport can be combined with a dibenzofuran (dibenzothiophene) moiety to serve as a host material with appropriate T1 energy.

[0076] In Chemical Formula 1 and Chemical Formula 2, when m1 is 2 or greater, R 1 Each may be the same as or different from each other.

[0077] In Chemical Formula 1 and Chemical Formula 2, when m2 is 2 or greater, R 2 Each may be the same as or different from each other.

[0078] In Chemical Formula 1 and Chemical Formula 2, when m3 is 2 or greater, R 3 Each may be the same as or different from each other.

[0079] In Chemical Formula 1 and Chemical Formula 2, when m4 is 2 or greater, R 4 Each may be the same as or different from each other.

[0080] In Chemical Formula 1 and Chemical Formula 2, when m5 is 2 or greater, R 5 Each may be the same as or different from each other.

[0081] In Chemical Formula 1 and Chemical Formula 2, when m6 is 2 or greater, R 6 Each may be the same as or different from each other.

[0082] The combination of Chemical Formula 1 and Chemical Formula 2 may be represented by, for example, Chemical Formula 1A or Chemical Formula 1B, depending on the condensation position and condensation direction.

[0083]

[0084] In Chemical Formula 1A and Chemical Formula 1B,

[0085] X 1 、X 2 、R 1 to R 11 , L 1 、Ar 1 and m1 to m6 are as defined in Chemical Formula 1.

[0086] A specific example of the combination of Chemical Formula 1 and Chemical Formula 2 may be represented by any one of Chemical Formula 1A-I to Chemical Formula 1A-IV and Chemical Formula 1B-I to Chemical Formula 1B-IV.

[0087]

[0088]

[0089]

[0090] In Chemical Formulas 1A-I to 1A-IV and Chemical Formulas 1B-I to 1B-IV,

[0091] X 1 、X 2 、R 1 to R 11 , L 1 、Ar 1 and m1 to m6 are as defined in Chemical Formula 1A and Chemical Formula 1B.

[0092] A more specific example of the combination of Chemical Formula 1 and Chemical Formula 2 can be represented by any one of Chemical Formulas 1A-I-1 to 1A-I-16, Chemical Formulas 1A-II-1 to 1A-II-16, Chemical Formulas 1A-III-1 to 1A-III-16, Chemical Formulas 1A-IV-1 to 1A-IV-16, Chemical Formulas 1B-I-1 to 1B-I-16, Chemical Formulas 1B-II-1 to 1B-II-16, Chemical Formulas 1B-III-1 to 1B-III-16, and Chemical Formulas 1B-IV-1 to 1B-IV-16.

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122] In Chemical Formulas 1A-I-1 to 1A-I-4, Chemical Formula 1A-II-1, Chemical Formula 1A-II-2, Chemical Formulas 1B-I-1 to 1B-I-4, Chemical Formula 1B-II-1, and Chemical Formula 1B-II-2,

[0123] X 1 , Z 1 to Z 3 、R 1 to R 7 、Ar 1 、Ar 2 , L 1 To L 3 , m1, m1′, m2 and m2′ are as defined in Formula 1A-I, Formula 1A-II, Formula 1B-I and Formula 1B-II.

[0124] A specific example of the combination of Chemical Formula 1 and Chemical Formula 2 can be represented by any one of Chemical Formula 1A-I-3, Chemical Formula 1A-II-3, Chemical Formula 1A-III-3, Chemical Formula 1A-IV-3, Chemical Formula 1B-I-3, Chemical Formula 1B-II-3, Chemical Formula 1B-III-3, and Chemical Formula 1B-IV-3.

[0125] The most specific example of the combination of Chemical Formula 1 and Chemical Formula 2 may be represented by any one of Chemical Formula 1A-I-3, Chemical Formula 1A-II-3, Chemical Formula 1B-I-3, and Chemical Formula 1B-II-3.

[0126] For example, R 1 to R 6Each of them may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzothiorol group, or a substituted or unsubstituted carbazolyl group.

[0127] For example, L 1 It may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0128] For example, Ar 1 The group 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 phenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted dibenzosilyl group.

[0129] For example, L 1 -Ar 1 The substituents listed in Group I may be selected.

[0130] [Group I]

[0131]

[0132] In Group I,

[0133] R 22 to R 25 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl,

[0134] Ar 5 and Ar 6 are each independently a substituted or unsubstituted C6 to C12 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0135] m16 is an integer from 1 to 5,

[0136] m17 is an integer from 1 to 4,

[0137] m18 is an integer from 1 to 3,

[0138] m19 is an integer of 1 or 2, and

[0139] * is the connection point.

[0140] In the most specific embodiment, a specific example of the combination of Chemical Formula 1 and Chemical Formula 2 may be one selected from the compounds listed in Group 1, but is not limited thereto.

[0141] [Group 1]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] A composition for an organic optoelectronic device according to another embodiment includes a first compound and a second compound, wherein the first compound is the above-described compound for an organic optoelectronic device, and the second compound may be represented by Chemical Formula 3.

[0157] [Chemical Formula 3]

[0158]

[0159] In Chemical Formula 3,

[0160] Z 1 to Z 6 Each independently is N or CL a -R a ,

[0161] Z 1 to Z 6 At least two of them are N,

[0162] L aare 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,

[0163] R a 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

[0164] R a Each exists independently, or adjacent groups are linked to form a substituted or unsubstituted aliphatic, aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aliphatic, aromatic or heteroaromatic polycyclic ring.

[0165] Since the second compound effectively expands the LUMO band by including the nitrogen-containing hexagonal ring portion, it is included together with the above-mentioned first compound for an organic optoelectronic device to improve the balance between holes and electrons, thereby greatly improving lifespan characteristics.

[0166] For example, Z 1 to Z 6 Two of them can be nitrogen (N) and the rest can be CL a -R a .

[0167] For example, Z 1 and Z 3 It can be nitrogen, Z 2 Can be N or CL a -R a , Z 4 Can be N or CL a -R a , Z 5 Can be N or CL a -R a , and Z 6 Can be N or CL a -R a .

[0168] For example, Z 1 to Z 6 Three of them can be nitrogen (N) and the rest can be CL a -R a .

[0169] For example, Z 1 , Z 3 and Z 5 It can be nitrogen, Z 2 Can be N or CLa -R a , Z 4 Can be N or CL a -R a , and Z 6 Can be N or CL a -R a .

[0170] As a specific example, depending on R a The second compound may be represented by any one of Chemical Formulae 3A to 3C, for example, depending on the specific substituents of .

[0171]

[0172] [Chemical formula 3C]

[0173]

[0174] In Chemical Formulae 3A to 3C,

[0175] Z 1 , Z 3 and Z 5 Each independently is N or CL a -R a ,

[0176] Z 1 , Z 3 and Z 5 At least two of them are N,

[0177] X 1 Is O, S or NR b ,

[0178] L a and L 2 To L 4 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,

[0179] R a 、R b and R 12 to R 18 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,

[0180] R 12 and R 13exist independently of each other, or adjacent groups therein are linked to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring,

[0181] Ar 2 and Ar 3 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,

[0182] R a 、Ar 2 and Ar 3 exist independently, or

[0183] R a 、Ar 2 and Ar 3 The adjacent groups in are connected to form a substituted or unsubstituted aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aromatic or heteroaromatic polycyclic ring,

[0184] m7, m8, m10, m12 and m13 are each independently one of integers from 1 to 4, and

[0185] m9 and m11 are each independently one of integers from 1 to 3.

[0186] In Chemical Formula 3A, when m7 is 2 or greater, R 12 Each may be the same as or different from each other.

[0187] In Chemical Formula 3A, when m8 is 2 or greater, R 13 Each may be the same as or different from each other.

[0188] In Chemical Formula 3B, when m9 is 2 or greater, R 14 Each may be the same as or different from each other.

[0189] In Chemical Formula 3B, when m10 is 2 or greater, R 15 Each may be the same as or different from each other.

[0190] In Chemical Formula 3C, when m11 is 2 or greater, R 16 Each may be the same as or different from each other.

[0191] In Chemical Formula 3C, when m12 is 2 or greater, R 17 Each may be the same as or different from each other.

[0192] In Chemical Formula 3C, when m13 is 2 or greater, R 18 They may be the same as or different from each other.

[0193] As used herein, "adjacent groups are linked to form a substituted or unsubstituted aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aromatic or heteroaromatic polycyclic ring" means that any two adjacent substituents are linked to each other to form a ring. For example, in Formula 3A, R 12 The adjacent groups or R 13 The adjacent groups in the group may be linked to each other to form a substituted or unsubstituted aromatic monocyclic ring. The aromatic monocyclic ring may be, for example, a substituted or unsubstituted phenyl group.

[0194] As a more specific example, Chemical Formula 3A may be represented by any one of Chemical Formula 3A-I to Chemical Formula 3A-XIII.

[0195]

[0196]

[0197]

[0198]

[0199] In Chemical Formulae 3A-I to 3A-XIII,

[0200] Z 1 , Z 3 , Z 5 and m7 are the same as above,

[0201] L 2 To L 4 may each independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group,

[0202] Ar 2 and Ar 3 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 triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,

[0203] R 12 、R 13 、R 19 to R 21 、R 12a 、R 12b 、R 12c 、R 12d 、R 13a 、R 13b 、R13c and R 13d may each independently be hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothienyl,

[0204] m7' and m8' can each independently be an integer of 1 or 2, and

[0205] m14 and m15 are each independently one of integers from 1 to 4.

[0206] For example, Chemical Formula 3B may be represented by any one of Chemical Formula 3B-I to Chemical Formula 3B-IV.

[0207]

[0208]

[0209] In Chemical Formulae 3B-I to 3B-IV, each substituent is the same as defined in Chemical Formula 3B.

[0210] For example, Chemical Formula 3C may be represented by Chemical Formula 3C-I or Chemical Formula 3C-II.

[0211]

[0212] In Chemical Formula 3C-I and Chemical Formula 3C-II, each substituent is the same as defined in Chemical Formula 3C.

[0213] In a specific embodiment, Chemical Formula 3 can be represented by Chemical Formula 3A-IV.

[0214] For example, in Formula 3A-IV, L 2 To L 4 may be each independently a single bond or a substituted or unsubstituted C6 to C12 aryl group, Ar 2 and Ar 3 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 triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group or a substituted or unsubstituted carbazolyl group, and R 12 、R 13 and R 19 and may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0215] The second compound may be, for example, one of the compounds selected from Group 2, but is not limited thereto.

[0216] [Group 2]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232] In a more specific embodiment, the first compound may be represented by Chemical Formula 1B-I-3 or Chemical Formula 1B-II-3 and the second compound may be represented by Chemical Formula 3A-IV.

[0233] The first compound and the second compound can be included in a weight ratio of, for example, 1:99 to 99:1. By including in the above range, the electron transport ability of the first compound and the hole transport ability of the second compound can be used to achieve a suitable weight ratio to achieve bipolar characteristics, thereby improving efficiency and lifespan. Within the above range, for example, they can be included in a weight ratio of 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 can be included in a weight ratio of 40:60, 50:50, or 60:40.

[0234] In addition to the first and second compounds described above, one or more additional compounds may be included.

[0235] The compound for an organic optoelectronic device or the composition for an organic optoelectronic device may be a composition further including a dopant.

[0236] 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.

[0237] A dopant is a material mixed in a small amount with a compound or composition used in an organic optoelectronic device to induce luminescence, and is generally 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.

[0238] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be 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 be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0239] [Chemical formula Z]

[0240] L 5 MX 5

[0241] In the chemical formula Z, M is a metal, and L 5 and X 5 are the same or different and are ligands that form a complex with M.

[0242] 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 5 and X 5 This may be, for example, a bidentate ligand.

[0243] By L 5 and X 5 Examples of the ligand represented by may be selected from the chemical formulae listed in Group A, but are not limited thereto.

[0244] [Group A]

[0245]

[0246] In Group A,

[0247] 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

[0248] 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.

[0249] For example, a dopant represented by Chemical Formula V may further be included.

[0250] [Chemical Formula V]

[0251]

[0252] In Chemical Formula V,

[0253] 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 ,

[0254] R 132 to R 134 are each independently a substituted or unsubstituted C1 to C6 alkyl group,

[0255] R 101 to R 116 At least one of them is a functional group represented by Chemical Formula V-1,

[0256] L 100 is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone pair of electrons on a carbon or heteroatom, and

[0257] m21 and m22 are each independently any one of integers from 0 to 3, and m21+m22 is any one of integers from 1 to 3,

[0258] [Chemical Formula V-1]

[0259]

[0260] In Chemical Formula V-1,

[0261] 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

[0262] * indicates a moiety attached to a carbon atom.

[0263] As an example, a dopant represented by Chemical Formula Z-1 may be included.

[0264] [Chemical Formula Z-1]

[0265]

[0266] 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;

[0267] R A 、R B 、R C and R D each independently represents mono-, di-, tri- or tetra-substituted or unsubstituted;

[0268] 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;

[0269] 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

[0270] R A 、R B 、R C 、R D R and R' are each independently selected from hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, 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 、RD , 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.

[0271] The dopant according to one embodiment may be a platinum complex, and may be represented, for example, by Chemical Formula VI.

[0272] [Chemical Formula VI]

[0273]

[0274] In Chemical Formula VI,

[0275] X 100 Selected from O, S and NR 131 ,

[0276] 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 ,

[0277] R 132 to R 134 are each independently a substituted or unsubstituted C1 to C6 alkyl group,

[0278] R 117 to R 131 At least one of them is -SiR 132 R 133 R 134 or tert-butyl, and

[0279] R 132 to R 134 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0280] Hereinafter, an organic optoelectronic device including the above-mentioned compound for an organic optoelectronic device or the composition for an organic optoelectronic device is described.

[0281] The organic optoelectronic 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.

[0282] Herein, an organic light emitting diode is described as one example of an organic optoelectronic device with reference to the accompanying drawings.

[0283] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0284] refer to Figure 1 , the 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 .

[0285] 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), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; or 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.

[0286] 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 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, LiF / Al, and BaF2 / Ca, but is not limited thereto.

[0287] The organic layer 105 may include the above-described composition for an organic optoelectronic device.

[0288] The organic layer 105 may include a light emitting layer 130 , and the light emitting layer 130 may include the above-described composition for an organic optoelectronic device.

[0289] The composition for an organic optoelectronic device further including a dopant may be, for example, a green light emitting composition.

[0290] The light-emitting layer 130 may include, for example, the first compound and the second compound described above as phosphorescent hosts, respectively.

[0291] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0292] The charge transport region may be, for example, a hole transport region 140 .

[0293] The hole transport region 140 may further improve hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.

[0294] 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 listed in group B may be included in at least one layer of the hole transport layer and the hole transport auxiliary layer.

[0295] [Group B]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302] (Dn refers to the number of hydrogens replaced by deuterium and represents a structure substituted with one or more deuteriums).

[0303] In the hole transport region 140 , in addition to the compounds described above, 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, etc., and compounds similar thereto can be used.

[0304] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0305] The electron transport region 150 may further enhance electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0306] 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 electron transport layer and the electron transport auxiliary layer may include at least one of the compounds in group C.

[0307] [Group C]

[0308]

[0309]

[0310]

[0311] One embodiment may be an organic light emitting diode including a light emitting layer as an organic layer.

[0312] Another embodiment may be an organic light emitting diode including a light emitting layer and a hole transport region as organic layers.

[0313] Another embodiment may be an organic light emitting diode including a light emitting layer and an electron transport region as organic layers.

[0314] like Figure 1 As shown, the organic light emitting diode according to one embodiment of the present invention may further include a hole transport region 140 and an electron transport region 150 as the organic layer 105 in addition to the light emitting layer 130 .

[0315] 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 the above-mentioned organic layer in addition to the light emitting layer.

[0316] The organic light emitting diode 100 may be produced 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 a cathode or anode thereon.

[0317] Organic light emitting diodes can be applied to organic light emitting display devices.

[0318] Invention Mode

[0319] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the scope of the claims is not limited thereto.

[0320] 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.

[0321] (Preparation of Compounds for Organic Optoelectronic Devices)

[0322] (Synthesis of the First Compound)

[0323] Synthesis Example 1: Synthesis of Compound 1

[0324] [Reaction formula 1]

[0325]

[0326] Step 1: Synthesis of intermediate I-1

[0327] 100g (404.86mmol) of 6-amino-2-bromo-3-fluorophenol (Merck & Co., Inc.) and 43g (485.83mmol) of benzaldehyde (Merck & Co., Inc.) were dissolved in 120g (2024.29mmol) of acetic acid and then reacted at room temperature for 3 hours. The reactant was then poured into a large amount of DIW (deionized water), stirred for 30 minutes, filtered, and washed with water twice or more. The solid was thus separated, extracted with dichloromethane and DIW, and dried over magnesium sulfate to remove all solvents. Subsequently, the solid was dissolved in dichloromethane equivalent to 10 times the amount of the solid, to which 84.9g (374mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) were then slowly added, followed by reaction at room temperature for 2 hours to obtain intermediate I-1 (70g, yield: 70%).

[0328] Step 2: Synthesis of intermediate I-2

[0329] Intermediate I-1 (70.0 g, 239.64 mmol), (2-chloro-6-hydroxyphenyl) boronic acid (45.44 g, 263.60 mmol), Pd(PPh 3 ) 4 (13.85 g, 11.98 mmol) and K 2 CO 3 (99.36 g, 718.91 mmol) were added to dioxane (600 ml) and DIW (3000 ml) and dissolved therein, and then heated to reflux under a nitrogen atmosphere. After 12 hours, the reaction solution was cooled, and after removing the aqueous layer, the solvent was removed by rotary evaporation and extracted with dichloromethane / DIW. The organic layer obtained in this way was passed through a column with hexane: EA=4:1 (v / v) to obtain intermediate I-2 (40.0 g, yield: 49%).

[0330] Step 3: Synthesis of intermediate I-3

[0331] Intermediate I-2 (40.0 g, 117.73 mmol) and K 3 PO 4 (50.0 g, 235.47 mmol) were added to DMF (200 ml) and dissolved therein, and then heated under reflux at 120° C. for 3 hours. When the reaction was completed, after removing the solvent with a rotary evaporator, the organic layer extracted with dichloromethane / DIW was dried over MgSO 4, concentrated, and stirred with a small amount of methanol to obtain a solid, which was recrystallized with 200 mL of toluene to obtain 30.0 g (yield: 80%) of Intermediate I-3.

[0332] Step 4: Synthesis of Compound 1

[0333] Intermediate I-3 (30 g, 93.83 mmol) and 9-phenyl-9H, 9'H-3,3'-bicarbazole (38.33 g, 93.83 mmol), sodium tert-butoxide (13.53 g, 140.74 mmol) and tri-tert-butylphosphine (7.59 g, 18.77 mmol) were dissolved in 300 ml of xylene, to which Pd (dba) 2 (4.3 g, 4.69 mmol) was added, and the mixture was stirred and refluxed under a nitrogen atmosphere for 12 hours. When the reaction was complete, after evaporating the solvent, the organic layer extracted with dichloromethane and distilled water was dried over anhydrous magnesium sulfate, filtered, and the filtrate obtained was concentrated under reduced pressure. The product obtained was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio 2: 1) and dried under reduced pressure to obtain 52.0 g (yield: 80.0%) of compound 1. LC / MS calculated for C49H29N3O2: exact mass: 691.23, found: 691.75 [M+H].

[0334] Synthesis Example 2: Synthesis of Compound 2

[0335] Compound 2 (55.0 g, yield: 85%) was obtained in the same manner as in Steps 2 to 4 of Synthesis Example 1, except that intermediate I-1 (70.0 g, 255.36 mmol) and (3-chloro-6-fluorophenyl)boronic acid (53.43 g, 306.44 mmol) purchased from Merck & Co., Inc. were used. LC / MS calculated for C49H29N3O2: exact mass: 691.23, measured: 691.79 [M+H].

[0336] Synthesis Example 3: Synthesis of Compound 51

[0337] [Reaction formula 2]

[0338]

[0339] Compound 51 (55.0 g, 75% yield) was obtained in the same manner as in Step 4 of Synthesis Example 2, except that Intermediate I-3 (30.0 g, 93.83 mmol) and 9-(dibenzo[b,d]furan-1-yl)-9H,9'H-3,3'-bicarbazole (46.78 g, 93.83 mmol) were used. LC / MS calculated for C55H31N3O3: Exact mass: 781.24, Measured: 782.15 [M+H].

[0340] Synthesis Example 4: Synthesis of Compound 71

[0341] [Reaction formula 3]

[0342]

[0343] Compound 71 (53.0 g, 71% yield) was obtained in the same manner as in Step 4 of Synthesis Example 2, except that Intermediate I-3 (30.0 g, 93.83 mmol) and 9-(dibenzo[b,d]thiophen-2-yl)-9H,9'H-3,3'-bicarbazole (48.29 g, 93.83 mmol) were used. LC / MS calculated for C55H31N3O2S: Exact mass: 797.21, Measured: 797.88 [M+H].

[0344] Synthesis Example 5: Synthesis of Compound 83

[0345] [Reaction formula 4]

[0346]

[0347] Step 1: Synthesis of intermediate I-4

[0348] 100g (404.86mmol) of 6-amino-5-bromo-4-fluorophenol (Merck & Co., Inc.) and 43g (485.83mmol) of benzaldehyde (Merck & Co., Inc.) were dissolved in 120g (2024.29mmol) of acetic acid and then reacted at room temperature for 3 hours. Subsequently, the reactant was poured into a large amount of DIW (deionized water), then stirred for 30 minutes, filtered, and washed with water twice or more. The solid was thus separated, extracted with dichloromethane and DIW, and dried over magnesium sulfate to remove all solvents. Subsequently, the obtained solid was dissolved in dichloromethane equivalent to 10 times the amount of the solid, to which 84.9g (374mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) were slowly added, and then reacted at room temperature for 2 hours to obtain (70g, yield: 70%) of intermediate I-4.

[0349] Step 2: Synthesis of intermediate I-5

[0350] Intermediate I-5 (40.0 g, yield: 49%) was obtained in the same manner as in Step 2 of Synthesis Example 1, except that intermediate I-4 (70.0 g, 239.64 mmol) and (2-chloro-6-hydroxyphenyl)boronic acid (45.44 g, 263.60 mmol) were used.

[0351] Step 3: Synthesis of intermediate I-6

[0352] Intermediate I-6 (30 g, yield: 80%) was obtained in the same manner as in Step 3 of Synthesis Example 1, except that intermediate I-5 (40.0 g, 117.73 mmol) and K3PO4 (50.0 g, 235.47 mmol) were used together with DMF (N,N-dimethylformamide) (200 ml).

[0353] Step 4: Synthesis of Compound 83

[0354] Compound 83 (53.0 g, yield: 71%) was obtained in the same manner as in Step 4 of Synthesis Example 1, except that Intermediate I-6 (30 g, 93.83 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (38.33 g, 93.83 mmol), and sodium tert-butoxide (13.53 g, 140.74 mmol) were used. LC / MS calculated for C55H31N3O2S: Exact mass: 797.21, Measured: 797.92 [M+H].

[0355] Synthesis Example 6: Synthesis of Compound 108

[0356] [Reaction formula 5]

[0357]

[0358] Step 1: Synthesis of intermediate I-7

[0359] Intermediate I-7 (70.0 g, yield: 78%) was obtained in the same manner as in Step 1 of Synthesis Example 1, except that 2-amino-6-bromophenol (100.0 g, 485.83 mmol) and benzaldehyde (43.0 g, 404.86 mmol) purchased from Merck & Co., Inc. were used.

[0360] Step 2: Synthesis of intermediate I-8

[0361] Intermediate I-8 (60.0 g, yield: 69%) was obtained in the same manner as in Step 2 of Synthesis Example 1, except that intermediate I-7 (70.0 g, 255.36 mmol) and (5-chloro-2-fluorophenyl)boronic acid (53.43 g, 306.44 mmol) purchased from Merck & Co., Inc. were used.

[0362] Step 3: Synthesis of intermediate I-9

[0363] Intermediate I-8 (60.0 g, 185.33 mmol) and K2CO3 (38.42 g, 277.99 mmol) were dissolved in 600 mL of dimethylformamide, and after the temperature of the reaction solution was set at 0° C., 15.0 g (203.86 mmol) of sodium thiomethoxide was slowly added thereto. When the addition was complete, the mixture was heated to reflux for 2 hours after the temperature was raised to 100° C. The solid was thus separated by filtration, extracted with ethyl acetate and DIW, and after the solvent layer was evaporated, recrystallized with hexane to obtain intermediate I-9 (38.0 g, yield: 58%).

[0364] Step 4: Synthesis of Intermediate I-10

[0365] Intermediate I-9 (38.0 g, 108.0 mmol) and sodium periodate (34.65 g, 162.0 mmol) were dissolved in 700 mL of a mixed solvent of ethanol / DIW, and then stirred and refluxed at 50° C. for 12 hours. When the reaction was complete, a 1 M aqueous sodium thiosulfate solution was added to the reaction solution, followed by stirring for 1 hour and extraction with excess dichloromethane, from which the solvent was evaporated to obtain Intermediate I-10 (35.0 g, yield: 88%).

[0366] Step 5: Synthesis of intermediate I-11

[0367] Intermediate I-10 (35.0 g, 95.15 mmol) was dissolved in 500 mL of 1,2-dichloroethane, and after the temperature of the reaction solution was set at 0 ° C, 53.69 g (190.29 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise thereto, and after the temperature was raised to room temperature, the mixture was stirred for 1 hour. After the internal temperature was adjusted to 5 ° C, pyridine (22.57 g, 142.72 mmol) was slowly added dropwise thereto, and then reacted at room temperature for 12 hours. The solid thus obtained was filtered and washed with ethanol, and then the solvent was removed therefrom to obtain intermediate I-11 (22.0 g, yield: 69%).

[0368] Step 6: Synthesis of Compound 108

[0369] Compound 108 (46.37 g, 82% yield) was obtained in the same manner as in Step 4 of Synthesis Example 1, except that Intermediate I-11 (22 g, 65.51 mmol) and 9-phenyl-9H,9'H-3,3'-bicarbazole (26.76 g, 65.51 mmol) were used. LC / MS calculated for C49H29N3OS: Exact mass: 707.20, Measured: 708.41 [M+H].

[0370] Synthesis Example 7: Synthesis of Compound B-136

[0371]

[0372] Compound B-136 was synthesized by referring to the synthesis method of patent EP3034581.

[0373] HRMS (70 eV, EI+): m / z calculated for C42H28N2: 560.2252, found: 560.

[0374] Elemental analysis: C, 90%; H, 5%.

[0375] Synthesis Example 8: Synthesis of Compound C-57

[0376]

[0377] Compound C-57 was synthesized by referring to the synthesis method of patent WO2018-095391.

[0378] HRMS (70 eV, EI+): m / z calculated for C48H32N2: 636.2565, found: 636.

[0379] Elemental analysis: C, 91%; H, 5%.

[0380] Synthesis Example 9: Synthesis of Body 1

[0381] [Reaction formula 6]

[0382]

[0383] Step 1: Synthesis of intermediate I-12

[0384] Intermediate I-12 (40.0 g, yield: 49%) was obtained in the same manner as in Step 2 of Synthesis Example 1, except that intermediate I-4 (70.0 g, 239.64 mmol) and (5-chloro-2-hydroxyphenyl)boronic acid (45.44 g, 263.60 mmol) were used.

[0385] Step 2: Synthesis of intermediate I-13

[0386] Intermediate I-13 (30 g, yield: 80%) was obtained in the same manner as in Step 3 of Synthesis Example 1, except that intermediate I-12 (40.0 g, 117.73 mmol) and K3PO4 (50.0 g, 235.47 mmol) were used together with DMF (N,N-dimethylformamide) (200 ml).

[0387] Step 3: Composition of Body 1

[0388] The subject 1 (43.0 g, yield: 81%) was obtained in the same manner as in Step 4 of Synthesis Example 1, except that intermediate I-13 (30 g, 93.83 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (26.78 g, 93.83 mmol) and sodium tert-butoxide (13.53 g, 140.74 mmol) were used. LC / MS calculated for C40H28N2O2: exact mass: 568.22, measured value: 569.33 [M+H].

[0389] (Synthesis of the Second Compound)

[0390] Synthesis Example 10: Synthesis of Compound C-21

[0391] [Reaction formula 7]

[0392]

[0393] Step 1: Synthesis of Intermediate 10-a

[0394] 1 eq (10 g) of 1-bromo-2-chloro-3-nitrobenzene, 1 eq (5.2 g) of phenylboronic acid, 0.05 eq (2.4 g) of Pd(PPh ) , and 2 eq (11.8 g) of K CO were suspended in 120 ml of tetrahydrofuran and 60 ml of distilled water, and then stirred and refluxed under a nitrogen stream for 12 hours. When the reaction was complete, the organic layer extracted with tetrahydrofuran and distilled water was dried over magnesium sulfate (MgSO ), filtered, and concentrated under reduced pressure. The solid product thus obtained was recrystallized from dichloromethane and hexane to obtain 8.3 g (Y=83%) of Intermediate 10-a.

[0395] Step 2: Synthesis of Intermediate 10-b

[0396] 1 eq (8.3 g) of intermediate 10-a, 1 eq (6.1 g) of 2-naphthaleneboronic acid, 0.05 eq (2.0 g) of Pd(PPh ) , and 2 eq (9.8 g) of K CO were suspended in 120 ml of tetrahydrofuran and 60 ml of distilled water, and then stirred and refluxed for 24 hours under a nitrogen stream. When the reaction was complete, the organic layer extracted with tetrahydrofuran and distilled water was dried over magnesium sulfate (MgSO ) and filtered, and the filtrate thus obtained was concentrated under reduced pressure. The solid product thus obtained was recrystallized from dichloromethane and hexane to obtain 6.4 g (Y=56%) of intermediate 10-b.

[0397] Step 3: Synthesis of Intermediate 10-c

[0398] 1 eq (6.4 g) of intermediate 10-b and 20 g of triphenylphosphine were suspended in 100 ml of 1,2-dichlorobenzene, and then stirred and refluxed under a nitrogen stream for 18 hours. When the reaction was complete, the organic layer obtained was extracted with a solvent and recrystallized with 80 ml of acetone to obtain 4.0 g (Y = 69%) of intermediate 10-c.

[0399] Step 4: Synthesis of Compound C-21

[0400] 1 eq (4.0 g) of intermediate 10-c, 1 eq (5.3 g) of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 2 eq (2.6 g) of sodium tert-butoxide, and 0.03 eq (0.38 g) of Pd2(dba)3 were suspended in 60 ml of xylene, and 0.09 eq of tri-tert-butylphosphine was added thereto, followed by stirring and reflux for 12 hours. When the reaction was complete, the organic layer extracted with xylene and distilled water was dried over magnesium sulfate and filtered, and the filtrate obtained was then concentrated under reduced pressure. After removing the organic solvent, recrystallization was performed with monochlorobenzene and hexane to obtain 7.5 g (Y = 91%) of compound C-21. LC-mass measurement (theoretical value: 600.71 g / mol, measured value: M = 601 g / mol).

[0401] Example 1

[0402] A glass substrate coated with ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned for 10 minutes using oxygen plasma, and moved to a vacuum depositor. The ITO transparent electrode thus obtained was used as an anode, and Compound A doped with 3% NDP-9 (available from Novaled) 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 to To form a hole transport layer. Compound B was deposited to a thickness of 1000 Å to form a hole transport auxiliary layer, and on the hole transport auxiliary layer, a hole transport auxiliary layer was formed by vacuum deposition using Compound 1 obtained in Synthesis Example 1 as a host and doping 7 wt % of PhGD as a dopant. Thick luminescent layer. For the examples and comparative examples, the ratios are described separately. Subsequently, compound C is applied to the luminescent layer in the form of The thickness of the film is deposited to form an electron transport auxiliary layer, and the compound D and Liq are simultaneously vacuum deposited at a weight ratio of 1:1 to form Thick electron transport layer. and Al The cathode is formed by vacuum deposition on the electron transport layer in sequence, thereby manufacturing a green organic light emitting diode.

[0403] An organic light emitting diode was manufactured to have the following structure: ITO / Compound A (3% NDP-9 doping, ) / Compound A / Compound B / EML[Compound 1 (93 wt%):PhGD (7 wt%)] Compound C / Compound D:LiQ / LiQ / Al

[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] Examples 2 to 6 and Comparative Examples 1 to 3

[0411] Each organic light emitting diode was manufactured in the same manner as in Example 1, except that the composition was changed to the composition described in Table 1.

[0412] Example 7

[0413] A glass substrate coated with ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned for 10 minutes using oxygen plasma, and moved to a vacuum depositor. The ITO transparent electrode thus prepared was used as an anode, and Compound A doped with 3% NDP-9 (Novaled GmbH) was vacuum deposited on the ITO substrate to form A thick hole injection layer is formed, and compound A is deposited on the hole injection layer to Compound E is deposited on the hole transport layer to a thickness of The hole transport auxiliary layer was formed by vacuum deposition of the compound 1 synthesized in Synthesis Example 1 and the compound C-21 synthesized in Synthesis Example 10 as a host on the hole transport auxiliary layer and doped with 10 wt% of PhGD as a dopant. Here, Compound 1 and Compound C-21 were used in a weight ratio of 6:4. Subsequently, Compound F was deposited on the light-emitting layer to form Thick electron transport auxiliary layer, and compound G and Liq were vacuum deposited at a weight ratio of 1:1 to form Thick electron transport layer. and Al Vacuum deposition is sequentially performed on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting diode.

[0414] An organic light emitting diode was manufactured to have the following structure: ITO / Compound A (3% NDP-9 doping, ) / Compound A / Compound E / EML[Compound 1:Compound C-21:PhGD=54:36:10 wt%)] / Compound F / Compound G:LiQ / LiQ / Al

[0415] Compound E: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluoren)-2-amine

[0416] Compound F: 2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine

[0417] Compound G: 2-[4-[4-(4'-cyano-1,1'-biphenyl-4-yl)-1-naphthyl]phenyl]-4,6-diphenyl-1,3,5-triazine

[0418] Examples 8 to 12

[0419] Each organic light emitting diode was manufactured in the same manner as in Example 7, except that the composition was changed to the composition described in Table 2.

[0420] Examples 13 to 18

[0421] Each organic light emitting diode according to Examples 13 to 18 was manufactured in the same manner as in Examples 8 to 12, except that the mixing ratio of the host was changed from 6:4 to 7:3.

[0422] Comparative Examples 4 to 6

[0423] Each of the organic light emitting diodes according to Comparative Examples 4 to 6 was manufactured using the composition shown in Table 2 with a host mixing ratio set to 7:3.

[0424] evaluate

[0425] The driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 18 and Comparative Examples 1 to 4 were evaluated.

[0426] The specific measurement method is as follows, and the results are shown in Tables 1 and 2.

[0427] (1) Measuring the change in current density according to voltage change

[0428] 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.

[0429] (2) Measuring brightness changes according to voltage changes

[0430] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured by using a luminance meter (Minolta Cs-1000A).

[0431] (3) Measure luminous efficiency

[0432] By using the luminance and current density and voltage from (1) and (2) above, calculate the 2 ) under the current efficiency (cd / A).

[0433] The luminous efficiency values ​​of Examples 1 to 6 and Comparative Examples 1 to 3 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0434] The luminous efficiency values ​​of Examples 7 to 18 and Comparative Examples 4 to 6 were calculated as relative values ​​based on Comparative Example 4 and are listed in Table 2.

[0435] (4) Measurement life

[0436] In the case of brightness (cd / m 2 ) maintained at 24000cd / m 2 At the same time, the results were obtained by measuring the time it takes for the current efficiency (cd / A) to drop to 95%.

[0437] The life measurement values ​​of Examples 1 to 6 and Comparative Examples 1 to 3 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0438] The life measurement values ​​of Examples 7 to 18 and Comparative Examples 4 to 6 were calculated as relative values ​​based on Comparative Example 4 and are listed in Table 2.

[0439] (5) Measure the driving voltage

[0440] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 Measure the driving voltage of each diode.

[0441] The driving voltages of Examples 1 to 6 and Comparative Examples 1 to 3 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0442] The driving voltages of Examples 7 to 18 and Comparative Examples 4 to 6 were calculated as relative values ​​based on Comparative Example 4 and are listed in Table 2.

[0443] [Table 1]

[0444]

[0445] [Table 2]

[0446]

[0447]

[0448] Referring to Table 1 and Table 2, the organic light emitting diodes according to Examples 1 to 18 have significantly improved driving voltage, luminous efficiency, and lifespan characteristics compared to the organic light emitting diodes according to Comparative Examples 1 to 6.

Claims

1. A compound for an organic optoelectronic device, the compound being represented by a combination of Chemical Formula 1 and Chemical Formula 2: In Chemical Formula 1 and Chemical Formula 2, X 1 and X 2 are each independently O or S, * Each is a connecting carbon (C), * in Chemical Formula 1 is connected to * in Chemical Formula 2, respectively, R 1 to R 6 are each independently hydrogen, deuterium, 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, R 7 to R 11 are each independently hydrogen, deuterium or substituted or unsubstituted phenyl, m1, m3 and m5 are each independently an integer from 1 to 3, m2 is an integer of 1 or 2, and m4 and m6 are each independently one of integers from 1 to 4.

2. The compound for an organic optoelectronic device according to claim 1, wherein The combination of Chemical Formula 1 and Chemical Formula 2 is represented by Chemical Formula 1A or Chemical Formula 1B: In Chemical Formula 1A and Chemical Formula 1B, X 1 、X 2 、R 1 to R 11 , L 1 、Ar 1 and m1 to m6 are defined in Chemical Formula 1.

3. The compound for an organic optoelectronic device according to claim 1, wherein The combination of Chemical Formula 1 and Chemical Formula 2 is represented by any one of Chemical Formula 1A-I to Chemical Formula 1A-IV and Chemical Formula 1B-I to Chemical Formula 1B-IV: In Chemical Formulas 1A-I to 1A-IV and Chemical Formulas 1B-I to 1B-IV, X 1 、X 2 、R 1 to R 11 , L 1 、Ar 1 and m1 to m6 are defined in Chemical Formula 1A and Chemical Formula 1B.

4. The compound for an organic optoelectronic device according to claim 1, wherein The combination of Chemical Formula 1 and Chemical Formula 2 is represented by any one of Chemical Formula 1A-I-3, Chemical Formula 1A-II-3, Chemical Formula 1A-III-3, Chemical Formula 1A-IV-3, Chemical Formula 1B-I-3, Chemical Formula 1B-II-3, Chemical Formula 1B-III-3, and Chemical Formula 1B-IV-3: In Chemical Formula 1A-I-3, Chemical Formula 1A-II-3, Chemical Formula 1A-III-3, Chemical Formula 1A-IV-3, Chemical Formula 1B-I-3, Chemical Formula 1B-II-3, Chemical Formula 1B-III-3, and Chemical Formula 1B-IV-3, X 1 、X 2 、R 1 to R 11 、Ar 1 , L 1 and m1 to m6 are defined in Chemical Formula 1.

5. The compound for an organic optoelectronic device according to claim 1, wherein Ar 1 is 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.

6. The compound for an organic optoelectronic device according to claim 1, wherein L 1 -Ar 1 is one of the substituents listed in Group I: [Group I] In Group I, R 22 to R 25 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, Ar 5 and Ar 6 are each independently a substituted or unsubstituted C6 to C12 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, m16 is an integer from 1 to 5, m17 is an integer from 1 to 4, m18 is an integer from 1 to 3, m19 is an integer of 1 or 2, and * is the connection point.

7. The compound for an organic optoelectronic device according to claim 1, wherein the compound is selected from the compounds listed in Group 1: [Group 1] 8. 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 3: [Chemical Formula 3] In Chemical Formula 3, Z 1 to Z 6 Each independently is N or CL a -R a , Z 1 to Z 6 At least two of them are N, L a 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 a 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 R a Each exists independently, or adjacent groups are linked to form a substituted or unsubstituted aliphatic, aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aliphatic, aromatic or heteroaromatic polycyclic ring.

9. The composition for an organic optoelectronic device according to claim 8, wherein Chemical Formula 3 is represented by any one of Chemical Formula 3A to Chemical Formula 3C: [Chemical formula 3C] In Chemical Formulae 3A to 3C, Z 1 , Z 3 and Z 5 Each independently is N or CL a -R a , Z 1 , Z 3 and Z 5 At least two of them are N, X 1 Is O, S or NR b , L a and L 2 To L 4 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 a 、R b and R 12 to R 18 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, R 12 and R 13 exist independently of each other, or adjacent groups therein are linked to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring, Ar 2 and Ar 3 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 a 、Ar 2 and Ar 3 exist independently, or R a 、Ar 2 and Ar 3 The adjacent groups in are connected to form a substituted or unsubstituted aromatic or heteroaromatic monocyclic ring or a substituted or unsubstituted aromatic or heteroaromatic polycyclic ring, m7, m8, m10, m12 and m13 are each independently one of integers from 1 to 4, and m9 and m11 are each independently one of integers from 1 to 3.

10. The composition for an organic optoelectronic device according to claim 8, wherein Chemical formula 3 is represented by Chemical formula 3A-IV: [Chemical Formula 3A-IV] In Chemical Formula 3A-IV, Z 1 , Z 3 and Z 5 Each independently is N or CL a -R a , Z 1 , Z 3 and Z 5 At least two of them are N, L a and L 2 To L 4 are each independently a single bond or a substituted or unsubstituted C6 to C12 aryl group, Ar 2 and Ar 3 are 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 triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted carbazolyl group, R a 、R 12 、R 13 and R 19 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl, m7 and m14 are each independently one of integers from 1 to 4, and m8' is an integer of 1 or 2.

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, in, The organic layer includes the compound for an organic optoelectronic device according to any one of claims 1 to 7 or the composition for an organic optoelectronic device according to any one of claims 8 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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