Organic optoelectronic devices and display devices

Abstract

An organic optoelectronic device and a display device are disclosed, wherein the display device includes an organic optoelectronic device. The organic optoelectronic device includes an anode and a cathode facing each other, a light-emitting layer between the anode and the cathode, a hole transport layer between the anode and the light-emitting layer, and a hole transport auxiliary layer between the light-emitting layer and the hole transport layer, wherein the light-emitting layer includes a composition containing a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2 and a second compound represented by Chemical Formula 3, and the hole transport auxiliary layer includes a third compound represented by Chemical Formula 4. The details of Chemical Formulas 1 to 4 are the same as described in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0146076 filed in the Korean Intellectual Property Office on November 14, 2019, the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] Organic optoelectronics are devices that convert electrical energy into light and vice versa.

[0005] Organic optoelectronic devices can be classified according to their driving principles as follows: one is a photoelectric 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; the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0006] Examples of organic optoelectronic devices include organic photovoltaic devices, organic light emitting diodes, organic solar cells, and organic photoconductors.

[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 an organic optoelectronic device having high efficiency and long lifespan.

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

[0010] According to one embodiment, an organic optoelectronic device includes an anode and a cathode facing each other, a light-emitting layer between the anode and the cathode, a hole transport layer between the anode and the light-emitting layer, and a hole transport auxiliary layer between the light-emitting layer and the hole transport layer, wherein the light-emitting layer includes a composition containing a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2 and a second compound represented by Chemical Formula 3, and the hole transport auxiliary layer includes a third compound represented by Chemical Formula 4.

[0011]

[0012] In Chemical Formulas 1 and 2,

[0013] Ar 1 To Ar 3 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0014] Two adjacent ones of a1* to a4* of Chemical Formula 1 are connected to b1* and b2* of Chemical Formula 2, respectively, and the remaining two of a1* to a4* not connected to b1* and b2* are independently CL a -R a ,

[0015] L a and L 1 To L 4 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0016] R a and R 1 To R 4 are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof;

[0017] [Chemical formula 3]

[0018]

[0019] Among them, in chemical formula 3,

[0020] Ar 4 and Ar 5 are independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

[0021] L 5 and L 6 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0022] R 5 To R 10 are independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0023] n is an integer from 0 to 2;

[0024] [Chemical formula 4]

[0025]

[0026] Among them, in chemical formula 4,

[0027] L 7 and L 8 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0028] R 11 To R 14 are independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0029] Ar 6 To Ar 9 are independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

[0030] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0031] Organic optoelectronic devices with high efficiency and long lifetime can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a schematic cross-sectional view of an organic light emitting diode according to one embodiment.

[0033] <Description of symbols>

[0034] 300: Organic light-emitting diode

[0035] 110: Anode

[0036] 120: cathode

[0037] 130: Luminous layer

[0038] 141: Hole transport layer

[0039] 142: Hole transport auxiliary layer

[0040] 105: Organic layer DETAILED DESCRIPTION

[0041] 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.

[0042] In the present specification, when no definition is otherwise provided, "substituted" means that at least one hydrogen of the substituent or the compound is replaced by deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl (silyl), C1 to C30 alkyl, C1 to C10 alkylsilyl (alkylsilyl), C6 to C30 arylsilyl (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.

[0043] In one example of the present invention, "substituted" means that at least one hydrogen of the 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 or C2 to C30 heteroaryl. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl or C2 to C30 heteroaryl. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, pyridyl, quinolyl, isoquinolyl, dibenzofuranyl, dibenzothienyl or carbazolyl. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl or dibenzothienyl. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, naphthyl, triphenyl, dibenzofuranyl or dibenzothienyl.

[0044] In the present specification, when a definition is not otherwise provided, "hetero" means including one to three hetero atoms selected from N, O, S, P and Si in one functional group and the rest are carbon.

[0045] In the present specification, "aryl group" refers to a group including at least one hydrocarbon aromatic part, and may include a group in which all elements of the hydrocarbon aromatic part have p-orbitals forming a conjugation, such as phenyl, naphthyl, etc., a group in which two or more hydrocarbon aromatic parts can be linked by a σ bond, such as biphenyl, terphenyl, quaterphenyl, etc., and a group in which two or more hydrocarbon aromatic parts are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl, etc.

[0046] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0047] In this specification, "heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si in place of carbon (C) in a cyclic compound, such as an aryl group, a cycloalkyl group, a condensed ring thereof, or a combination thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.

[0048] 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 may be fused. When the heteroaryl is a fused ring, each ring may include 1 to 3 heteroatoms.

[0049] 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 naphthacenyl 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 (triphenylene group), a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0050] 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 benzothiophenyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, or a combination thereof, but are not limited thereto.

[0051] In this specification, hole characteristics refer to the ability to give 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.

[0052] In addition, the electronic property refers 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 the conductive property according to the lowest unoccupied molecular orbital (LUMO) energy level.

[0053] Hereinafter, an organic optoelectronic device according to an embodiment is described.

[0054] The organic optoelectronic 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 photoelectric device, an organic light emitting diode, an organic solar cell, an organic photoconductor, and the like.

[0055] Herein, an organic light emitting diode is described as an example of an organic optoelectronic device, but the present invention is not limited thereto and can be applied to other organic optoelectronic devices in the same manner.

[0056] In the accompanying drawings, the thickness of layers, films, plates, regions, etc., is exaggerated for clarity. The same reference numerals denote the same elements throughout the specification. It should be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or there can be intermediate elements. On the contrary, when an element is referred to as being "directly on" another element, there are no intermediate elements.

[0057] Figure 1 is a schematic cross-sectional view of an organic light emitting diode according to an embodiment.

[0058] Reference Figure 1 The organic light emitting diode 300 according to the embodiment includes an anode 110 and a cathode 120 facing each other, and an organic layer 105 between the anode 110 and the cathode 120 , wherein the organic layer 105 includes a light emitting layer 130 , a hole transport auxiliary layer 142 , and a hole transport layer 141 .

[0059] The anode 110 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 110 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or the like, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0060] The cathode 120 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 120 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc., or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0061] The light emitting layer 130 may be disposed between the anode 110 and the cathode 120 and include a plurality of hosts and at least one type of dopant.

[0062] The light emitting layer 130 may include a first compound having relatively strong electron characteristics and a second compound having relatively strong hole characteristics as a host, and the host may be a composition including the first compound and the second compound.

[0063] The hole transport auxiliary layer 142 may be disposed between the light emitting layer 130 and the hole transport layer 141 to be described later, and may be disposed in contact with the light emitting layer 130, thereby precisely controlling the mobility of holes at the interface between the light emitting layer 130 and the hole transport layer 141. The hole transport auxiliary layer 142 may include a third compound, and may include a plurality of layers.

[0064] The first compound may be a compound having relatively strong electronic properties and may be formed by chemical

[0065] The combination of Formula 1 and Formula 2 represents:

[0066]

[0067] In Chemical Formulas 1 and 2,

[0068] Ar 1 To Ar 3 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0069] Two adjacent ones of a1* to a4* of Chemical Formula 1 are connected to b1* and b2* of Chemical Formula 2, respectively, and the remaining two of a1* to a4* not connected to b1* and b2* are independently CL a -R a ,

[0070] L a and L 1 To L 4 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0071] R a and R 1 To R 4 are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof.

[0072] The second compound may be a compound having relatively strong hole characteristics, and may be represented by Chemical Formula 3.

[0073] [Chemical formula 3]

[0074]

[0075] In chemical formula 3,

[0076] Ar 4 and Ar5 are independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

[0077] L 5 and L 6 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0078] R 5 To R 10 are independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0079] n is an integer from 0 to 2.

[0080] The third compound may be a compound included in the hole transport auxiliary layer 142 and accurately controls the mobility of holes at the interface between the light emitting layer 130 and the hole transport layer 141 , and may be represented by Chemical Formula 4.

[0081] [Chemical formula 4]

[0082]

[0083] In chemical formula 4,

[0084] L 7 and L 8 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0085] R 11 To R 14 are independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0086] Ar 6 To Ar 9 are independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

[0087] The first compound is a compound that can accept both holes and electrons when an electric field is applied, that is, a compound having bipolar properties. Specifically, since the indole carbazole core is substituted with triazine, the glass transition temperature relative to the molecular weight can be increased to ensure heat resistance. In addition, by combining a bicarbazole (bicarbazole) compound as a second host, holes and electrons in the device can be balanced due to the first host material having fast and stable electron transport properties and the second host material having fast and stable hole transport properties.

[0088] In addition, by applying a compound such as the third compound to the hole transport auxiliary layer, holes or electrons can be prevented from accumulating at the interface between the hole transport layer and the light emitting layer and the charge balance can be increased. Therefore, the driving voltage and life characteristics of the organic optoelectronic device can be greatly improved.

[0089] For example, the first compound may be represented by any one of Chemical Formula 1A to Chemical Formula 1E.

[0090]

[0091]

[0092] In Chemical Formulae 1A to 1E, Ar 1 To Ar 3 , L a , L 1 To L 4 , R a and R 1 To R 4 Same as above.

[0093] As a specific example, the first compound may be represented by Chemical Formula 1B.

[0094] For example, Ar in formula 1 1 and Ar 2 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 fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,

[0095] L in chemical formula 1 1 and L 2 may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,

[0096] L in chemical formula 1 3 may be a single bond or a substituted or unsubstituted phenylene group, and

[0097] R in Formula 11 and R 2 and may independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0098] In addition, Ar in Formula 2 3 may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,

[0099] L in chemical formula 2 4 may be a single bond or a substituted or unsubstituted phenylene group, and

[0100] R in chemical formula 2 3 and R 4 and may independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0101] For example, Ar in formula 1 1 and Ar 2 may independently be one of the substituents in Group I-1, and

[0102] Ar in chemical formula 2 3 It may be one of the substituents in Group I-2.

[0103] [Group I-1]

[0104]

[0105] [Group I-2]

[0106]

[0107] According to an exemplary embodiment of the present invention, Ar of Chemical Formula 1 1 and Ar 2 may independently be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group,

[0108] L in chemical formula 1 1 and L 2 may independently be a single bond, unsubstituted m-phenylene or unsubstituted p-phenylene,

[0109] L in chemical formula 1 3 can be a single bond, and

[0110] R in Formula 1 1 and R 2 It may be hydrogen or phenyl.

[0111] In addition, Ar in Formula 2 3 may independently be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group,

[0112] L in chemical formula 1 4 may be a single bond or unsubstituted m-phenylene or unsubstituted p-phenylene, and

[0113] R in Formula 1 3 and R 4 may independently be hydrogen or phenyl.

[0114] The first compound may be, for example, one of the compounds selected from Group 1, but is not limited thereto.

[0115] [Group 1]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] By including the second compound together with the first compound, the balance between holes and electrons can be increased, and thus the driving or lifespan characteristics of a device including the compound can be greatly improved.

[0125] For example, Chemical Formula 3 can be represented by Chemical Formula 3-1.

[0126] [Chemical formula 3-1]

[0127]

[0128] In chemical formula 3-1, Ar 4 ,Ar 5 , L 5 , L 6 and R 5 To R 10 Same as above.

[0129] In one embodiment, the second compound may be represented by Chemical Formula 3-1, wherein R5 To R 10 can be all hydrogen, and *-L 5 -Ar 4 and *-L 6 -Ar 5 may independently be one of the substituents of Group II.

[0130] [Group II]

[0131]

[0132] In Group II, * is the connection point.

[0133] For example, Ar 4 and Ar 5 The groups may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl or substituted or unsubstituted terphenyl.

[0134] In addition, L 5 and L 6 Each of the phenylene groups may independently be a single bond or a substituted or unsubstituted phenylene group.

[0135] In addition, R 5 To R 10 May independently be hydrogen or C6 aryl.

[0136] The second compound may be, for example, one of compounds selected from the following Group 2, but is not limited thereto.

[0137] [Group 2]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] The first compound and the second compound may be included, for example, in a weight ratio of 1:99 to 99:1. Within the above range, bipolar characteristics may be achieved by matching an appropriate weight ratio using the electron transport capability of the first compound and the hole transport capability of the second compound to improve efficiency and lifespan. Within this range, for example, they may be included in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, about 20:80 to 70:30, about 20:80 to 60:40. For example, they may be included in a weight ratio of 30:70 to 50:50, for example, 30:70.

[0144] The light emitting layer may further include one or more compounds in addition to the above-mentioned host.

[0145] The light emitting layer may further include a dopant. The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, such as a red phosphorescent dopant.

[0146] The dopant is a material mixed with the above-mentioned host in a small amount to cause luminescence, and is generally a material such as a metal complex, which emits light by multiple excitation 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.

[0147] Examples of dopants may be phosphorescent dopants and examples of phosphorescent dopants may be organic metal compounds 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 chemical formula Z, but is not limited thereto.

[0148] [Chemical formula Z]

[0149] L 11 MX

[0150] In the chemical formula Z, M is a metal, L is 11 and X may be the same as or different from X and is a ligand to form a complex with M.

[0151] 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 11 and X may be, for example, a bidentate ligand.

[0152] The hole transport auxiliary layer 142 may include a third compound.

[0153] The third compound may be a compound having a high HOMO energy level and may have good hole injection characteristics. Therefore, the third compound is applied to the hole transport auxiliary layer 142 to effectively increase the mobility of holes at the interface between the light emitting layer 130 and the hole transport layer 141, thereby effectively reducing the driving voltage of the organic optoelectronic device.

[0154] For example, L in formula 4 7 and L 8 may independently be substituted or unsubstituted phenylene,

[0155] Ar 6 To Ar 9may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or a combination thereof, and

[0156] R 11 To R 14 The alkyl radicals may independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl radicals, substituted or unsubstituted C6 to C12 aryl radicals, or a combination thereof.

[0157] For example, the third compound may be represented by Chemical Formula 4-1.

[0158] [Chemical formula 4-1]

[0159]

[0160] In chemical formula 4-1, L 7 , L 8 , R 11 To R 14 and Ar 6 To Ar 9 Same as described above,

[0161] X is O, S or CR b R c ,as well as

[0162] R b , R c and R 15 To R 17 and independently are hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0163] As a more specific example, L in Chemical Formula 4-1 7 and L 8 may independently be m-phenylene or p-phenylene,

[0164] Ar 6 It can be phenyl,

[0165] Ar 7 and Ar 8 may independently be substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothienyl, and

[0166] R 11 To R 17 may independently be hydrogen or phenyl.

[0167] The third compound may be, for example, one of the compounds selected from Group 3, but is not limited thereto.

[0168] [Group 3]

[0169]

[0170]

[0171]

[0172]

[0173] In a more specific embodiment, the first compound may be represented by Chemical Formula 1B, the second compound may be represented by Chemical Formula 3-1, and the third compound may be represented by Chemical Formula 4-1.

[0174] In this case, Ar of Formula 1B 1 and Ar 3 may independently be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group,

[0175] L 1 and L 2 may independently be a single bond or a substituted or unsubstituted phenylene group,

[0176] L a , L 3 and L 4 can be a single key, and

[0177] R a , R 1 To R 4 Each may be hydrogen.

[0178] In addition, Ar in Chemical Formula 3-1 4 and Ar 5 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted fluorenyl group,

[0179] L 5 and L 6 may independently be a single bond or a substituted or unsubstituted phenylene group, and

[0180] R 5 To R 10 Each may be hydrogen.

[0181] In addition, X in Chemical Formula 4-1 may be O, S or CR b R c ,

[0182] Ar 6may be substituted or unsubstituted phenyl,

[0183] Ar 7 and Ar 8 may independently be substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothienyl,

[0184] L 7 and L 8 may independently be substituted or unsubstituted phenylene,

[0185] R b and R c may independently be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, and

[0186] R 11 To R 17 Each may be hydrogen.

[0187] The hole transport layer 141 may be disposed between the anode 110 and the light emitting layer 130 and may facilitate hole transport from the anode 110 to the light emitting layer 130. For example, the hole transport layer 141 may include a material having a HOMO energy level between the work function of the conductor constituting the anode 110 and the HOMO energy level of the material constituting the light emitting layer 130.

[0188] The hole transport layer 141 may include, for example, an amine derivative.

[0189] The hole transport layer 141 may include, for example, a compound represented by Chemical Formula 5, but is not limited thereto.

[0190] [Chemical formula 5]

[0191]

[0192] In Chemical Formula 5,

[0193] Ar 10 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0194] R 18 To R 23 are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof,

[0195] R 18 and R 19 exist independently or combine with each other to form a ring,

[0196] R20 and R 21 exist independently or combine with each other to form a ring,

[0197] R 22 and R 23 are independently substituted or unsubstituted C6 to C30 aryl or substituted or unsubstituted C2 to C30 heterocyclic, and

[0198] L 9 To L 12 and R is independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

[0199] For example, Ar 10 It may be a substituted or unsubstituted C6 to C30 aryl group, for example, Ar 10 It may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

[0200] For example, R 18 To R 23 The groups may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted bifluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or a combination thereof.

[0201] The compound represented by Chemical Formula 5 may be, for example, one of the compounds of Group 4, but is not limited thereto.

[0202] [Group 4]

[0203]

[0204]

[0205] In addition to the above-mentioned light emitting layer 130, hole transport auxiliary layer 142 and hole transport layer 141, the organic layer 105 may further include a hole injection layer, an electron blocking layer, an electron transport layer, an electron injection layer and / or a hole blocking layer (not shown).

[0206] The organic light emitting diode 300 may be manufactured by forming an anode and a cathode on a substrate, forming an organic layer using a dry film forming method such as evaporation, sputtering, plasma plating, and ion plating or a solution process, and forming a cathode or an anode thereon.

[0207] The organic optoelectronic device can be applied to a display device. For example, the organic light emitting diode can be applied to an organic light emitting diode (OLED) display.

[0208] 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.

[0209] (Synthesis of the First Compound)

[0210] Synthesis Example 1: Synthesis of Compound B-12

[0211] a) Synthesis of intermediate M-2

[0212] [Reaction Scheme 1]

[0213]

[0214] 11,12-dihydroindole [2,3-a] carbazole (78.35 g, 305.69 mmol, CAS No. 60511-85-5), 3-bromobiphenyl (59.38 g, 254.74 mmol), NaOt-Bu (26.93 g, 280.22 mmol), Pd2(dba)3 (7 g, 7.64 mmol) were suspended in 1,400 ml of toluene, and then P(t-Bu)3 (3.64 ml, 15.28 mmol) was added, and the mixture was stirred under reflux for 12 hours. Distilled water was added to the reaction solution, and the mixture was separated. The obtained product was purified by silica gel column to obtain intermediate M-2 (68.7 g, 57%).

[0215] b) Synthesis of intermediate M-3

[0216] [Reaction Scheme 2]

[0217]

[0218] After 2,4-dichloro-6-phenyl-1,3,5-triazine (74.50 g, 329.56 mmol) and 4-biphenylboronic acid (55.47 g, 280.12 mmol) were dissolved in a mixed solution of 0.7 L tetrahydrofuran (THF) and distilled water (3:1), sodium tert-butoxide (68.32 g, 494.34 mmol) was added and the resultant was stirred under reflux for 12 hours. The reaction solution was cooled, separated, the organic layer was collected and concentrated. The concentrated residue was purified using a silica gel column to obtain intermediate M-3 (75.9 g, 67%).

[0219] c) Synthesis of Compound B-12

[0220] [Reaction Scheme 3]

[0221]

[0222] By using Intermediate M-2 and Intermediate M-3, Compound B-12 was obtained in the same manner as in the synthesis of Intermediate M-2.

[0223] Synthesis Example 2: Synthesis of Compound B-13

[0224] a) Synthesis of intermediate M-4

[0225] [Reaction Scheme 4]

[0226]

[0227] Intermediate M-4 was synthesized in the same manner as Intermediate M-3 using 3-biphenylboronic acid.

[0228] b) Synthesis of Compound B-13

[0229] [Reaction Scheme 5]

[0230]

[0231] Compound B-13 was synthesized in the same manner as compound B-12.

[0232] Synthesis Example 3: Synthesis of Compound B-15

[0233] [Reaction Scheme 6]

[0234]

[0235] Compound B-15 was synthesized in the same manner as compound B-12.

[0236] (Synthesis of the Second Compound)

[0237] Synthesis Example 4: Synthesis of Compound H-74

[0238]

[0239] Compound H-74 was synthesized according to the known method in KR 10-1773363 B1.

[0240] LC mass M+H+=637.33

[0241] Synthesis Example 5: Synthesis of Compound H-23

[0242]

[0243] Compound H-23 was synthesized according to the known method of KR 10-1773363 B1.

[0244] LC mass M+H+=561.23

[0245] Synthesis Example 6: Synthesis of Compound H-13

[0246]

[0247] Compound H-13 was synthesized according to the known method in KR 10-1773363 B1.

[0248] (Synthesis of the Third Compound)

[0249] Synthesis Example 7: Synthesis of Compound I-53

[0250] [Reaction Scheme 7]

[0251]

[0252] Compound I-53 was synthesized according to the method known from KR 10-2019-0038303 A.

[0253] Synthesis Example 8: Synthesis of Compound I-55

[0254] [Reaction Scheme 8]

[0255]

[0256] Compound I-55 was synthesized according to the method known from KR 10-2019-0038303 A.

[0257] Synthesis Example 9: Synthesis of Compound I-50

[0258] [Reaction Scheme 9]

[0259]

[0260] Compound I-50 was synthesized according to the method known from KR 10-2019-0038303 A.

[0261] Synthesis Example 10: Synthesis of Compound I-8

[0262] [Reaction Scheme 10]

[0263]

[0264] Compound I-8 was synthesized according to the method known in KR 10-2019-0038303 A.

[0265] (Synthesis of Comparative Compounds)

[0266] Reference Synthesis Example 1: Synthesis of Comparative Compound R-1

[0267]

[0268] The comparative compound R-1 was synthesized according to the method known in KR 10-2019-0038303 A.

[0269] Reference Synthesis Example 2: Synthesis of Comparative Compound R-2

[0270]

[0271] Comparative compound R-2 was synthesized according to the method known in KR10-2018-0099436 A.

[0272] Reference Synthesis Example 3: Synthesis of Comparative Compound R-3

[0273]

[0274] Comparative compound R-3 was synthesized in the same manner as the comparative compound R-2 using the intermediate 5-phenyl-5,12-dihydroindole[3,2-a]carbazole (CAS No. 1247053-55-9).

[0275] (Manufacturing of organic light-emitting diodes)

[0276] Example 1

[0277] Wash with distilled water A glass substrate of ITO (indium tin oxide) is prepared. After washing with distilled water, the glass substrate is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and moved to a vacuum depositor. The obtained ITO transparent electrode is used as an anode, and N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazole-3-yl)biphenyl-4,4'-diamine (Compound A) is vacuum deposited on the ITO substrate to form A thick hole injection layer is formed, and 1,4,5,8,9,11-hexaazatriphenylene-hexanitrile (HATCN, compound B) is added to A thick layer was deposited on the injection layer, and then N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine) (Compound C) was deposited as The compound I-53 obtained in Synthesis Example 7 was vacuum deposited on the hole transport layer to form Subsequently, the compound B-12 obtained in Synthesis Example 1 and the compound H-74 obtained in Synthesis Example 4 were simultaneously used as the host on the hole transport auxiliary layer, and 10 wt % of Ir(ppy)3 as a dopant was doped by vacuum evaporation to form Thick light-emitting layer. Herein, compound B-12 and compound H-74 were used in a weight ratio of 3:7. Then, 8-(4-(4-(naphthalene-2-yl)-6-(naphthalene-3-yl)-1,3,5-triazine-2-yl)phenyl)quinoline (compound D) and Liq were simultaneously vacuum deposited on the light-emitting layer in a weight ratio of 1:1 to form thick electron transport layer, and Liq and Al Vacuum deposition is sequentially performed on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting diode.

[0278] The organic light-emitting diode has a structure of six organic thin film layers, specifically ITO / A / B / C / Hole transport auxiliary layer [D-53 ] / EML[B-12:H-74:Ir(ppy)3=3:7:10%] / E:Liq / Liq / Al

[0279] Example 2 to Example 5, Comparative Example 1 to Comparative Example 4

[0280] As shown in Tables 1 to 3, an organic light emitting diode was prepared in the same manner as in Example 1 by applying each compound to the hole transport auxiliary layer and the light emitting layer.

[0281] Evaluation: Improve current efficiency, improve driving voltage or improve life characteristics

[0282] The luminous efficiency and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated. The specific measurement method is as follows, and the results are shown in Tables 1 to 3.

[0283] (1) Measurement of current density changes depending on voltage changes

[0284] For the prepared organic light emitting diode, while increasing the voltage from 0 V to 10 V, the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400), and the measured current value was divided by each area to obtain a result.

[0285] (2) Measurement of brightness changes depending on voltage changes

[0286] With respect to the prepared organic light emitting diode, while increasing the voltage from 0 V to 10 V, the luminance at that time was measured using a luminance meter (Minolta Cs-1000A), and the results were obtained.

[0287] (3) Measurement of luminous efficiency

[0288] The same current density (10 mA / cm2) was calculated using the luminance and current density and voltage measured from (1) and (2). 2 )’s current efficiency (cd / A).

[0289] (4) Lifespan measurement

[0290] The T90 lifetimes of the organic light emitting diodes according to Examples 1 to 5 and Comparative Examples 1 to 5 were measured as their luminance relative to that of the organic light emitting diodes using 24,000 cd / m 2 Emitted light as initial brightness (cd / m 2 ) after initial brightness (cd / m 2 ) to 90%, and their brightness reduction over time was measured using the Polanonix lifetime measurement system.

[0291] (5) Measurement of driving voltage

[0292] An ampere-voltmeter (Keithley 2400) was used to measure the 2 Measure the driving voltage of the organic light emitting diode.

[0293] (6) Calculation of T90 life ratio (%)

[0294] In Table 1, the T90 lifespan was evaluated with reference to Comparative Example 1.

[0295] (7) Calculation of Luminous Efficiency (Luminous Efficiency) Ratio (%) In Table 2, the evaluation was performed based on the luminous efficiency of Comparative Example 2.

[0296] (8) Calculation of driving voltage ratio (%)

[0297] In Table 3, the evaluation was performed based on the driving voltage value of Comparative Example 3.

[0298] [Table 1]

[0299]

[0300] [Table 2]

[0301]

[0302] [Table 3]

[0303]

[0304] Referring to Tables 1 to 3, the driving voltage of the compound for an organic optoelectronic device according to the present invention is reduced compared with those of the compound for an organic optoelectronic device of the comparative example, and the luminous efficiency and lifespan characteristics of the compound for an organic optoelectronic device according to the present invention are improved.

[0305] While the invention has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. An organic optoelectronic device, comprising The anode and cathode face each other, a light-emitting layer between the anode and the cathode, a hole transport layer between the anode and the light-emitting layer, and a hole transport auxiliary layer between the light emitting layer and the hole transport layer, in, The light emitting layer includes a composition containing a first compound represented by Chemical Formula 1B and a second compound represented by Chemical Formula 3-1, and The hole transport auxiliary layer includes a third compound represented by Chemical Formula 4-1: [Chemical formula 1B] Wherein, in Chemical Formula 1B, Ar 1 To Ar 3 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, L 1 and L 2 are independently a single bond or a substituted or unsubstituted phenylene group, L a , L 3 and L 4 are independently single bonds, and R a and R 1 To R 4 independently hydrogen or deuterium; [Chemical formula 3-1] Among them, in chemical formula 3-1, Ar 4 and Ar 5 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl or substituted or unsubstituted fluorenyl, L 5 and L 6 are independently a single bond or a substituted or unsubstituted phenylene group, and R 5 To R 10 independently hydrogen or deuterium; [Chemical formula 4-1] Among them, in chemical formula 4-1, X is O or S, L 7 and L 8 are independently substituted or unsubstituted phenylene, R 11 To R 17 are independently hydrogen or deuterium, and Ar 6 is a substituted or unsubstituted phenyl group, Ar 7 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothienyl group, Ar 8 is a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothienyl group, and Here, "substituted" means that at least one hydrogen of the substituent is replaced by deuterium, C1 to C5 alkyl or C6 to C18 aryl.

2. The organic optoelectronic device according to claim 1, wherein: Ar 1 To Ar 3 is independently one of the substituents of Group I-1: [Group I-1] Among them, in group I-1, * is the connection point.

3. The organic optoelectronic device according to claim 1, wherein: *-L 5 -Ar 4 and *-L 6 -Ar 5 is independently one of the substituents of Group II, [Group II] Where, in Group II, * is the connection point.

4. The organic optoelectronic device according to claim 1, wherein: The light emitting layer further includes a dopant. 5 . A display device, comprising the organic optoelectronic device according to claim 1 .

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