Composition for organic optoelectronic device, organic optoelectronic device and display device

Abstract

The present invention relates to: a composition for an organic optoelectronic device, the composition comprising a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2, and a second compound represented by Chemical Formula 3 or a combination of Chemical Formula 4 and Chemical Formula 5; an organic optoelectronic device comprising the composition; and a display device. Details of Chemical Formulae 1 to 5 are as defined in the specification.

Description

Technical Field

[0001] Disclosed are 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 composition for an organic optoelectronic device capable of realizing an organic optoelectronic device with high efficiency and a long lifespan.

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

[0009] Another embodiment provides a display device including an organic optoelectronic device.

[0010] Technical Solution

[0011] According to one embodiment, a composition for an organic optoelectronic device includes a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2; and a second compound represented by Chemical Formula 3 or a combination of Chemical Formula 4 and Chemical Formula 5.

[0012]

[0013] In Chemical Formula 1 and Chemical Formula 2,

[0014] X 1 and X 2 Each is O or S,

[0015] a1* to a4* are each independently a connecting carbon (C) or CRa ,

[0016] * in Chemical Formula 1 is connected to adjacent two of a1* to a4* in Chemical Formula 2,

[0017] Among a1* to a4* in Chemical Formula 2, the remaining two not connected to * in Chemical Formula 1 are CR a ,

[0018] R a and R 1 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 2 is hydrogen, deuterium or substituted or unsubstituted phenyl,

[0020] m1 is an integer from 1 to 4,

[0021] When m1 is 2 or greater, each R 1 Same or different from each other,

[0022] m15 is an integer from 1 to 5,

[0023] When m15 is 2 or greater, each R 2 are the same as or different from each other, and

[0024] R a 、R 1 and R 2 At least one of them is a group represented by chemical formula a,

[0025] [Chemical formula a]

[0026]

[0027] In chemical formula a,

[0028] Z 1 to Z 3 Each independently is N or CL a -R b ,

[0029] Z 1 to Z 3 At least two of them are N,

[0030] L a , L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0031] R b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0032] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group;

[0033] [Chemical Formula 3]

[0034]

[0035] In Chemical Formula 3,

[0036] R 7 to R 11 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0037] Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0038] L 3 and L 4 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0039] m2, m5 and m6 are each independently an integer from 1 to 4,

[0040] m3 and m4 are each independently one of integers from 1 to 3, and

[0041] n is an integer from 0 to 2;

[0042]

[0043] In Chemical Formula 3 and Chemical Formula 4,

[0044] In Chemical Formula 3, b1* to b4* are each independently a linking carbon (C) or CL b -R c ,

[0045] Among a1* to a4* in Chemical Formula 3, adjacent two are each connected to * in Chemical Formula 4,

[0046] Among a1* to a4* in Chemical Formula 3, the remaining two not connected to * in Chemical Formula 4 are CL b -R c ,

[0047] L b , L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0048] R c 、R 12 and R 13 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0049] 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, and

[0050] m7 and m8 are each independently one of integers from 1 to 4.

[0051] 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 composition for an organic optoelectronic device.

[0052] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0053] Beneficial effects

[0054] An organic optoelectronic device with high efficiency and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0056] <Description of Reference Numerals>

[0057] 100: Organic Light-Emitting Diode

[0058] 105: Organic layer

[0059] 110: cathode

[0060] 120: Anode

[0061] 130: Luminous layer

[0062] 140: Hole transport zone

[0063] 150: Electron transport region DETAILED DESCRIPTION

[0064] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary and the present disclosure is not limited thereto.

[0065] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, halogen, hydroxy, 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.

[0066] In one embodiment 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 embodiment 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 embodiment 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 embodiment 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.

[0067] "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and that a hydrogen atom remains.

[0068] In the present specification, "hydrogen substitution (—H)" may include "deuterium substitution (—D)" or "tritium substitution (—T)".

[0069] As used herein, when no definition is otherwise provided, "hetero" means containing one to three heteroatoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0070] As used herein, "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 linked 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.

[0071] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0072] As used herein, "heterocyclyl" 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 fused ring thereof or a combination thereof. When the heterocyclyl is a fused ring, the entire ring or each ring of the heterocyclyl may include one or more heteroatoms.

[0073] As an 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.

[0074] 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.

[0075] 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 or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzonaphthofuranyl, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofluorenyl, a substituted or unsubstituted benzothiophenefluorenyl group, or a combination thereof, but is not limited thereto.

[0076] As used herein, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductive properties 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.

[0077] 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.

[0078] Hereinafter, a composition for an organic optoelectronic device according to one embodiment is described.

[0079] A composition for an organic optoelectronic device according to one embodiment includes a first compound and a second compound.

[0080] The first compound is represented by a combination of Chemical Formula 1 and Chemical Formula 2.

[0081]

[0082] In Chemical Formula 1 and Chemical Formula 2,

[0083] X 1 and X 2Each is O or S,

[0084] a1* to a4* are each independently a connecting carbon (C) or CR a ,

[0085] * in Chemical Formula 1 is connected to adjacent two of a1* to a4* in Chemical Formula 2,

[0086] Among a1* to a4* in Chemical Formula 2, the remaining two not connected to * in Chemical Formula 1 are CR a ,

[0087] R a and R 1 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,

[0088] R 2 is hydrogen, deuterium or substituted or unsubstituted phenyl,

[0089] m1 is an integer from 1 to 4,

[0090] m15 is an integer from 1 to 5, and

[0091] R a 、R 1 and R 2 At least one of them is a group represented by chemical formula a,

[0092] [Chemical formula a]

[0093]

[0094] In chemical formula a,

[0095] Z 1 to Z 3 Each independently is N or CL a -R b ,

[0096] Z 1 to Z 3 At least two of them are N,

[0097] L a , L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0098] R bis hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0099] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0100] The first compound includes an oxadibenzofuran (or oxadibenzothiophene) core, which has the advantages of high charge mobility, large current on / off ratio, extremely low driving voltage, and excellent efficiency and lifespan characteristics.

[0101] Additionally, the benzoxazole moiety is structurally characterized by a low dielectric constant and has a low dipole moment value, which enables excellent image quality to be achieved when applied to a final device.

[0102] Meanwhile, carbon between two heteroatoms (nitrogen and oxygen) of oxazole has a weak bonding force, so side reactions easily occur when heat is applied, etc. In the present invention, this is substituted with an aromatic ring such as a phenyl group to compensate for the weakness and improve the durability of the material.

[0103] In addition, by using the second compound in combination, excellent characteristics of the organic light-emitting diode can be achieved.

[0104] In Chemical Formula 1 and Chemical Formula 2, when two or more R 1 When replacing, each R 1 They may be the same as or different from each other.

[0105] In Chemical Formula 1 and Chemical Formula 2, when two or more R 2 When replacing, each R 2 They may be the same as or different from each other.

[0106] In Chemical Formula 1 and Chemical Formula 2, when the two R a When replacing, each R a They may be the same as or different from each other.

[0107] In the combination of Chemical Formula 1 and Chemical Formula 2 of the first compound, R a 、R 1 and R 2 One of them may be a group represented by chemical formula a.

[0108] The first compound may be represented by any one of Chemical Formula 1A, Chemical Formula 1B, Chemical Formula 1C, Chemical Formula 1D, Chemical Formula 1E, and Chemical Formula 1F according to a condensation position and a condensation direction.

[0109]

[0110]

[0111] In Chemical Formulas 1A to 1F,

[0112] X 1 、X 2 、R a 、R 1 、R 2 , m1 and m15 are the same as above, and m9 is an integer of 1 or 2.

[0113] Specific examples of the first compound can be represented by Formula 1A-I, Formula 1A-II, Formula 1A-III, Formula 1B-I, Formula 1B-II, Formula 1B-III, Formula 1C-I, Formula 1C-II, Formula 1C-III, Formula 1D-I, Formula 1D-II, Formula 1D-III, Formula 1E-I, Formula 1E-II, Formula 1E-III, Formula 1F-I, Formula 1F-II, and Formula 1F-III.

[0114] Any one of Formulas 1F-III is represented.

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] In Formula 1A-I, Formula 1A-II, Formula 1A-III, Formula 1B-I, Formula 1B-II, Formula 1B-III, Formula 1C-I, Formula 1C-II, Formula 1C-III, Formula 1D-I, Formula 1D-II, Formula 1D-III, Formula 1E-I, Formula 1E-II, Formula 1E-III, Formula 1F-I, Formula 1F-II, and Formula 1F-III,

[0121] X 1 、X 2 , Z 1 to Z 3 、Ar 1 、Ar 2 , L 1 , L 2 , m1, m9 and m15 are the same as above,

[0122] Ra and R 1 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,

[0123] m1' is an integer from 1 to 3,

[0124] m9' is 1, and

[0125] m15' is one of integers from 1 to 4.

[0126] As a specific example, the first compound may be represented by any one of Chemical Formula 1A-I, Chemical Formula 1A-II, and Chemical Formula 1A-III.

[0127] As a more specific example, the first compound may be represented by Chemical Formula 1A-I or the above Chemical Formula 1A-II.

[0128] For example, the first compound may be represented by Chemical Formula 1A-I.

[0129] Since the benzoxazole portion having excellent hole mobility is fused with the portion having high electron mobility via a1* and a2* of Chemical Formula 2, the first compound has excellent overall carrier mobility characteristics, and thus the organic light emitting diode including it has low voltage / high efficiency / long life characteristics.

[0130] For example, R a and R 1 Each of the radicals may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene 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.

[0131] For example, L a , L 1 and L 2 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0132] For example, Ar 1 and Ar 2Each of them may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzothiorol group, a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted indolocarbazolyl group.

[0133] For example, L 1 -Ar 1 and L 2 -Ar 2 The substituents listed in Group I may be each independently selected.

[0134] [Group I]

[0135]

[0136] In Group I,

[0137] R 14 to R 17 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl, or C6 to C12 aryl,

[0138] Ar 7 is a substituted or unsubstituted C6 to C12 aryl group,

[0139] m11 is an integer from 1 to 5,

[0140] m12 is an integer from 1 to 4,

[0141] m13 is an integer from 1 to 3,

[0142] m14 is an integer of 1 or 2, and

[0143] * is the connection point.

[0144] In Group I, when two or more R 14 When replacing, each R 16 They may be the same as or different from each other.

[0145] In Group I, when two or more R 15 When replacing, each R 17 They may be the same as or different from each other.

[0146] In Group I, when two or more R 16 When replacing, each R 18 They may be the same as or different from each other.

[0147] In Group I, when two or more R 17 When replacing, each R 19They may be the same as or different from each other.

[0148] In Group I, when two or more R 18 When replacing, each R 20 They may be the same as or different from each other.

[0149] In the most specific embodiment, the first compound may be one selected from the compounds listed in Group 1, but is not limited thereto.

[0150] [Group 1]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] The second compound is represented by Chemical Formula 3; or by a combination of Chemical Formulas 4 and 5 below.

[0162] [Chemical Formula 3]

[0163]

[0164] In Chemical Formula 3,

[0165] R 7 to R 11 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0166] Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0167] L3 and L 4 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, m2, m5 and m6 are each independently an integer from 1 to 4,

[0168] m3 and m4 are each independently one of integers from 1 to 3, and

[0169] n is an integer from 0 to 2;

[0170]

[0171]

[0172] In Chemical Formula 3 and Chemical Formula 4,

[0173] In Chemical Formula 3, b1* to b4* are each independently a linking carbon (C) or CL b -R c ,

[0174] Among a1* to a4* in Chemical Formula 3, adjacent two are each connected to * in Chemical Formula 4,

[0175] Among a1* to a4* in Chemical Formula 3, the remaining two not connected to * in Chemical Formula 4 are CL b -R c ,

[0176] L b , L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0177] R c 、R 12 and R 13 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0178] 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, and

[0179] m7 and m8 are each independently one of integers from 1 to 4.

[0180] The second compound may be used together with the above-mentioned first compound in the light-emitting layer to improve light-emitting efficiency and lifespan characteristics by increasing charge mobility and enhancing stability.

[0181] In Chemical Formula 3, when two or more R 7 When replacing, each R 7 They may be the same as or different from each other.

[0182] In Chemical Formula 3, when two or more R 8 When replacing, each R 8 They may be the same as or different from each other.

[0183] In Chemical Formula 3, when two or more R 9 When replacing, each R 9 They may be the same as or different from each other.

[0184] In Chemical Formula 3, when two or more R 10 When replacing, each R 10 They may be the same as or different from each other.

[0185] In Chemical Formula 3, when two or more R 11 When replacing, each R 11 They may be the same as or different from each other.

[0186] In Formula 4 and Formula 5, when two or more R 12 When replacing, each R 12 They may be the same as or different from each other.

[0187] In Formula 4 and Formula 5, when two or more R 13 When replacing, each R 13 They may be the same as or different from each other.

[0188] In Formula 4 and Formula 5, when the two R c When replacing, each R c They may be the same as or different from each other.

[0189] For example, in Chemical Formula 3, Ar 3 and Ar 4 each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 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.

[0190] In Chemical Formula 3, L 3 and L 4 may each independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,

[0191] In Chemical Formula 3, R 7to R 11 may each independently be hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group, and

[0192] n can be 0 or 1.

[0193] For example, in Chemical Formula 3, “substituted” means that at least one hydrogen is substituted with deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.

[0194] For example, in Chemical Formula 3, Ar 3 and Ar 4 Each independently may be 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.

[0195] In a specific embodiment of the present invention, Chemical Formula 3 may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-15.

[0196]

[0197]

[0198] In Chemical Formulae 3-1 to 3-15, m2 to m6 are the same as above, and R 7 to R 11 may each independently be hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, and L 3 -Ar 3 and L 4 -Ar 4 and each independently may be one of the substituents listed in Group II.

[0199] [Group II]

[0200]

[0201] In Group II,

[0202] R 18 to R 22 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl,

[0203] m18 is an integer from 1 to 5,

[0204] m19 is an integer from 1 to 4,

[0205] m20 is an integer from 1 to 3,

[0206] m21 is an integer of 1 or 2,

[0207] m22 is one of integers from 1 to 7, and

[0208] * is the connection point.

[0209] In Group II, when two or more R 18 When replacing, each R 16 They may be the same as or different from each other.

[0210] In Group II, when two or more R 19 When replacing, each R 17 They may be the same as or different from each other.

[0211] In Group II, when two or more R 20 When replacing, each R 18 They may be the same as or different from each other.

[0212] In Group II, when two or more R 21 When replacing, each R 19 They may be the same as or different from each other.

[0213] In Group II, when two or more R 22 When replacing, each R 20 They may be the same as or different from each other.

[0214] The second compound may be represented, for example, by any one of Chemical Formula 4A, Chemical Formula 4B, Chemical Formula 4C, Chemical Formula 4D, and Chemical Formula 4E.

[0215]

[0216]

[0217] In Chemical Formulae 4A to 4E, m12, m13, L 5 , L 6 、Ar 5 、Ar 6 、R 12 and R 13 Same as above,

[0218] L b1 To L b4 Such as L 5 and L 6 defined, and

[0219] R c1 to R c4 Such as R 12 and R 13 defined.

[0220] For example, in Chemical Formula 4 and Chemical Formula 5, Ar 5 and Ar 6 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

[0221] R c1 to R c4 、R 12 and R 13 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.

[0222] In a specific embodiment of the present invention, in Chemical Formula 4 and Chemical Formula 5, *-L 5 -Ar 5 and *-L 6 -Ar 6 may be each independently selected from the substituents listed in Group II.

[0223] In one embodiment, R c1 to R c4 、R 12 and R 13 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.

[0224] For example, R c1 to R c4 、R 12 and R 13 may each independently be hydrogen, deuterium, cyano or substituted or unsubstituted phenyl, and

[0225] In a specific embodiment, R c1 to R c4 、R 12 and R 13 and may each independently be hydrogen, deuterium, or a substituted or unsubstituted phenyl group.

[0226] In a specific embodiment of the present invention, the second compound can be represented by Chemical Formula 3-8, in which Ar 3 and Ar 4L 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, 3 and L 4 may each independently be a single bond or a substituted or unsubstituted C6 to C20 arylene group, and R 7 to 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.

[0227] For example, in Chemical Formula 3-8, R 7 to R 10 may each independently be hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, and L 3 -Ar 3 and L 4 -Ar 4 and each independently may be one of the substituents listed in Group II.

[0228] In another embodiment of the present invention, the second compound can be represented by Chemical Formula 4C or Chemical Formula 4D. In Chemical Formula 4C and Chemical Formula 4D, L b1 To L b4 Can be a single bond, L 5 and L 6 may be each independently a single bond or a substituted or unsubstituted C6 to C12 arylene group, R 12 、R 13 and R c1 to R c4 can each be hydrogen, deuterium or phenyl, and Ar 5 and Ar 6 Each 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.

[0229] For example, in Chemical Formula 4C and Chemical Formula 4D, L b1 To L b4 Can be a single bond, R 12 、R 13 and R c1 to R c4 may each independently be hydrogen, deuterium or C6 to C12 aryl, and L 5 -Ar 5 and L 6 -Ar6 and each independently may be one of the substituents listed in Group II.

[0230] 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.

[0231] [Group 2]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] In the most specific embodiment, the first compound can be represented by Chemical Formula 1A-I, and the second compound can be represented by any one of Chemical Formula 3-8, Chemical Formula 4C, and Chemical Formula 4D.

[0247] For example, the first compound and the second compound can be included in a weight ratio of 1:99 to 99:1. Within this range, the electron transport ability of the first compound and the hole transport ability of the second compound can be used to adjust the desired weight ratio to achieve bipolar characteristics, and thus improve efficiency and lifespan. Within the above range, for example, they can be included in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20 (for example, 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.

[0248] In addition to the above-mentioned first compound and second compound, one or more compounds may be further contained.

[0249] The composition for an organic optoelectronic device may further include a dopant.

[0250] 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.

[0251] A dopant is a material mixed in a small amount with a composition for an organic optoelectronic device to induce light emission, 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.

[0252] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organometallic compound containing 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.

[0253] [Chemical formula Z]

[0254] L 7 MX 3

[0255] In the chemical formula Z, M is a metal, and L 7 and X 3 The same or different ligands that form a complex with M.

[0256] 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 7 and X 3 This may be, for example, a bidentate ligand.

[0257] By L 7 and X 3 Examples of the ligand represented by may be selected from the chemical formulae listed in Group A, but are not limited thereto.

[0258] [Group A]

[0259]

[0260] In Group A,

[0261] 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

[0262] 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.

[0263] For example, it may include a dopant represented by Chemical Formula V.

[0264] [Chemical Formula V]

[0265]

[0266] In Chemical Formula V,

[0267] 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 ,

[0268] R 132 to R 134 are each independently C1 to C6 alkyl,

[0269] R 101 to R116 At least one of them is a functional group represented by Chemical Formula V-1,

[0270] L 100 is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone electron pair of carbon or a heteroatom, and

[0271] 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,

[0272] [Chemical Formula V-1]

[0273]

[0274] In Chemical Formula V-1,

[0275] 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

[0276] * indicates a moiety attached to a carbon atom.

[0277] For example, it may include a dopant represented by Chemical Formula Z-1.

[0278] [Chemical Formula Z-1]

[0279]

[0280] In formula Z-1, rings A, B, C, and D are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0281] R A 、R B 、R C and R D each independently mono-, di-, tri- or tetra-substituted or unsubstituted;

[0282] L B , L C and L D are each independently a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof,

[0283] When nA is 1, L EIt can be a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof; and when nA is 0, L E does not exist;

[0284] R A 、R B 、R C 、R D R and R' are each independently 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, or a combination 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 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.

[0285] According to one embodiment, the dopant may be a platinum complex, and may be represented, for example, by Chemical Formula VI.

[0286] [Chemical Formula VI]

[0287]

[0288] In Chemical Formula VI,

[0289] X 100 Selected from O, S and NR 131 ,

[0290] 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 ,

[0291] R 132 to R 134 are each independently C1 to C6 alkyl,

[0292] R 117 to R 131At least one of them is -SiR 132 R 133 R 134 or tert-butyl, and

[0293] R 132 to R 134 Each is independently a C1 to C6 alkyl group.

[0294] Hereinafter, an organic optoelectronic device including the above-mentioned composition for an organic optoelectronic device is described.

[0295] The organic optoelectronic device may be a suitable device that converts electrical energy into light energy and vice versa, for example, an organic photovoltaic device, an organic light emitting diode, an organic solar cell, or an organic photosensitive drum.

[0296] Herein, an organic light emitting diode as one example of an organic optoelectronic device is described with reference to the accompanying drawings.

[0297] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0298] 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 .

[0299] 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 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.

[0300] 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.

[0301] The organic layer 105 may include the above-described composition for an organic optoelectronic device.

[0302] 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.

[0303] The composition for an organic optoelectronic device further including a dopant may be, for example, a green light emitting composition.

[0304] The light emitting layer 130 may include, for example, the first compound and the second compound described above as phosphorescent hosts, respectively.

[0305] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0306] The charge transport region may be, for example, a hole transport region 140 .

[0307] 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.

[0308] 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.

[0309] [Group B]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315] In the hole transport region 140 , in addition to the above-described compounds, known compounds disclosed in US Pat. No. 5,061,569 A, JP 1993-009471 A, WO 1995-009147 A1, JP 1995-126615 A, JP 1998-095973 A, etc., and compounds having similar structures can be used.

[0316] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0317] The electron transport region 150 may also improve electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0318] 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.

[0319] [Group C]

[0320]

[0321]

[0322]

[0323] One embodiment may be an organic light emitting diode including a light emitting layer as an organic layer.

[0324] Another embodiment may be an organic light emitting diode including a light emitting layer and a hole transport region as organic layers.

[0325] Another embodiment may be an organic light emitting diode including a light emitting layer and an electron transport region as organic layers.

[0326] In addition to the light emitting layer 130, the organic light emitting diode according to one embodiment further includes a hole transport region 140 and an electron transport region 150 as the organic layer 105. Figure 1 shown.

[0327] 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.

[0328] 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.

[0329] Organic light emitting diodes can be applied to organic light emitting display devices.

[0330] 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.

[0331] Detailed description of implementation methods

[0332] 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.

[0333] (Preparation of Compounds for Organic Optoelectronic Devices)

[0334] (Synthesis of the First Compound)

[0335] Synthesis Example 1: Synthesis of Compound 1

[0336] [Reaction formula 1]

[0337]

[0338] Step 1: Synthesis of intermediate I-1

[0339] 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. Subsequently, the reactant was poured into a large amount of DIW (deionized water), then stirred for 30 minutes, filtered, and washed twice or more. The solid was thus separated, extracted with dichloromethane and DIW and dried with magnesium sulfate, and all solvents were removed. Subsequently, the solid was dissolved in dichloromethane 10 times the amount of the solid, and 84.9g (374mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was slowly added thereto, followed by reaction at room temperature for 2 hours to obtain intermediate I-1 (70g, yield: 70%).

[0340] Step 2: Synthesis of intermediate I-2

[0341] 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 water layer and removing the solvent with a rotary evaporator, extracted with dichloromethane / DIW. The organic layer thus obtained was subjected to column separation with hexane: EA=4:1 (v / v), thereby obtaining 40.0 g (yield: 49%) of intermediate I-2.

[0342] Step 3: Synthesis of intermediate I-3

[0343] Intermediate I-2 (40.0 g, 117.73 mmol) and K 3 PO 4 (50.0 g, 235.47 mmol) were added to DMF (N, N-dimethylformamide) (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 was extracted with dichloromethane / DIW, dried with MgSO 4 and concentrated, and then 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.

[0344] Step 4: Synthesis of intermediate I-4

[0345] 30.0 g (93.83 mmol) of Intermediate I-3, 24.0 g (93.83 mmol) of bis-boronic acid pinacol ester, 5.16 g (5.63 mmol) of Pd2(dba)3, 6.31 g (22.52 mmol) of P(Cy)3, and 27.63 g (281.48 mmol) of KOAc were dissolved in 300 mL of xylene, and then stirred and refluxed at 150° C. for 12 hours. When the reaction was complete, the reaction solvent was removed by rotary evaporation, and the organic layer was extracted with dichloromethane and separated by a hexane:EA=4:1 (v / v) column to obtain 30.0 g (yield: 78%) of Intermediate I-4.

[0346] Step 5: Synthesis of Compound 1

[0347] In a round-bottom flask, 30.0 g (69.81 mmol) of intermediate I-4, 24.0 g (69.81 mmol) of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine purchased from P&HTech Co., Ltd. (http: / / www.phtech.co.kr / ), 4.03 g (3.49 mmol) of Pd(PPh3)4, and 24.12 g (174.51 mmol) of K2CO3 were dissolved in 150 mL of THF and 70 mL of distilled water, and then heated to reflux under a nitrogen atmosphere. After 12 hours, the reaction solution was cooled and the organic layer was dried under reduced pressure after removing the water layer. The resulting solid was washed with water and methanol and recrystallized twice with 200 mL of toluene to obtain 33.0 g (yield: 80%) of compound 1. LC / MS theoretical value of C40H24N4O2: 592.19, experimental value: 592.88 [M+H]

[0348] Synthesis Example 2: Synthesis of Compound 11

[0349] Compound 11 (38.22 g, 80%) was obtained in the same manner as in Step 5 of Synthesis Example 1, except that intermediate I-4 (30.0 g, 71.44 mmol) obtained in the same manner as in Steps 1 to 4 of Synthesis Example 1 and 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (30.0 g, 71.44 mmol) purchased from P&H Tech Co., Ltd. (http: / / www.phtech.co.kr / ) were used. LC / MS theoretical value for C46H28N4O2: 668.22, found: 669.75 [M+H]

[0350] Synthesis Example 3: Synthesis of Compound 41

[0351] Compound 41 (36.0 g, yield: 75%) was obtained in the same manner as in Step 5 of Synthesis Example 1, except that Intermediate I-4 (30.0 g, 71.79 mmol) obtained in the same manner as in Steps 1 to 4 of Synthesis Example 1 and 2-chloro-4-phenyl-6-(triphenyl-2-yl)-1,3,5-triazine (30.0 g, 71.79 mmol) purchased from P&H Tech Co., Ltd. (http: / / www.phtech.co.kr / ) were used. LC / MS theoretical value for C46H26N4O2: 666.21, found: 667.85 [M+H]

[0352] Synthesis Example 4: Synthesis of Compound 69

[0353] [Reaction formula 2]

[0354]

[0355] Step 1: Synthesis of intermediate I-5

[0356] Intermediate I-5 (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.

[0357] Step 2: Synthesis of intermediate I-6

[0358] Intermediate I-6 (60.0 g, yield: 69%) was obtained in the same manner as in Step 2 of Synthesis Example 1, except that intermediate I-5 (70.0 g, 255.36 mmol) and (2-chloro-6-fluorophenyl)boronic acid (53.43 g, 306.44 mmol) purchased from Merck & Co., Inc. were used.

[0359] Step 3: Synthesis of intermediate I-7

[0360] Intermediate I-6 (60.0 g, 185.33 mmol) and 38.42 g (277.99 mmol) of K CO 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 methyl mercaptan 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 separated from the mixture by a filter, extracted with ethyl acetate and DIW, and after the solvent layer was evaporated from the mixture, recrystallized with hexane to obtain intermediate I-7 (38.0 g, yield: 58%).

[0361] Step 4: Synthesis of intermediate I-8

[0362] Intermediate I-7 (38.0 g, 108.0 mmol) and 34.65 g (162.0 mmol) of sodium periodate were dissolved in a mixed solvent of 700 mL 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, and the solvent was evaporated to obtain Intermediate I-8 (35.0 g, yield: 88%).

[0363] Step 5: Synthesis of Intermediate I-9

[0364] Intermediate I-8 (35.0g, 95.15mmol) is dissolved in 500mL 1,2-dichloroethane, and the reaction solution is set at 0 ° C, 53.69g (190.29mmol) trifluoromethanesulfonic anhydride is slowly added dropwise thereto, and after the reaction temperature is raised to room temperature, the mixture is stirred for 1 hour. After its internal temperature is set at 5 ° C, pyridine (22.57g, 142.72mmol) is slowly added dropwise thereto, and then reacted at room temperature for 12 hours. The solid thus obtained is filtered and washed with ethanol, and the solvent is removed to obtain intermediate I-9 (22.0g, yield: 69%).

[0365] Step 6: Synthesis of Intermediate I-10

[0366] Intermediate I-10 (16.0 g, yield: 57%) was obtained in the same manner as in Step 4 of Synthesis Example 1, except that Intermediate I-9 (22.0 g, 65.51 mmol) was used instead of Intermediate I-4.

[0367] Step 7: Synthesis of Compound 69

[0368] In a round-bottom flask, intermediate I-10 (16 g, 46.54 mmol) and 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (22.0 g, 69.81 mmol) purchased from P&H Tech Co., Ltd. (http: / / www.phtech.co.kr / ) were used in the same manner as in Synthesis Example 5 to obtain compound 69 (20 g, yield: 71%). LC / MS theoretical value of C₄₀₄₀₄NOS: 608.17, found: 609.33 [M+H]

[0369] Synthesis Example 5: Synthesis of Compound 1

[0370]

[0371] The main compound 1 was synthesized by referring to the synthesis method of patent WO2016-194604.

[0372] HRMS (70 eV, EI+): m / z theoretical value of C45H29N5: 639.2423, experimental value: 639.

[0373] Elemental analysis: C, 84%; H, 5%

[0374] (Synthesis of the Second Compound)

[0375] Synthesis Example 6: Synthesis of Compound B-136

[0376]

[0377] Compound B-136 was synthesized by referring to the synthesis method of patent EP3034581.

[0378] HRMS (70 eV, EI+): m / z theoretical value of C42H28N2: 560.2252, experimental value: 560.

[0379] Elemental analysis: C, 90%; H, 5%

[0380] Synthesis Example 7: Synthesis of Compound B-99

[0381]

[0382] Compound B-99 was synthesized by referring to the synthesis method of patent KR10-2019-0000597.

[0383] HRMS (70 eV, EI+): m / z theoretical value of C48H32N2: 636.2565, experimental value: 636.

[0384] Elemental analysis: C, 91%; H, 5%

[0385] Synthesis Example 8: Synthesis of Compound B-31

[0386]

[0387] Compound B-31 was synthesized by referring to the synthesis method of patent EP2947071.

[0388] HRMS (70 eV, EI+): m / z theoretical value of C48H32N2: 636.2565, experimental value: 636.

[0389] Elemental analysis: C, 91%; H, 5%

[0390] Synthesis Example 9: Synthesis of Compound C-4

[0391]

[0392] Compound C-4 was synthesized by referring to the synthesis method of patent KR2031300.

[0393] HRMS (70 eV, EI+): m / z theoretical value of C42H28N2: 560.2252, experimental value: 560.

[0394] Elemental analysis: C, 90%; H, 5%

[0395] Synthesis Example 10: Synthesis of Compound C-57

[0396]

[0397] Compound C-57 was synthesized by referring to the synthesis method of patent WO2018-095391.

[0398] HRMS (70 eV, EI+): m / z theoretical value of C48H32N2: 636.2565, experimental value: 636.

[0399] Elemental analysis: C, 91%; H, 5%

[0400] Synthesis Example 11: Synthesis of Compound 2

[0401] [Reaction formula 3]

[0402]

[0403] Step 1: Synthesis of intermediate 2a

[0404] Refer to patent KR10-1423173B1 to synthesize the intermediate body 2a.

[0405] Step 2: Synthesis of Compound 2

[0406] 20.0g (62.22mmol) of intermediate body 2a, 19.84g (62.22mmol) of amine intermediate body 2b, 8.97g (93.34mmol) of sodium tert-butoxide and 2.52g (6.22mmol) of tri-tert-butylphosphine were dissolved in 200mL of toluene, and 1.71g (1.87mmol) of Pd (dba) 2 was added thereto, and then stirred and refluxed under a nitrogen atmosphere for 12 hours. When the reaction was complete, the organic layer was extracted with toluene and distilled water, and dried over anhydrous magnesium sulfate and 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 30.0g (yield: 80.0%) of compound body 2.

[0407] Example 1

[0408] A glass substrate coated with ITO (indium tin oxide) was cleaned with distilled water and ultrasonic waves. After cleaning 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 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 (available from Novaled) doped with 3% NDP-9 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 form Compound E is deposited on the hole transport layer to On the hole transport auxiliary layer, the compound 1 synthesized in Synthesis Example 1 and the compound B-136 synthesized in Synthesis Example 6 were used as the host and doped with 10 wt% of PhGD as a dopant to form a hole transport auxiliary layer by vacuum deposition. Here, compound 1 and compound B-136 were used in a weight ratio of 3:7. Then, compound C was deposited on the light-emitting layer to form Thick electron transport auxiliary layer, and compound D and LiQ are 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 an organic light emitting diode.

[0409] The organic light emitting diode has the following structure: ITO / compound A (3% NDP-9 doping, ) / Compound A / Compound E / EML[{host (Compound 1: Compound B-136): dopant (PhGD)}=90 wt%:10 wt%)] Compound C / Compound D:LiQ / LiQ / Al .

[0410] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0411] Compound C: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluoren)-2-amine

[0412] Compound D: 2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine

[0413] Compound E: 2-[4-[4-(4'-cyano-1,1'-biphenyl-4-yl)-1-naphthyl]phenyl]-4,6-diphenyl-1,3,5-triazine

[0414] Examples 2 to 11 and Comparative Examples 1 to 7

[0415] An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compositions were changed to those shown in Table 1.

[0416] evaluate

[0417] The driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 11 and Comparative Examples 1 to 7 were evaluated.

[0418] The specific measurement method is shown below, and the results are shown in Table 1.

[0419] (1) Measuring the change in current density according to voltage change

[0420] While increasing the voltage from 0 V to 10 V, the current value flowing through the unit diode 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.

[0421] (2) Measuring the brightness change according to the voltage change

[0422] 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).

[0423] (3) Measure luminous efficiency

[0424] Using the luminance and current density and voltage measured by (1) and (2) above, calculate the current density (10 mA / cm 2 ) under the current efficiency (cd / A).

[0425] The luminous efficiency values ​​of Examples 1 to 11 and Comparative Examples 1 to 7 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0426] (4) Measurement life

[0427] In the case of brightness (cd / m 2 ) maintained at 24000cd / m 2 At the same time, the time until the current efficiency (cd / A) each dropped to 97% was measured as the lifespan.

[0428] The life measurement values ​​of Examples 1 to 11 and Comparative Examples 1 to 7 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0429] (5) Measure the driving voltage

[0430] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 The driving voltage of each diode is measured to obtain the result.

[0431] The driving voltages of Examples 1 to 11 and Comparative Examples 1 to 7 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1.

[0432] [Table 1]

[0433]

[0434]

[0435] Referring to Table 1, the organic light emitting diodes according to Examples 1 to 11 have significantly improved driving voltage, luminous efficiency, and lifespan characteristics compared to the organic light emitting diodes according to Comparative Examples 1 to 7.

Claims

1. A composition for an organic optoelectronic device, comprising: a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2; and A second compound represented by Chemical Formula 3 or a combination of Chemical Formula 4 and Chemical Formula 5: In Chemical Formula 1 and Chemical Formula 2, X 1 and X 2 Each is O or S, a1* to a4* are each independently a connecting carbon (C) or CR a , * in Chemical Formula 1 is connected to adjacent two of a1* to a4* in Chemical Formula 2, Among a1* to a4* in Chemical Formula 2, the remaining two not connected to * in Chemical Formula 1 are CR a , R a and R 1 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 2 is hydrogen, deuterium or substituted or unsubstituted phenyl, m1 is an integer from 1 to 4, When m1 is 2 or greater, each R 1 Same or different from each other, m15 is an integer from 1 to 5, When m15 is 2 or greater, each R 2 are the same as or different from each other, and R a 、R 1 and R 2 At least one of them is a group represented by chemical formula a, [Chemical formula a] In chemical formula a, Z 1 to Z 3 Each independently is N or CL a -R b , Z 1 to Z 3 At least two of them are N, L a , L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group, R b is 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, and Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group; [Chemical Formula 3] In Chemical Formula 3, R 7 to R 11 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, L 3 and L 4 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, m2, m5 and m6 are each independently an integer from 1 to 4, m3 and m4 are each independently one of integers from 1 to 3, and n is an integer from 0 to 2; In Chemical Formula 4 and Chemical Formula 5, In Chemical Formula 4, b1* to b4* are each independently a linking carbon (C) or CL b -R c , among a1* to a4* in Chemical Formula 4, two adjacent ones are each connected to * in Chemical Formula 4, Among a1* to a4* in Chemical Formula 4, the remaining two not connected to * in Chemical Formula 4 are CL b -R c , L b , L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, R c 、R 12 and R 13 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, 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, and m7 and m8 are each independently one of integers from 1 to 4.

2. The composition for an organic optoelectronic device according to claim 1, wherein The first compound is represented by any one of Chemical Formula 1A, Chemical Formula 1B, Chemical Formula 1C, Chemical Formula 1D, Chemical Formula 1E, and Chemical Formula 1F: In Chemical Formulas 1A to 1F, X 1 、X 2 、R a 、R 1 、R 2 , m1 and m15 as defined in claim 1, and m9 is an integer of 1 or 2.

3. The composition for an organic optoelectronic device according to claim 2, wherein The first compound is represented by any one of Chemical Formula 1A-I, Chemical Formula 1A-II, and Chemical Formula 1A-III: [Chemical Formula 1A-III] In Chemical Formula 1A-I to Chemical Formula 1A-III, X 1 、X 2 , Z 1 to Z 3 、R a 、R 1 、R 2 、Ar 1 、Ar 2 , L 1 , L 2 , m1, m9 and m15 as defined in claim 2, m1' is an integer from 1 to 3, m9' is 1, and m15' is one of integers from 1 to 4.

4. The composition for an organic optoelectronic device according to claim 1, wherein Ar 1 and Ar 2 Each is independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzothiorol group, a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted indolocarbazolyl group.

5. The composition for an organic optoelectronic device according to claim 1, wherein L 1 -Ar 1 and L 2 -Ar 2 Each is independently one of the substituents listed in Group I: [Group I] In Group I, R 14 to R 17 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, Ar 7 is a substituted or unsubstituted C6 to C12 aryl group, 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, and * is the connection point.

6. The composition for an organic optoelectronic device according to claim 1, wherein The first compound is selected from the compounds listed in Group 1: [Group 1] 7. The composition for an organic optoelectronic device according to claim 1, wherein The second compound is represented by Chemical Formula 3-8: [Chemical Formula 3-8] In Chemical Formula 3-8, R 7 to R 10 are each independently hydrogen, deuterium or a substituted or unsubstituted C6 to C12 aryl group, m2 and m5 are each independently an integer from 1 to 4, m3 and m4 are each independently one of integers from 1 to 3, and L 3 -Ar 3 and L 4 -Ar 4 are each independently one of the substituents listed in Group II, [Group II] In Group II, R 18 to R 22 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, m18 is an integer from 1 to 5, m19 is an integer from 1 to 4, m20 is an integer from 1 to 3, m21 is an integer of 1 or 2, m22 is one of integers from 1 to 7, and * is the connection point.

8. The composition for an organic optoelectronic device according to claim 1, wherein The second compound is represented by Chemical Formula 4C or Chemical Formula 4D: [Chemical Formula 4C] [Chemical Formula 4D] In Chemical Formula 4C and Chemical Formula 4D, L b1 To L b4 is a single bond, R 12 、R 13 and R c1 to R c4 are each independently hydrogen, deuterium or C6 to C12 aryl, m7 and m8 are each independently an integer from 1 to 4, and L 5 -Ar 5 and L 6 -Ar 6 Each is independently one of the substituents listed in Group II, [Group II] In Group II, R 18 to R 22 are each independently hydrogen, deuterium, cyano, C1 to C10 alkyl or C6 to C12 aryl, m18 is an integer from 1 to 5, m19 is an integer from 1 to 4, m20 is an integer from 1 to 3, m21 is an integer of 1 or 2, m22 is one of integers from 1 to 7, and * is the connection point.

9. 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 composition for an organic optoelectronic device according to any one of claims 1 to 8.

10. The organic optoelectronic device according to claim 9, wherein The organic layer includes a light-emitting layer, and The light-emitting layer includes the composition for an organic optoelectronic device. 11 . A display device comprising the organic optoelectronic device according to claim 9 .

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