Organic optoelectronic device and display device

Abstract

The present invention discloses an organic optoelectronic device and a display device, the organic optoelectronic device including 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 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 a combination of Chemical Formula 4 and Chemical Formula 5. The details of Chemical Formulas 1 to 5 are as defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0148811 filed in the Korean Intellectual Property Office on November 9, 2020, the entire contents of which are incorporated herein by reference Technical Field

[0003] The present application discloses an organic optoelectronic device and a display device. Background Art

[0004] An organic optoelectronic device (organic optoelectronic diode) is a device that can convert electrical energy into light and vice versa.

[0005] Organic optoelectronic devices can be roughly divided into two types according to the operating principle. One is a photoelectric device that generates electrical energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively, while 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 photoelectric devices, organic light emitting diodes, organic solar cells, and organic photoconductor drums.

[0007] Among them, organic light emitting diodes (OLEDs) have attracted attention in recent years due to an increase in demand for flat panel display devices. Organic light emitting diodes are devices that convert electrical energy into light, and the organic material between electrodes greatly affects the performance of organic light emitting diodes. Summary of the invention

[0008] One embodiment provides an organic optoelectronic device having high efficiency, long life, and low driving.

[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 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 a combination of Chemical Formula 4 and Chemical Formula 5.

[0011]

[0012] In Chemical Formula 1 and Chemical Formula 2,

[0013] L1 To L 3 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group,

[0014] 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,

[0015] X 1 is O or S,

[0016] Two adjacent ones of a1* to a4* in Chemical Formula 1 are connected to the carbon atoms * in Chemical Formula 2.

[0017] The remaining two of a1* to a4* in Chemical Formula 1 that are not connected to * in Chemical Formula 2 are each independently CR a ,and

[0018] R a and R 1 To R 8 Each is independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group;

[0019] [Chemical formula 3]

[0020]

[0021] Among them, in chemical formula 3,

[0022] Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0023] L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0024] R b and R 9 To R 18 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0025] m is an integer from 0 to 2;

[0026]

[0027] Among them, in Chemical Formula 4 and Chemical Formula 5,

[0028] Y 1 and Y 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

[0029] X 2 is O or S,

[0030] Two adjacent ones of b1* to b4* in Chemical Formula 4 are connected to the carbon atoms * in Chemical Formula 5.

[0031] The remaining two of b1* to b4* in Chemical Formula 4 that are not connected to * in Chemical Formula 5 are each independently CR c ,

[0032] R c and R 19 To R 23 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0033] L 6 To L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0034] Ar 5 and Ar 6 Each is independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0035] According to another embodiment, a display device including an organic optoelectronic device is provided.

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

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

[0038] 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.

[0039] In the present specification, 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.

[0040] 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, C2 to C30 heteroaryl or cyano. 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 cyano. 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 or cyano. In a specific example of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl or naphthyl.

[0041] In the present specification, when a definition is not otherwise provided, "hetero" means that a functional group includes one to three hetero atoms selected from N, O, S, P and Si, and the rest are carbon.

[0042] In the present specification, "aryl" refers to a group including at least one hydrocarbon aromatic portion, and all elements of the hydrocarbon aromatic portion have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic portions may be connected by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic portions may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl.

[0043] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0044] In the present 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.

[0045] For example, "heteroaryl" may refer to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl includes two or more rings, the two or more rings may be fused. When the heteroaryl is a fused ring, each ring may include one to three heteroatoms.

[0046] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysene group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted peryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof, but is not limited thereto.

[0047] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be 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, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted The invention may include substituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzofuranpyrimidinyl, substituted or unsubstituted benzothiophenepyrimidinyl, 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, or substituted or unsubstituted dibenzothiophenyl, or a combination thereof, but is not limited thereto.

[0048] 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.

[0049] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied, and due to the conductive property according to the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0050] Hereinafter, an organic optoelectronic device according to one embodiment is described.

[0051] The organic optoelectronic device may be a device that converts electrical energy into light energy and vice versa without particular limitation, and may be, for example, an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photoconductor drum.

[0052] Herein, an organic light emitting diode is described as an example of an organic optoelectronic device. However, the present invention is not limited thereto and may be equally applicable to other organic optoelectronic devices.

[0053] In the accompanying drawings, the thickness of layers, films, panels, regions, etc. is exaggerated for clarity. Throughout the specification, the same reference numerals represent the same elements. 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. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements.

[0054] Figure 1 is a schematic cross-sectional view showing an organic light emitting diode according to one embodiment.

[0055] See also Figure 1 , an organic light emitting diode 300 according to an exemplary 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 .

[0056] The anode 110 may be made of a conductor having a large work function to assist 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.

[0057] The cathode 120 may be made of a conductor having a small work function to assist 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, or the like, or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0058] The light emitting layer 130 is disposed between the anode 110 and the cathode 120 and includes various hosts and at least one type of dopant.

[0059] The light emitting layer 130 may include a first compound having a relatively strong hole characteristic and a second compound having a relatively strong electron characteristic together as a host.

[0060] The first compound is a compound having relatively strong electronic characteristics and may be represented by a combination of Chemical Formula 1 and Chemical Formula 2.

[0061]

[0062] In Chemical Formula 1 and Chemical Formula 2,

[0063] L 1 To L 3 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group,

[0064] 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,

[0065] X 1 is O or S,

[0066] Two adjacent ones of a1* to a4* in Chemical Formula 1 are connected to the carbon atoms * in Chemical Formula 2.

[0067] The remaining two of a1* to a4* in Chemical Formula 1 that are not connected to * in Chemical Formula 2 are each independently CR a ,and

[0068] R a and R 1 To R 8 Each is independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group.

[0069] The first compound has a form in which benzofuran carbazole or benzothiophene carbazole is substituted with a substituted or unsubstituted triazine, and since benzofuran or benzothiophene is fused to the carbazole part, the HOMO electron cloud is expanded to promote hole injection and transport characteristics. In the case of an organic light emitting diode including the first compound, the driving voltage of the device can be reduced due to the stability of the hole and electron balance, and the lifespan characteristics can be improved.

[0070] In particular, due to the substitution by triazine in the N-direction of the carbazole moiety, electrons and holes are well separated in the molecule, further improving the charge injection and transport properties.

[0071] On the other hand, it is included together with the second compound to exhibit good interface properties and hole and electron transport capabilities, thereby reducing the driving voltage of a device including it.

[0072] For example, L 2 and L 3Each of them may independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, or a substituted or unsubstituted carbazolylene group.

[0073] For example, L 2 and L 3 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted carbazolylene group.

[0074] For example, Ar 1 and Ar 2 Each of the groups may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted carbazolyl group.

[0075] As a specific example, Ar 1 and Ar 2 It may be unsubstituted or substituted with phenyl.

[0076] For example, Ar 1 and Ar 2 Each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted carbazolyl group.

[0077] In one embodiment, L 2 -Ar 1 and L 3 -Ar 2 Each may be independently a substituent selected from Group I.

[0078] [Group I]

[0079]

[0080] In group I, * is the connection point.

[0081] For example, L 1 It may be a single bond or a substituted or unsubstituted phenylene group.

[0082] For example, L 1 Can be a single bond.

[0083] For example, R a and R 1 To R 8 Each independently may be hydrogen, or a substituted or unsubstituted phenyl group.

[0084] As a specific example, R a , R 5, R 6 and R 8 One of the may be substituted or unsubstituted phenyl and the rest are hydrogen.

[0085] For example, R a and R 1 To R 8 Each may be hydrogen.

[0086] For example, according to the fusion position of Chemical Formula 1 and Chemical Formula 2, the first compound may be represented by one of Chemical Formula 1A to Chemical Formula 1F.

[0087]

[0088]

[0089] In Chemical Formulae 1A to 1F,

[0090] L 1 To L 3 ,Ar 1 ,Ar 2 , X 1 and R 1 To R 8 Same as above, and R a1 To R a4 Independently with R a The definition is the same.

[0091] As a specific example, the first compound may be represented by one of Chemical Formula 1A, Chemical Formula 1B, Chemical Formula 1C, Chemical Formula 1D, and Chemical Formula 1F.

[0092] As a more specific example, the first compound may be represented by Chemical Formula 1A or Chemical Formula 1C.

[0093] The first compound may be, for example, one of the compounds selected from Group 1, but is not limited thereto.

[0094] [Group 1]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] The second compound may be a compound having relatively strong hole characteristics and may be represented by Chemical Formula 3.

[0107] [Chemical formula 3]

[0108]

[0109] In chemical formula 3,

[0110] Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0111] L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0112] R b and R 9 To R 18 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0113] m is an integer from 0 to 2.

[0114] The second compound may be used together with the first compound in the light emitting layer to improve light emitting efficiency and lifespan characteristics by increasing charge mobility and increasing stability.

[0115] For example, Ar in formula 3 3 and Ar 4may be each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzothienyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted fluorenyl, or a substituted or unsubstituted pyridyl,

[0116] L in chemical formula 3 4 and L 5 may each independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,

[0117] R in chemical formula 3 9 To R 18 may each independently be hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group, and

[0118] m can be 0 or 1.

[0119] For example, “substituted” of Chemical Formula 3 means that at least one hydrogen is replaced with deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.

[0120] In one embodiment of the present invention, Chemical Formula 3 may be represented by one of Chemical Formulas 3-1 to 3-15.

[0121]

[0122]

[0123] In Chemical Formulae 3-1 to 3-15, R 9 To R 18 may be each independently hydrogen, or a substituted or unsubstituted C6 to C12 aryl group, and *-L 4 -Ar 3 and *-L 5 -Ar 4 Each may independently be one of the substituents in Group II.

[0124] [Group Ⅱ]

[0125]

[0126] In Group II, * is the connection point.

[0127] In one embodiment, Chemical Formula 3 may be represented by Chemical Formula 3-8.

[0128] In addition, *-L in Chemical Formula 3-8 4 -Ar 3 and *-L 5 -Ar 4 Each may be independently selected from Group II, for example, any one of C-1, C-2, C-3 and C-19.

[0129] In a more specific embodiment, all *-L 4 -Ar 3 and *-L 5 -Ar 4 It may be represented by C-1, C-2 or C-3 of Group II, but is not limited thereto.

[0130] In one embodiment of the present invention, the second compound can be represented by Chemical Formula 3-8, wherein in Chemical Formula 3-8, Ar 3 and Ar 4 may be each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, L 4 and L 5 may each independently be a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and R 9 To R 18 Each of them may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

[0131] For example, the second compound may be one of the compounds selected from Group 2, but is not limited thereto.

[0132] [Group 2]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] 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, the hole transport capability of the first compound and the electron transport capability of the second compound for the organic optoelectronic device may be used to adjust a suitable weight ratio to achieve bipolar characteristics and improve efficiency and lifespan. Within the above range, for example, they may be included in a weight ratio of about 10:90 to 90:10, about 10:90 to 80:20, about 10:90 to 70:30, about 10:90 to 60:40, or about 10:90 to about 50:50. For example, they may be included in a weight ratio of 20:80 to 50:50, such as 30:70 or 40:60.

[0140] In one embodiment of the present invention, the first compound and the second compound may each include a host as a light-emitting layer, for example, a phosphorescent host.

[0141] The light emitting layer may further include one or more compounds other than the aforementioned host.

[0142] 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, and may be, for example, a red phosphorescent dopant.

[0143] The dopant is a material that promotes light emission by mixing with the aforementioned host in a trace amount, and generally can be a material that emits light by multiple excitation to a triplet state or a multiplet state, such as a metal complex. The dopant can be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types thereof can be used.

[0144] 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.

[0145] [Chemical formula Z]

[0146] L 9 MX 3

[0147] In the chemical formula Z, M is a metal and L 9 and X 3 They are the same as or different from each other and are ligands that form a complex with M.

[0148] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L 9 and X3 For example, it may be a bidentate ligand.

[0149] The hole transport auxiliary layer may be disposed between the light emitting layer 130 and the hole transport layer 141 described later, and in particular, may be disposed in contact with the light emitting layer 130. Since the hole transport auxiliary layer 142 is disposed in contact with the light emitting layer 130, the mobility of holes may be precisely controlled at the interface between the light emitting layer 130 and the hole transport layer 141. The hole transport auxiliary layer 142 may include a plurality of layers.

[0150] The hole transport auxiliary layer 142 may include, for example, a third compound represented by a combination of Chemical Formula 4 and Chemical Formula 5.

[0151]

[0152] In Chemical Formula 4 and Chemical Formula 5,

[0153] Y 1 and Y 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

[0154] X 2 is O or S,

[0155] Two adjacent ones of b1* to b4* in Chemical Formula 4 are connected to the carbon atoms * in Chemical Formula 5.

[0156] The remaining two of b1* to b4* in Chemical Formula 4 that are not connected to * in Chemical Formula 5 are each independently CR c ,

[0157] R c and R 19 To R 23 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0158] L 6 To L 8 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0159] Ar 5 and Ar 6 Each is independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0160] The third compound is a compound having a high HOMO energy level and having good hole injection characteristics. Therefore, the third compound is applied to the hole transport auxiliary layer 142 to effectively improve the hole mobility 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.

[0161] For example, L 7 and L 8 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

[0162] For example, L 7 and L 8 Each independently may be a single bond, or a substituted or unsubstituted phenylene group.

[0163] For example, Ar 5 and Ar 6 Each of the above groups may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group.

[0164] For example, Ar 5 and Ar 6 Each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group.

[0165] In one embodiment, L 7 -Ar 5 and L 8 -Ar 6 The substituents may be each independently selected from group III.

[0166] [Group III]

[0167]

[0168] In group III, * is the connection point.

[0169] For example, L 6 It may be a single bond or a substituted or unsubstituted phenylene group.

[0170] For example, Y 1 and Y 2 Each independently may be a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0171] For example, Y 1 and Y 2 Each independently may be an unsubstituted methyl group or an unsubstituted phenyl group.

[0172] For example, R c and R 19 To R 23 They may each independently be hydrogen, a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0173] For example, R c and R 19 To R 23 Each is hydrogen.

[0174] For example, the third compound may be represented by one of Chemical Formulae 4A to 4F, depending on the fusion position of Chemical Formulae 4 and 5.

[0175]

[0176]

[0177] In Chemical Formulae 4A to 4F,

[0178] Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 and Ar 6 As mentioned above, and R c1 To R c4 Independently with R c The definition is the same.

[0179] Chemical Formula 4A may be represented, for example, by one of Chemical Formulae 4A-1 to 4A-4, depending on a specific substitution position of the amine group.

[0180]

[0181] In Chemical Formulae 4A-1 to 4A-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 ,Ar 6 , R c3and R c4 Same as above.

[0182] Chemical Formula 4B may be represented, for example, by one of Chemical Formulae 4B-1 to 4B-4, depending on a specific substitution position of the amine group.

[0183]

[0184]

[0185] In Chemical Formulae 4B-1 to 4B-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 ,Ar 6 , R c1 and R c4 Same as above.

[0186] Chemical Formula 4C may be represented, for example, by one of Chemical Formulae 4C-1 to 4C-4, depending on a specific substitution position of the amine group.

[0187]

[0188]

[0189] In Chemical Formulae 4C-1 to 4C-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 ,Ar 6 , R c1 and R c2 Same as above.

[0190] Chemical Formula 4D may be represented, for example, by one of Chemical Formulae 4D-1 to 4D-4, depending on a specific substitution position of the amine group.

[0191]

[0192] In Chemical Formulae 4D-1 to 4D-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L8 ,Ar 5 ,Ar 6 , R c3 and R c4 Same as above.

[0193] Chemical Formula 4E may be represented, for example, by one of Chemical Formulae 4E-1 to 4E-4, depending on a specific substitution position of the amine group.

[0194]

[0195] In Formula 4E-1 to Formula 4E-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 ,Ar 6 , R c1 and R c4 Same as above.

[0196] Chemical Formula 4F may be represented, for example, by one of Chemical Formulae 4F-1 to 4F-4, depending on a specific substitution position of the amine group.

[0197]

[0198] In Chemical Formulae 4F-1 to 4F-4, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 ,Ar 6 , R c1 and R c2 Same as above.

[0199] As a specific example, the third compound may be represented by Chemical Formula 4A or Chemical Formula 4B.

[0200] As a more specific example, the first compound may be represented by Chemical Formula 4A-4 or Chemical Formula 4B-1.

[0201] The third compound may be, for example, one of the compounds selected from Group 3, but is not limited thereto.

[0202] [Group 3]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] According to a more specific embodiment of the present invention, the first compound may be represented by the aforementioned Chemical Formula 1A, the second compound may be represented by the aforementioned Chemical Formula 3-8, and the third compound may be represented by the aforementioned Chemical Formula 4B-1.

[0214] 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 forming the anode 110 and the HOMO energy level of the material forming the light emitting layer 130.

[0215] The hole transport layer 141 may include, for example, an amine derivative.

[0216] The hole transport layer 141 may include, for example, a compound represented by Chemical Formula 6, but is not limited thereto.

[0217]

[0218] In Chemical Formula 6,

[0219] R 24 To R 27 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0220] R 24 and R 25 They exist independently or combine with each other to form a ring.

[0221] R 26 and R 27They exist independently or combine with each other to form a ring.

[0222] Ar 7 and Ar 9 are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0223] L 10 To L 13 Each 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.

[0224] For example, Ar 7 It may be a substituted or unsubstituted C6 to C30 aryl group, and for example R 26 It may be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.

[0225] For example, Ar 8 and Ar 9 Each of the above groups may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted bifluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

[0226] The compound represented by Chemical Formula 6 may be, for example, one of the compounds of Group 4, but is not limited thereto.

[0227] [Group 4]

[0228]

[0229] In addition to the light emitting layer 130 , the hole transport auxiliary layer 142 , and the hole transport layer 141 , the organic layer 105 may further include an electron transport region (not shown).

[0230] The electron transport region may further increase electron injection and / or electron mobility between the cathode 120 and the light emitting layer 130 and block holes.

[0231] Specifically, the electron transport region may include an electron transport layer between the cathode 120 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 A compounds may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[0232] [Group A]

[0233]

[0234]

[0235]

[0236] Another embodiment of the present invention may provide an organic light emitting diode, which further includes an electron injection layer, a hole injection layer, etc. in addition to the light emitting layer 130 as the organic layer 105 .

[0237] The organic light emitting diode 300 may be manufactured by forming an anode or a cathode on a substrate, then forming an organic layer by a dry film method or a solution process such as vacuum deposition, sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0238] The organic optoelectronic device may be applied to a display device. For example, the organic light emitting diode may be applied to an organic light emitting diode (OLED) display.

[0239] Hereinafter, the embodiments will be described in more detail with reference to examples. However, these examples are exemplary, and the scope of the claims is not limited thereto.

[0240] Hereinafter, unless otherwise specified, 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.

[0241] The compounds presented as more specific examples of the present invention were synthesized by the following steps.

[0242] (Preparation of the first compound)

[0243] <Nucleosynthesis 1>

[0244]

[0245] Synthesis Example 1: Synthesis of Intermediate Int-1

[0246] [Reaction Scheme 1]

[0247]

[0248] 4-Bromodibenzofuran (50 g, 202.36 mmol), 2-chloroaniline (38.72 g, 303.53 mmol), Pd2(dba)3 (9.26 g, 10.12 mmol), P(t-bu)3 (7.39 ml, 30.35 mmol) and NaO(t-Bu) (29.17 g 303.53 mmol) were placed in a round-bottom flask, dissolved in toluene (650 ml), and then refluxed at 130° C. with stirring for 12 hours. When the reaction was complete, after removing the aqueous layer, 38 g (64%) of intermediate Int-1 was obtained by column chromatography (hexane: DCM (20%)).

[0249] Synthesis Example 2: Synthesis of Intermediate Int-2

[0250] [Reaction Scheme 2]

[0251]

[0252] Under nitrogen conditions, intermediate Int-1 (50g, 170.21mmol), Pd2(dba)3 (7.79g, 8.51mmol), CS2CO3 (110.91g, 340.43mmol) and PCy3.H.BF4 (6.27g, 17.02mmol) were placed in a round-bottom flask, dissolved in DMAc (550ml), and then refluxed and stirred at 160°C for 12 hours. When the reaction was completed, an excess of distilled water was poured into it, and then stirred for 1 hour. The solid was filtered out and then dissolved in MCB (monochlorobenzene) at high temperature. After removing moisture from it with MgSO4, the organic solvent (MCB) was filtered through a silica gel pad and the filtrate obtained was stirred. The solid produced therein was filtered and vacuum dried to obtain 26.9g (62%) of intermediate Int-2.

[0253] Intermediates Int-3, Int-4, Int-5, Int-6, Int-7 and Int-8 were synthesized in the same manner as Synthesis Examples 1 and 2 except that the bromodibenzofuran intermediate was changed.

[0254]

[0255]

[0256] Synthesis Example 3: Synthesis of Intermediate Int-10

[0257] [Reaction Scheme 3]

[0258]

[0259] 2,4-Dichloro-6-phenyl-1,3,5-triazine (36 g, 159.25 mmol), intermediate Int-9 (4-biphenylboronic acid (42.5 g, 151.67 mmol), K2CO3 (41.92 g, 303.33 mmol) and Pd(PPh3)4 (5.26 g, 4.55 mmol) were placed in a round-bottom flask, dissolved in THF (500 ml) and distilled water (200 ml), and then refluxed and stirred at 60°C for 12 hours. When the reaction was completed, the water layer was removed therefrom, and the organic solvent was removed under reduced pressure to obtain a solid. The obtained solid was dissolved in MCB at high temperature. After removing moisture therefrom with MgSO4, the organic solvent (MCB) was filtered through a silica gel pad, and the filtrate obtained therefrom was stirred. The solid produced therein was filtered and vacuum dried to obtain 28 g (52%) of intermediate Int-10.

[0260] Intermediates Int-11 and Int-12 were synthesized in the same manner as in Synthesis Example 3 except that the triazine intermediate and Int-9 were changed.

[0261] Synthesis Example 4: Synthesis of Compound 1-7

[0262] [Reaction Scheme 4]

[0263]

[0264] Under nitrogen conditions, intermediate Int-2 (12 g, 46.7 mmol), intermediate Int-10 (2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine (17.6 g, 51.35 mmol) and NaH (3.17 g, 79.35 mmol) were placed in a round-bottom flask, dissolved in 230 ml of DMF, and then refluxed and stirred at room temperature for 12 hours. When the reaction was completed, an excess of distilled water was poured into it, and then stirred for 1 hour. The solid was filtered out and then dissolved in MCB at high temperature. After removing moisture therefrom with MgSO4, the organic solvent (MCB) was filtered through a silica gel pad, and the filtrate obtained therefrom was stirred. The solid produced therein was filtered and vacuum dried to obtain 23.7 g (90%) of compound 1-7.

[0265] The following compounds were synthesized in the same manner as in Synthesis Example 4 except that the intermediates were changed as shown in Table 1.

[0266] (Table 1)

[0267]

[0268]

[0269] (Preparation of the Second Compound)

[0270] Synthesis Example 19: Synthesis of Compound 2-142

[0271]

[0272] Compound 2-142 was synthesized according to the method known from KR 10-1773363 B1.

[0273] Synthesis Example 20: Synthesis of Compound 2-99

[0274]

[0275] Compound 2-99 was synthesized according to the method known from KR 10-1773363 B1.

[0276] (Preparation of the Third Compound)

[0277] Synthesis Example 21: Synthesis of Compound 3-20

[0278]

[0279] Compound 3-20 was synthesized according to the method known from KR 10-2018-0037889A.

[0280] Synthesis Example 22: Synthesis of Compound 3-28

[0281]

[0282] Compound 3-28 was synthesized according to the method known from KR 10-2018-0037889A.

[0283] Comparative Synthesis Example 1: Synthesis of Compound P-1

[0284]

[0285] Compound P-1 was synthesized by referring to the method known from KR 10-1476231 B1.

[0286] Comparative Synthesis Example 2: Synthesis of Compound P-2

[0287] [Reaction Scheme 5]

[0288]

[0289] Under nitrogen conditions, bis(4-biphenyl)amine (10 g, 31.14 mmol), 2-chloro-9,9-diphenyl-9H-fluorene (10.4 g, 29.66 mmol), NaOtBu (4.28 g, 44.48 mmol), Pd2(dba)3 (1.63 g, 1.78 mmol) and SPhos (2.19 g, 5.34 mmol) were placed in a round-bottom flask, dissolved in toluene (150 ml), and then refluxed at 90 ° C for 4 hours. When the reaction was completed, an excess of distilled water was poured therein, and the organic layer was separated using a split funnel. The product obtained therefrom was treated with MgSO4 to remove moisture, and 10.5 g (56%) of compound P-2 was obtained by column chromatography (hexane: DCM (20%)).

[0290] Comparative Synthesis Example 3: Synthesis of Intermediate Int-13

[0291] [Reaction Scheme 6]

[0292]

[0293] Under nitrogen conditions, 9H-carbazole-3-boronic acid pinacol ester (20 g, 68.22 mmol), 2-bromodibenzothiophene (17.87 g, 68.22 mmol), K2CO3 (18.86 g, 136.44 mmol) and Pd(PPh3)4 (3.94 g, 3.41 mmol) were placed in a round-bottom flask, dissolved in THF (230 ml) and distilled water (80 ml), and then refluxed and stirred at 60°C for 12 hours. When the reaction was completed, after removing the water layer therefrom, the organic solvent was removed therefrom under reduced pressure to obtain a solid. The obtained solid was dissolved in MCB at high temperature. After removing the moisture therefrom with MgSO4, the organic solvent (MCB) was filtered through a silica gel pad, and the filtrate obtained therefrom was stirred. The solid produced therein was filtered and vacuum dried to obtain 14.77 g (62%) of intermediate Int-13.

[0294] Comparative Synthesis Example 4: Synthesis of Compound H-1

[0295] [Reaction Scheme 7]

[0296]

[0297] Under nitrogen conditions, intermediate Int-13 (14.77 g, 42.31 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (16.38 g, 42.31 mmol), NaOtBu (5.03 g, 50.77 mmol), Pd2(dba)3 (2.32 g, 2.54 mmol) and P(t-Bu)3 (1.03 ml, 4.23 mmol) were placed in a round-bottom flask, dissolved in xylene (150 ml), and then refluxed and stirred at 120°C for 12 hours. When the reaction was completed, an excess of distilled water was poured into it and stirred for 1 hour. The solid was filtered and then dissolved in MCB at high temperature. After removing moisture from it using MgSO4, the organic solvent (MCB) was filtered through a silica gel pad and the filtrate obtained was stirred. The solid produced therein was filtered and vacuum dried to obtain 20 g (72%) of compound H-1.

[0298] (Manufacturing of organic light-emitting diodes)

[0299] Example 1

[0300] A glass substrate coated with an indium tin oxide (ITO) thin film was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and moved to a vacuum deposition machine. The obtained ITO transparent electrode was used as an anode, and compound A doped with 1% NDP-9 (commercially available from Novaled) was vacuum deposited on the ITO substrate to form -thick hole transport layer, and depositing compound 3-20 obtained in Synthesis Example 21 on the hole transport layer to form -thick hole transport auxiliary layer. On the hole transport auxiliary layer, the compound 1-7 obtained in Synthesis Example 4 and the compound 2-142 obtained in Synthesis Example 19 were used as the main body and doped with 10 wt% PhGD as a dopant to form a -thick light-emitting layer. In this article, compound 1-7 and compound 2-142 are used in a weight ratio of 4:6. Then, compound C is deposited on the light-emitting layer to form -thick electron transport auxiliary layer, and vacuum depositing compound D and Liq at a weight ratio of 1:1 simultaneously to form -thick electron transport layer. Vacuum deposited on the electron transport layer LiQ and Al is used to form the cathode to manufacture organic light-emitting diodes.

[0301] ITO / Compound A (1% NDP-9 doping, ) / Compound 3-20 / EML[Compound 1-7: Synthetic Compound 2-142: PhGD = 4:6:10 wt%] / Compound C / Compound D: LiQ / LiQ / Al

[0302] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0303] Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-diphenyl-1,3,5-triazine

[0304] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazine-2-yl)phenyl)quinolone

[0305] [PhGD]

[0306]

[0307] Examples 2 to 4 and Comparative Examples 1 to 3

[0308] Diodes according to Examples 2 to 4 and Comparative Examples 1 to 3 were manufactured in the same method as Example 1 except that the host or the hole transport auxiliary layer was changed as shown in Tables 2 and 3.

[0309] evaluate

[0310] The driving voltage and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated. The specific measurement method is as follows, and the results are shown in Tables 2 and 3.

[0311] (1) Measuring the change in current density based on the change in voltage

[0312] While increasing the voltage from 0 V to 10 V, the current value flowing in the obtained organic light emitting diode with respect to the unit device was measured using a current-voltage meter (Keithley 2400), and the measured current value was divided by the area to obtain the result.

[0313] (2) Measuring brightness changes based on voltage changes

[0314] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured using a luminance meter (Minolta Cs-1000A).

[0315] (3) Measurement life

[0316] At 24,000cd / m 2 As the initial brightness (cd / m 2 ) to emit light, the Polanonix lifetime measurement system was used to measure the decrease in brightness over time. The T98 lifetime of the organic light emitting diodes manufactured according to Examples 1 to 4 and Comparative Examples 1 to 3 was measured as the time when the brightness was relative to the initial brightness (cd / m 2 ) drops to 98%.

[0317] (4) Measure the driving voltage

[0318] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 Measure the driving voltage of each diode.

[0319] (5) Calculation of T98 life ratio (%)

[0320] Table 3 shows the relative comparison values ​​of T98(h) between Example 4 and Comparative Example 3.

[0321] T98 life ratio (%) = {T98 (h) of Example 4 / T98 (h) of Comparative Example 3} × 100

[0322] (6) Calculation of driving voltage ratio (%)

[0323] Table 2 shows relative comparison values ​​of driving voltages of Example 1, Examples 2 and 3, and Comparative Examples 1 and 2.

[0324] Driving voltage ratio (%) = {driving voltage of Example 1 (V) / (driving voltage of Comparative Examples 1 and 2 or Examples 2 and 3) (V)} × 100

[0325] (Table 2)

[0326]

[0327] (Table 3)

[0328]

[0329]

[0330] Referring to Table 2, the organic light emitting diodes according to Examples 1 to 3 exhibited a low driving voltage compared to the organic light emitting diodes according to Comparative Examples 1 and 2. This result indicates that since the compound represented by the combination of Chemical Formula 4 and Chemical Formula 5 and exhibiting excellent hole transporting ability was used in the hole transport auxiliary layer of the organic light emitting diodes according to Examples 1 to 3, overall charge balance was achieved in the diodes compared to the organic light emitting diodes according to Comparative Examples 1 and 2.

[0331] In addition, referring to Table 3, the organic light emitting diode according to Example 4 exhibits improved life characteristics compared to the organic light emitting diode according to Comparative Example 3. This result indicates that the compound represented by the combination of Chemical Formula 1 and Chemical Formula 2 and achieving excellent hole injection and transport characteristics is used in the light emitting layer of the organic light emitting diode according to Example 4, compared to the organic light emitting diode according to Comparative Example 3. Since benzofuran or benzothiophene is fused to the carbazole part, the compound represented by the combination of Chemical Formula 1 and Chemical Formula 2 expands the HOMO electron cloud, thereby exhibiting smooth hole injection and transport characteristics, and therefore, the life characteristics of the organic light emitting diode manufactured by applying the compound are improved due to the stability brought about by the balance of holes and electrons.

[0332] In other words, the compound represented by the combination of Chemical Formula 1 and Chemical Formula 2, the compound represented by Chemical Formula 3, and the compound represented by the combination of Chemical Formula 4 and Chemical Formula 5 showed significantly improved performance and thus proved to be the most ideal combination.

[0333] While the invention has been described in connection with what are presently considered to be practical 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.

[0334] <Description of Reference Numerals>

[0335] 300: Organic light-emitting diode

[0336] 110: Anode

[0337] 120: cathode

[0338] 130: Luminous layer

[0339] 141: Hole transport layer

[0340] 142: Hole transport auxiliary layer

[0341] 105: Organic layer.

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 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 a combination of Chemical Formula 4 and Chemical Formula 5: Wherein, in Chemical Formula 1 and Chemical Formula 2, L 1 is a single key, L 2 and 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, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted carbazolyl group, X 1 is O or S, Two adjacent ones of a1* to a4* in Chemical Formula 1 are connected to the carbon atoms * in Chemical Formula 2. The remaining two of a1* to a4* in Chemical Formula 1 that are not connected to * in Chemical Formula 2 are each independently CR a , R a is hydrogen or deuterium, and R 1 To R 8 Each is independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted phenyl; [Chemical formula 3] Wherein, in Chemical Formula 3, Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted dibenzofuranyl group, L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, R b and R 9 To R 18 are each independently hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group, and m is 0; Among them, in Chemical Formula 4 and Chemical Formula 5, Y 1 and Y 2 are each independently a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, X 2 is O or S, Two adjacent ones of b1* to b4* in Chemical Formula 4 are connected to the carbon atoms * in Chemical Formula 5. The remaining two of b1* to b4* in Chemical Formula 4 that are not connected to * in Chemical Formula 5 are each independently CR c , R c and R 19 To R 23 are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted phenyl, L 6 To L 8 are each independently a single bond, or a substituted or unsubstituted phenylene group, Ar 5 and Ar 6 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothienyl, or a substituted or unsubstituted carbazolyl, and Herein, "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 organic optoelectronic device according to claim 1, wherein the first compound is represented by one of Chemical Formula 1A to Chemical Formula 1F: in, In Chemical Formulae 1A to 1F, L 1 To L 3 ,Ar 1 ,Ar 2 , X 1 and R 1 To R 8 As defined in claim 1, and R a1 To R a4 Each independently of R defined in claim 1 a The definition is the same.

3. The organic optoelectronic device according to claim 1, wherein L 2 -Ar 1 and L 3 -Ar 2 Each is independently a substituent selected from Group I: [Group I] in, In group I, * is the connection point.

4. The organic optoelectronic device according to claim 1, wherein the first compound is selected from the compounds of Group 1: [Group 1] 5. The organic optoelectronic device according to claim 1, wherein the second compound is represented by Chemical Formula 3-8: [Chemical formula 3-8] in, In chemical formula 3-8, R 9 To R 18 are each independently hydrogen, or a substituted or unsubstituted C6 to C12 aryl group, and *-L 4 -Ar 3 and *-L 5 -Ar 4 are each independently one of the substituents of Group II, [Group Ⅱ] Among them, in group II, * is the connection point.

6. The organic optoelectronic device according to claim 1, wherein the third compound is represented by Chemical Formula 4A to Chemical Formula 4F: in, In Chemical Formulae 4A to 4F, Y 1 , Y 2 , X 2 , R 19 To R 23 , L 6 To L 8 ,Ar 5 and Ar 6 Same as in claim 1, and R c1 To R c4 Each independently of R defined in claim 1 c The definition is the same.

7. The organic optoelectronic device according to claim 1, wherein L 7 -Ar 5 and L 8 -Ar 6 Substituents independently selected from Group III: [Group III] in, In Group III, * is the connection point.

8. The organic optoelectronic device according to claim 1, wherein the third compound is selected from the group consisting of: [Group 3] 9. The organic optoelectronic device according to claim 1, wherein the first compound is represented by Chemical Formula 1A, The second compound is represented by Chemical Formula 3-8, and The third compound is represented by Chemical Formula 4B-1: [Chemical Formula 1A] in, In Chemical Formula 1A, X 1 is O or S, L 1 is a single key, L 2 and 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, or a substituted or unsubstituted carbazolyl group, and R a3 , R a4 and R 1 To R 8 are each independently hydrogen, or substituted or unsubstituted phenyl; [Chemical formula 3-8] Among them, in chemical formula 3-8, Ar 3 and Ar 4 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothiophenyl group, L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and R 9 To R 18 are each independently hydrogen, deuterium, substituted or unsubstituted phenyl, or substituted or unsubstituted biphenyl; [Chemical formula 4B-1] Wherein, in Chemical Formula 4B-1, X 2 is O or S, L 6 is a single bond, or a substituted or unsubstituted phenylene group, L 7 and L 8 are each independently a single bond, or a substituted or unsubstituted phenylene group, Ar 5 and Ar 6 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group, Y 1 and Y 2 are each independently a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, and R c1 , R c4 and R 19 To R 23 Each is hydrogen. 10 . A display device comprising the organic optoelectronic device according to claim 1 .

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