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

Abstract

The present invention relates to a compound for an organic photoelectric device, an organic photoelectric device and a display device, wherein the compound is represented by Chemical Formula 1, and the organic photoelectric device and the display device include the compound. The content of Chemical Formula 1 is defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0134190 filed in the Korean Intellectual Property Office on October 8, 2021, the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] An organic photovoltaic device (organic photodiode) is a device that converts electrical energy into light energy (or vice versa).

[0005] Organic photoelectric devices can be classified as follows according to their driving principles: one is an optoelectronic device in which excitons generated by light energy are separated into electrons and holes and the electrons and holes are transferred to different electrodes, respectively, and generate electrical energy, and the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

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

[0007] Among them, organic light emitting diodes (OLEDs) have recently attracted attention due to the increasing demand for flat panel displays. Organic light emitting diodes convert electrical energy into light, and organic materials disposed between electrodes have a great influence on the performance of organic light emitting diodes. Summary of the invention

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

[0009] Another embodiment provides an organic photoelectric device including the compound.

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

[0011] According to one embodiment, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[0012] [Chemical formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] Z 1 To Z 3 Each independently is N or CR a ,

[0016] Z 1 To Z 3 At least two of them are N,

[0017] 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,

[0018] L 3 is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

[0019] 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,

[0020] R a and R 1 To R 10 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl, and

[0021] m1 to m4 are each independently one of integers of 1 to 4.

[0022] According to another embodiment, an organic photoelectric device includes an anode and a cathode facing each other, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes a compound for an organic photoelectric device.

[0023] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0024] High-efficiency and long-life organic photovoltaic devices can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0026] <Description of Reference Numerals>

[0027] 100: Organic light-emitting diode

[0028] 105: Organic layer

[0029] 110: cathode

[0030] 120: Anode

[0031] 130: Luminous layer

[0032] 140: Hole transport region

[0033] 150: Electron transport region DETAILED DESCRIPTION

[0034] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0035] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of the substituent or compound is replaced with 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.

[0036] In one example of the present invention, "substituted" means that at least one hydrogen of a substituent or a 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 addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl, or cyano. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen in a substituent or a compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0037] As used herein, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and that a hydrogen atom remains.

[0038] As used herein, "hydrogen substitution (—H)" may include "deuterium substitution (—D)" or "tritium substitution (—T)".

[0039] As used herein, when no definition is otherwise provided, "hetero" means including one to three heteroatoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0040] As used herein, "aryl" refers to a group including at least one hydrocarbon aromatic portion, and may include a group in which all elements of the hydrocarbon aromatic portion have p orbitals forming a conjugation, such as phenyl, naphthyl, etc., a group in which two or more hydrocarbon aromatic portions may be linked by a σ bond, such as biphenyl, terphenyl, quaterphenyl, etc., and a group in which two or more hydrocarbon aromatic portions are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl, etc.

[0041] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0042] As used herein, "heterocyclic group" is a general concept of heteroaryl, and may contain at least one heteroatom selected from N, O, S, P, and Si instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a condensed ring thereof, or a combination thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms.

[0043] For example, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl includes two or more rings, the two or more rings can be fused. When the heteroaryl is a fused ring, each ring can include 1 to 3 heteroatoms.

[0044] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted peryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0045] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted The invention may include quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted dibenzosilolyl, or a combination thereof, but is not limited thereto.

[0046] In this specification, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, and due to the 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.

[0047] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level.

[0048] Hereinafter, a compound for an organic photoelectric device according to one embodiment is described.

[0049] The compound for an organic photoelectric device according to one embodiment is represented by Chemical Formula 1.

[0050] [Chemical formula 1]

[0051]

[0052] In Chemical Formula 1,

[0053] Z 1 To Z 3 Each independently is N or CR a ,

[0054] Z 1 To Z 3 At least two of them are N,

[0055] 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,

[0056] L 3 is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

[0057] 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,

[0058] R a and R 1 To R 10 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl, and

[0059] m1 to m4 are each independently one of integers of 1 to 4.

[0060] The compound represented by Chemical Formula 1 has a structure in which carbazole is substituted with triazine at the 9th position, and the carbazole substituted with triazine at the 9th position is substituted with two 9-carbazoles at the 1st position and the 5th position, respectively.

[0061] Since two 9-carbazoles are substituted at the 1st and 5th positions respectively, the problem of halving the π-bonding, which is a movement path for electrons and holes, can be solved, thereby improving the mobility of electrons and holes, and since the 1st and 5th positions are substituted, the plate-like molecular structure has a distorted structure due to the steric hindrance of adjacent hydrogen or substituents, thereby achieving a low deposition temperature.

[0062] Organic light emitting diodes using the above materials can achieve low driving voltage and long life characteristics.

[0063] In addition, a material with a reduced difference between T1 and S1 (ΔEst) can be prepared through a rigid structure design, and an organic light emitting diode using such a material can achieve high efficiency.

[0064] For example, L 3 It may be a single bond or a substituted or unsubstituted phenylene group.

[0065] For example, L 3It may be substituted or unsubstituted ortho-phenylene.

[0066] When L 3 When it is a substituted or unsubstituted o-phenylene group, it has steric hindrance compared to p-phenylene, thereby achieving a low deposition temperature. In addition, when a carbazole group having HT characteristics and a triazine group having ET characteristics are connected to p-phenylene, localization (electron cloud localization) occurs only by breaking the CN bond of the π-bond, and when they are connected to o-phenylene, structurally, the group having HT characteristics and the group having ET characteristics are combined at a certain angle to prevent electron movement, thereby making the HOMO / LUMO electron cloud localization clearer, the difference between T1 and S1 is reduced, and a material with a small ΔEst can be achieved. It is well known in the art that materials with a small ΔEst can generally achieve high efficiency.

[0067] For example, Ar 1 and Ar 2 Each of them may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzosilyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0068] For example, Ar 1 and Ar 2 Each 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 dibenzosilyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0069] For example, L 1 and L 2 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

[0070] For example, *-L 1 -Ar 1 and *-L 2 -Ar 2 The substituents may be each independently selected from Group I.

[0071] [Group I]

[0072]

[0073] In group I, * is the connection point,

[0074] Substituents may be unsubstituted or substituted.

[0075] When substituted, the substituent may be deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano.

[0076] For example, the compound for an organic photoelectric device represented by Chemical Formula 1 may be one of the compounds selected from Group 1, but is not limited thereto.

[0077] [Group 1]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] Here, D is deuterium.

[0084] For example, the above-mentioned compound for an organic photoelectric device may be used as a host, and may be mixed with a known host material.

[0085] The compound for an organic photoelectric device may be a composition further comprising a dopant.

[0086] 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.

[0087] A dopant is a material mixed in a small amount with a compound or composition for an organic photoelectric device to cause light emission, and generally may be a material that emits light by multiple excitations to a triplet state or more, such as a metal complex. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types thereof may be used.

[0088] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0089] [Chemical formula Z]

[0090] L 4 MX

[0091] In the chemical formula Z, M is a metal and L 4and X are the same as or different from each other and are ligands that form a coordination compound with M.

[0092] 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 4 and X may be, for example, a bidentate ligand.

[0093] By L 4 Examples of the ligand represented by and X may be selected from the chemical formulae of Group A, but are not limited thereto.

[0094] [Group A]

[0095]

[0096] In Group A,

[0097] 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

[0098] 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.

[0099] As an example, it may include a dopant represented by Chemical Formula I.

[0100] [Chemical Formula I]

[0101]

[0102] In Chemical Formula I,

[0103] R 101 To R 116 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R134 ,

[0104] R 132 To R 134 are each independently C1 to C6 alkyl,

[0105] R 101 To R 116 At least one of them is a functional group represented by Chemical Formula I-1,

[0106] L 100 is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone pair of electrons of a carbon or heteroatom, and

[0107] n1 and n2 are each independently any one of integers from 0 to 3, and n1+n2 is any one of integers from 1 to 3,

[0108] [Chemical Formula I-1]

[0109]

[0110] Wherein, in Chemical Formula I-1,

[0111] 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 ,as well as

[0112] * indicates a moiety attached to a carbon atom.

[0113] As an example, a dopant represented by Chemical Formula Z-1 may be included.

[0114] [Chemical formula Z-1]

[0115]

[0116] 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;

[0117] R A , R B , R C , and R D each independently represents mono-, di-, tri-, or tetra-substituted, or unsubstituted;

[0118] L B , L C and L DEach is independently selected from direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' and combinations thereof;

[0119] When nA is 1, L E is selected from the group consisting of direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' and combinations thereof; when nA is 0, L E does not exist; and

[0120] R A , R B , R C , R D R, R and R' are each independently selected from hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; any adjacent R A , R B , R C , R D , R and R' are optionally linked to each other to provide a ring; X B , X C , X D and X 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.

[0121] The dopant according to one embodiment may be a platinum complex, and may be represented, for example, by Chemical Formula II.

[0122] [Chemical Formula II]

[0123]

[0124] In Chemical Formula II,

[0125] X 100 Selected from O, S and NR 131 ,

[0126] 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 ,

[0127] R 132 To R 134 are each independently C1 to C6 alkyl, and

[0128] R 117 To R 131 At least one of them is -SiR 132 R 133 R 134 or tert-butyl.

[0129] Hereinafter, an organic photoelectric device including the above-mentioned compound for an organic photoelectric device is described.

[0130] The organic photoelectric device may be any device that converts electrical energy into light energy, or vice versa, without particular limitation, and may be, for example, an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0131] Herein, an organic light emitting diode as one example of an organic photoelectric device is described with reference to the accompanying drawings.

[0132] Figure 1 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0133] Reference Figure 1 , an organic light emitting diode 100 according to an 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 .

[0134] 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), etc.; 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.

[0135] 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; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0136] The organic layer 105 may include the above-described compound for an organic photoelectric device.

[0137] The organic layer 105 may include a light emitting layer 130 , and the light emitting layer 130 may include the above-described compound for an organic photoelectric device.

[0138] For example, the composition for an organic photoelectric device further including a dopant may be a red light emitting composition.

[0139] For example, the light emitting layer 130 may include the above-described compounds for an organic photoelectric device as each phosphorescent host.

[0140] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0141] The charge transport region may be, for example, a hole transport region 140 .

[0142] The hole transport region 140 may further increase hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 , and block electrons.

[0143] Specifically, the hole transport zone 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 group B compounds may be included in at least one of the hole transport layer and the hole transport auxiliary layer.

[0144] [Group B]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] In the hole transporting region 140, in addition to this compound, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc., and compounds similar thereto can be used.

[0152] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0153] The electron transport region 150 may further increase electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0154] 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 group C compounds may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[0155] [Group C]

[0156]

[0157]

[0158]

[0159]

[0160] One embodiment may be an organic light emitting diode including a light emitting layer as an organic layer.

[0161] Another embodiment may provide an organic light emitting diode including a light emitting layer and a hole transport region as an organic layer.

[0162] Another embodiment may provide an organic light emitting diode including a light emitting layer and an electron transport region as an organic layer.

[0163] like Figure 1 As shown, in addition to the light emitting layer 130 as the organic layer 105 , the organic light emitting diode according to the embodiment of the present invention may further include a hole transport region 140 and an electron transport region 150 .

[0164] On the other hand, the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), and the like in addition to the light emitting layer as the above-mentioned organic layer.

[0165] The organic light emitting diode 100 may be manufactured by forming an anode or a 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 an anode thereon.

[0166] The organic light emitting diode may be applied to an organic light emitting display device.

[0167] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the scope of the present invention is not limited thereto.

[0168] Hereinafter, unless otherwise specifically noted, 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.

[0169] (Preparation of compounds for organic optoelectronic devices)

[0170] The compound presented as a more specific example of the compound of the present invention is synthesized by the following steps.

[0171] Synthesis Example 1: Synthesis of Intermediate I-1

[0172]

[0173] In a nitrogen environment, 9H-carbazole (100 g, 598 mmol) purchased from Tokyo Chemical Industry Co., Ltd. was dissolved in 0.1 L of dimethylformamide (DMF), and sodium hydride (28.7 g, 1,196 mmol) was added thereto, and then stirred at 0°C. After 1 hour, 1-bromo-3-fluoro-2-nitrobenzene (132 g, 598 mmol) purchased from Tokyo Chemical Industry Co., Ltd. was added thereto, and then stirred for 1 hour. When the reaction was completed, water was added to the reaction solution at 0°C, and then extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified by rapid column chromatography to obtain intermediate I-1 (182 g, 83%).

[0174] HRMS (70 eV, EI+): m / z calculated for C18H11BrN2O2: 366.0004, measured: 366.

[0175] Elemental analysis: C, 59%; H, 3%

[0176] Synthesis Example 2: Synthesis of Intermediate I-2

[0177]

[0178] In a nitrogen environment, intermediate I-1 (182g, 496mmol) was dissolved in 0.8L of tetrahydrofuran (THF), 2-fluorophenylboric acid (76.3g, 545mmol) and tetrakis (triphenylphosphine) palladium (11.5g, 9.92mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were added thereto, and then stirred. Subsequently, potassium carbonate (171g, 1,240mmol) saturated in water was added thereto, and then heated to reflux at 80°C for 24 hours. When the reaction was complete, water was added to the reaction solution, which was then extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained was separated and purified by rapid column chromatography to obtain intermediate I-2 (95g, 50%).

[0179] HRMS (70 eV, EI+): m / z calculated for C24H15FN2O2: 382.1118, measured: 382.

[0180] Elemental analysis: C, 75%; H, 4%

[0181] Synthesis Example 3: Synthesis of Intermediate I-3

[0182]

[0183] In a nitrogen environment, intermediate I-2 (95g, 248mmol) was dissolved in 0.1L of dichlorobenzene (DCB), and triphenylphosphine (195g, 745mmol) was added thereto, and then heated to reflux at 200°C for 7 days. When the reaction was complete, water was added to the reaction solution, then extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained was separated and purified by rapid column chromatography to obtain intermediate I-3 (36g, 41%).

[0184] HRMS (70 eV, EI+): m / z calculated for C24H15FN2: 350.1219, measured: 350.

[0185] Elemental analysis: C, 82%; H, 4%

[0186] Synthesis Example 4: Synthesis of Intermediate I-4

[0187]

[0188] In a nitrogen environment, intermediate I-3 (36g, 94.1mmol) was dissolved in 0.3L of N-methyl-2-pyrrolidone (NMP), and 9H-carbazole (31.5g, 188mmol) and cesium carbonate (61.3g, 188mmol) (Mw: 325.82g / mol, 2 equivalents) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were added thereto, and then heated under reflux for 2 days. When the reaction was complete, after removing the solvent by distillation, water was added to the reaction solution, and then extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained was separated and purified by rapid column chromatography to obtain intermediate I-4 (26g, 56%).

[0189] HRMS (70 eV, EI+): m / z calculated for C36H23N3: 497.1892, measured: 497.

[0190] Elemental analysis: C, 87%; H, 5%

[0191] Synthesis Example 5: Synthesis of Compound 1

[0192]

[0193] Compound 1 (13.2 g, 90%) was obtained in the same manner as in Synthesis Example 1, except that Intermediate I-4 (10 g, 20.1 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (6.46 g, 24.1 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0194] HRMS (70 eV, EI+): m / z calculated for C51H32N6: 728.2688, measured: 728.

[0195] Elemental analysis: C, 84%; H, 4%

[0196] Synthesis Example 6: Synthesis of Compound 2

[0197]

[0198] Compound 2 (17.7 g, 88%) was obtained in the same manner as in Synthesis Example 1, except that Intermediate I-4 (10 g, 20.1 mmol) and 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (8.29 g, 24.1 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0199] HRMS (70 eV, EI+): m / z calculated for C57H36N6: 804.3001, measured: 804.

[0200] Elemental analysis: C, 85%; H, 5%

[0201] Synthesis Example 7: Synthesis of Compound 8

[0202]

[0203] Compound 8 (15.3 g, 93%) was obtained in the same manner as in Synthesis Example 1, except that Intermediate I-4 (10 g, 20.1 mmol) and 2-chloro-4-(dibenzofuran-3-yl)-6-phenyl-1,3,5-triazine (8.62 g, 24.1 mmol) purchased from P&H Tech Co., Ltd. (http: / / www.phtech.co.kr / ) were used.

[0204] HRMS (70 eV, EI+): m / z calculated for C57H34N6O: 818.2794, measured: 818.

[0205] Elemental analysis: C, 84%; H, 4%

[0206] Synthesis Example 8: Synthesis of Intermediate I-5

[0207]

[0208] Intermediate I-5 (29.5 g, 60%) was obtained in the same manner as in Synthesis Example 4 except that Intermediate I-3 (30 g, 85.6 mmol) and 2-phenyl-9H-carbazole (41.7 g, 171 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0209] HRMS (70 eV, EI+): m / z calculated for C42H27N3: 573.2205, measured: 573.

[0210] Elemental analysis: C, 88%; H, 5%

[0211] Synthesis Example 9: Synthesis of Compound 17

[0212]

[0213] Compound 17 (13.0 g, 85%) was obtained in the same manner as in Synthesis Example 5, except that Intermediate I-5 (10 g, 17.4 mmol) and 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (7.19 g, 20.9 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0214] HRMS (70 eV, EI+): m / z calculated for C63H40N6: 880.3314, measured: 880.

[0215] Elemental analysis: C, 86%; H, 5%

[0216] Synthesis Example 10: Synthesis of Intermediate I-6

[0217]

[0218] Intermediate I-6 (24.8 g, 53%) was obtained in the same manner as in Synthesis Example 4 except that Intermediate I-3 (30 g, 85.6 mmol) and 11H-benzo[a]carbazole (37.2 g, 171 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0219] HRMS (70 eV, EI+): m / z calculated for C40H25N3: 547.2048, found: 547.

[0220] Elemental analysis: C, 88%; H, 5%

[0221] Synthesis Example 11: Synthesis of Compound 25

[0222]

[0223] Compound 25 (13.9 g, 89%) was obtained in the same manner as in Synthesis Example 1, except that Intermediate I-6 (10 g, 18.3 mmol) and 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (7.53 g, 21.9 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0224] HRMS (70 eV, EI+): m / z calculated for C61H38N6: 854.3158, measured: 854.

[0225] Elemental analysis: C, 86%; H, 4%

[0226] Synthesis Example 12: Synthesis of Intermediate I-7

[0227]

[0228] Intermediate I-7 (32.1 g, 91%) was obtained in the same manner as in Synthesis Example 2, except that 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (30 g, 87.3 mmol) and 2-fluorophenylboric acid (14.7 g, 105 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0229] HRMS (70 eV, EI+): m / z calculated for C27H18FN3: 403.1485, measured: 403.

[0230] Elemental analysis: C, 80%; H, 5%

[0231] Synthesis Example 13: Synthesis of Compound 36

[0232]

[0233] Compound 36 (16.8 g, 95%) was obtained in the same manner as in Synthesis Example 4, except that Intermediate I-4 (10 g, 20.1 mmol) and Intermediate I-7 (12.2 g, 30.1 mmol) were used.

[0234] HRMS (70 eV, EI+): m / z calculated for C63H40N6: 880.3314, measured: 880.

[0235] Elemental analysis: C, 86%; H, 5%

[0236] Synthesis Example 14: Synthesis of Intermediate I-8

[0237]

[0238] Intermediate I-8 (16.9 g, 62%) was obtained in the same manner as in Synthesis Example 2, except that 2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 133 mmol) and 3-cyanophenylboronic acid (13.7 g, 92.9 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0239] HRMS (70 eV, EI+): m / z calculated for C16H9ClN4: 292.0516, measured: 292.

[0240] Elemental analysis: C, 67%; H, 3%

[0241] Synthesis Example 15: Synthesis of Intermediate I-9

[0242]

[0243] Intermediate I-9 (18.3 g, 95%) was obtained in the same manner as in Synthesis Example 2 except that Intermediate I-8 (16 g, 54.7 mmol) and 2-fluorophenylboric acid (9.18 g, 65.6 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http: / / www.tcichemicals.com / ) were used.

[0244] HRMS (70 eV, EI+): m / z calculated for C22H13FN4: 352.1124, measured: 352.

[0245] Elemental analysis: C, 75%; H, 4%

[0246] Synthesis Example 16: Synthesis of Compound 69

[0247]

[0248] Compound 69 (14.0 g, 84%) was obtained in the same manner as in Synthesis Example 4, except that Intermediate I-4 (10 g, 20.1 mmol) and Intermediate I-9 (9 g, 25.5 mmol) were used.

[0249] HRMS (70 eV, EI+): m / z calculated for C58H35N7: 829.2954, measured: 829.

[0250] Elemental analysis: C, 84%; H, 4%

[0251] Synthesis Example 17: Synthesis of Main Body 1

[0252]

[0253] The main body 1 was synthesized by referring to the synthesis method of patent KR2019-0043840.

[0254] HRMS (70 eV, EI+): m / z calculated for C57H36N6: 804.3001, measured: 804.

[0255] Elemental analysis: C, 85%; H, 5%

[0256] Synthesis Example 18: Synthesis Subject 2

[0257]

[0258] The main body 2 was synthesized by referring to the synthesis method of patent KR2011-0043342.

[0259] HRMS (70 eV, EI+): m / z calculated for C51H32N6: 728.2688, measured: 728.

[0260] Elemental analysis: C, 84%; H, 4%

[0261] Synthesis Example 19: Synthesis of Body 3

[0262]

[0263] The main body 3 was synthesized by referring to the synthesis method of patent KR2020-0078254.

[0264] HRMS (70 eV, EI+): m / z calculated for C39H25N5: 563.2110, found: 563.

[0265] Elemental analysis: C, 83%; H, 4%

[0266] Synthesis Example 20: Synthesis of Intermediate I-10

[0267]

[0268] Intermediate I-10 (21.4 g, 50%) was obtained in the same manner as in Synthesis Example 4 except that Intermediate I-3 (30 g, 85.6 mmol) and diphenylamine (28.9 g, 171 mmol) purchased from Sigma aldrich (http: / / www.sigmaaldrich.com / ) were used.

[0269] HRMS (70 eV, EI+): m / z calculated for C36H25N3: 499.2048, measured: 499.

[0270] Elemental analysis: C, 87%; H, 5%

[0271] Synthesis Example 21: Synthesis of Compound 4

[0272]

[0273] The subject 4 (13.4 g, 83%) was obtained in the same manner as in Synthesis Example 1, except that Intermediate I-10 (10 g, 20 mmol) and 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (8.26 g, 24.0 mmol) purchased from Tokyo Chemical Industry were used.

[0274] HRMS (70 eV, EI+): m / z calculated for C57H38N6: 806.3158, measured: 806.

[0275] Elemental analysis: C, 85%; H, 5%

[0276] Manufacturing of organic light-emitting diodes (green)

[0277] Example 1

[0278] Organic light-emitting diodes were fabricated using compound 1 as the host and Ir(PPy)3 as the dopant. As the anode, ITO was used with a thickness of And as the cathode, aluminum (Al) is used with a thickness of Specifically, when explaining the manufacturing method of the organic light emitting diode, it will have 15Ω / cm 2 The ITO glass substrate of the sheet resistance was cut into a size of 50 mm × 50 mm × 0.7 mm, and each was cleaned in acetone, isopropyl alcohol and pure water for 15 minutes by ultrasonic cleaning and 30 minutes by UV ozone cleaning, and the resultant was used as an anode. -7 Pa and a deposition rate of 0.1 to 0.3 nm / s, N4,N4'-di(naphthalene-1-yl)-N4,N4'-diphenylbiphenyl-4,4'-diamine (NPB) was deposited on the substrate to form Subsequently, under the same vacuum deposition conditions, compound 1 was used to form a hole transport layer having A light-emitting layer with a thickness of 100 wt % was prepared, and at this time, Ir(PPy)3 as a phosphorescent dopant was simultaneously deposited. At this time, by controlling the deposition rate of the phosphorescent dopant, when the total amount of the light-emitting layer was 100 wt %, the phosphorescent dopant was deposited so that the compounding amount was 7 wt %. Under the same vacuum deposition conditions, bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminum (BAlq) was deposited on the light-emitting layer to form a Then, Alq3 was deposited under the same vacuum deposition conditions to form a hole blocking layer with a thickness of The electron transport layer is deposited on the electron transport layer. and Al as cathode to make organic light emitting diodes.

[0279] The organic light emitting diode has a structure of ITO / NPB (80 nm) / EML (Compound 1 (93 wt %) + Ir(PPy)3 (7 wt %), 30 nm) / BAlq (5 nm) / Alq3 (20 nm) / LiF (1 nm) / Al (100 nm).

[0280] The structures of NPB, BAlq, CBP and Ir(PPy)3 used to make organic light-emitting diodes are as follows.

[0281]

[0282] Examples 2 to 7 and Comparative Examples 1 to 5

[0283] An organic light emitting diode was manufactured in the same manner as in Example 1, except that the composition shown in Table 1 was changed instead of Compound 1.

[0284] evaluate

[0285] Current density variation according to voltage, luminance variation, and light emitting efficiency of the organic light emitting diodes according to Examples 1 to 7 and Comparative Examples 1 to 5 were measured.

[0286] The specific measurement method is as follows, and the results are shown in Table 1.

[0287] (1) Measurement of current density changes according to voltage changes

[0288] While increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), a current value flowing in a unit device of the fabricated organic light emitting diode was measured, and the measured current value was divided by the area to provide a result.

[0289] (2) Measurement of brightness changes based on voltage changes

[0290] While the voltage of the organic light emitting diode was increased from 0V to 10V, the luminance was measured by using a luminance meter (Minolta Cs-1000A).

[0291] (3) Measurement of luminous efficiency

[0292] Using the luminance and current density and voltage from items (1) and (2), calculate the same current density (10 mA / cm 2 )'s luminous efficiency (cd / A).

[0293] (4) Lifespan measurement

[0294] To be maintained at 5000cd / m 2 Brightness (cd / m 2 ) and the time when the current efficiency (cd / A) drops to 90% to obtain the results.

[0295] (5) Driving voltage

[0296] The current-voltage meter (Keithley 2400) was used to measure the current of each diode at 15 mA / cm 2 The driving voltage is set to 0.

[0297] (Table 1)

[0298]

[0299] CBP: 4,4'-bis(9-carbazol-9-yl)biphenyl

[0300] Referring to Table 1, the organic light emitting diodes according to Examples 1 to 7 exhibited low driving voltage, high efficiency, and long lifespan, compared with the organic light emitting diodes according to Comparative Examples 1 to 5.

[0301] While the invention has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic optoelectronic device, the compound being represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, Z 1 To Z 3 All are N, L 1 To L 3 are each independently a single bond or a substituted or unsubstituted phenylene group, Ar 1 and Ar 2 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group, R 1 To R 10 are each independently hydrogen, deuterium or substituted or unsubstituted phenyl, m1 to m4 are each independently one of integers from 1 to 4, and "Substituted" means that at least one hydrogen of the substituent is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano.

2. The compound for an organic optoelectronic device according to claim 1, wherein L 3 It is a substituted or unsubstituted o-phenylene group.

3. The compound for an organic optoelectronic device according to claim 1, wherein *-L 1 -Ar 1 and *-L 2 -Ar 2 Each is independently selected from one of the substituents listed in Group I: [Group I] in, In Group I, * is the connection point.

4. The compound for an organic optoelectronic device according to claim 1, wherein The compound is one selected from the compounds listed in Group 1: [Group 1] in, D is for deuterium.

5. 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 a light-emitting layer, and The light-emitting layer comprises the compound for an organic photoelectric device according to any one of claims 1 to 4.

6. The organic optoelectronic device according to claim 5, wherein The compound for an organic photoelectric device is included as a host of the light-emitting layer. 7 . A display device comprising the organic optoelectronic device according to claim 5 .

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