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 Chemical Formula 4. The details of Chemical Formulas 1 to 5 are as defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2020-0148812 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 these, organic light emitting diodes (OLEDs) have attracted attention in recent years due to an increase in demand for flat panel display devices. An organic light emitting diode is a device that converts electrical energy into light, and an organic material between electrodes greatly affects the performance of the organic light emitting diode. Summary of the invention

[0008] One embodiment provides an organic optoelectronic device having high efficiency, long lifespan, 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 Chemical Formula 4.

[0011]

[0012]

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

[0014] 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,

[0015] 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,

[0016] X 1 is O or S,

[0017] a1* to a4* are each independently a connecting carbon (C) or CR a ,

[0018] Two adjacent ones of a1* to a4* in Chemical Formula 1 are connected to the carbon atoms * in Chemical Formula 2.

[0019] 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 ,

[0020] * is a connection point, and

[0021] 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;

[0022] [Chemical formula 3]

[0023]

[0024] In chemical formula 3,

[0025] 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,

[0026] L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0027] R b and R 9 To R 18are 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

[0028] m is an integer from 0 to 2;

[0029] [Chemical formula 4]

[0030]

[0031] Among them, in chemical formula 4,

[0032] L 6 To L 8 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,

[0033] R 19 To R 26 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

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

[0035] Ar 6 and Ar 7 Each is independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or an amine group substituted with a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0036] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0037] An organic optoelectronic device with low driving force, high efficiency and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment. DETAILED DESCRIPTION

[0039] 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.

[0040] 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.

[0041] 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.

[0042] In the present specification, when a definition is not otherwise provided, "hetero" means that a functional group includes 1 to 3 hetero atoms selected from N, O, S, P and Si, and the remainder is carbon.

[0043] 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.

[0044] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0045] 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.

[0046] 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 group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Hereinafter, an organic optoelectronic device according to one embodiment is described.

[0052] 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.

[0053] 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.

[0054] 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.

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

[0056] 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 .

[0057] 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.

[0058] 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.

[0059] 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.

[0060] The light emitting layer 130 may include a first compound having a stronger hole characteristic and a second compound having a stronger electron characteristic together as a host.

[0061] 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.

[0062]

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

[0064] 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,

[0065] 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,

[0066] X 1 is O or S,

[0067] a1* to a4* are each independently a connecting carbon (C) or CR a ,

[0068] Two adjacent ones of a1* to a4* in Chemical Formula 1 are connected to the carbon atoms * in Chemical Formula 2.

[0069] 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 ,

[0070] * is a connection point, and

[0071] 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.

[0072] 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 and the lifespan characteristics can be improved due to the balance of holes and electrons.

[0073] In particular, due to the substitution with 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.

[0074] 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 the second compound.

[0075] For example, L 2 and L 3 Each 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.

[0076] 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.

[0077] For example, Ar 1 and Ar 2Each 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.

[0078] As a specific example, Ar 1 and Ar 2 It may be unsubstituted or substituted with phenyl.

[0079] 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.

[0080] In one embodiment, L 2 -Ar 1 and L 3 -Ar 2 The substituents may be each independently selected from Group I.

[0081] [Group I]

[0082]

[0083] In group I, * is the connection point.

[0084] For example, L 1 It may be a single bond, or a substituted or unsubstituted phenylene group.

[0085] For example, L 1 Can be a single bond.

[0086] For example, R a and R 1 To R 8 Each independently may be hydrogen, or a substituted or unsubstituted phenyl group.

[0087] 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 may be hydrogen.

[0088] For example, R a and R 1 To R 8 Each of may be hydrogen.

[0089] For example, the first compound may be represented by one of Chemical Formulae 1A to 1F according to the fusion position of Chemical Formulae 1 and 2, for example.

[0090]

[0091]

[0092] In Chemical Formulae 1A to 1F,

[0093] 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 Each independently is a The definition is the same.

[0094] 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.

[0095] As a more specific example, the first compound may be represented by Chemical Formula 1A or Chemical Formula 1C.

[0096] The first compound may be, for example, one selected from the compounds of Group 1, but is not limited thereto.

[0097] [Group 1]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] The second compound may be a compound having relatively strong hole characteristics, and may be represented by Chemical Formula 3.

[0109] [Chemical formula 3]

[0110]

[0111] In chemical formula 3,

[0112] 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,

[0113] L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0114] 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

[0115] m is an integer from 0 to 2.

[0116] The second compound may be used in the light emitting layer together with the first compound to improve light emitting efficiency and lifespan characteristics by increasing charge mobility and increasing stability.

[0117] For example, Ar in formula 3 3 and Ar 4 may 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,

[0118] 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,

[0119] 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

[0120] m can be 0 or 1.

[0121] 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.

[0122] In a specific embodiment of the present invention, Chemical Formula 3 may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-15.

[0123]

[0124]

[0125] 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.

[0126] [Group Ⅱ]

[0127]

[0128] In group II, * is the connection point.

[0129] In one embodiment, Chemical Formula 3 may be represented by Chemical Formula 3-8.

[0130] 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.

[0131] In a more specific embodiment, *-L 4 -Ar 3 and *-L 5 -Ar 4 All are represented by C-1, C-2 or C-3 of Group II, but are not limited thereto.

[0132] In a more specific 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 4may 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.

[0133] For example, the second compound may be one selected from the compounds of Group 2, but is not limited thereto.

[0134] [Group 2]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] For example, the first compound and the second compound may be included 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 may be used to adjust a suitable weight ratio for an organic optoelectronic device to achieve bipolar characteristics and improve efficiency and lifespan. Within the above range, for example, they may be included in a weight ratio of 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40. For example, they may be included in a weight ratio of 40:60 to 50:50, for example, 40:60.

[0141] 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.

[0142] The light emitting layer may further include one or more compounds other than the aforementioned host.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] [Chemical formula Z]

[0147] L 9 MX 4

[0148] In the chemical formula Z, M is a metal and L 9 and X 4 They are the same as or different from each other and are ligands that form a complex with M.

[0149] 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 X 4 This may be, for example, a bidentate ligand.

[0150] It 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 hole mobility at the interface between the light-emitting layer 130 and the hole transport layer 141 may be precisely controlled. The hole transport auxiliary layer 142 may include a plurality of layers.

[0151] The hole transport auxiliary layer 142 may include, for example, a third compound represented by Chemical Formula 4.

[0152] [Chemical formula 4]

[0153]

[0154] In chemical formula 4,

[0155] L 6 To L 8 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,

[0156] R 19 To R 26 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0157] Ar 5 is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0158] Ar 6 and Ar 7 Each is independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or an amine group substituted with a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0159] 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.

[0160] For example, Ar 6 and Ar 7 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazolyl group, or an amine group substituted with a phenyl group, a biphenyl group, a fluorenyl group, a dibenzofuranyl group, a dibenzothienyl group or a carbazolyl group.

[0161] For a specific example, Ar 6 and Ar 7 Each of them 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 an amine group substituted with a biphenyl group, a fluorenyl group, a dibenzofuranyl group or a dibenzothienyl group.

[0162] For example, Ar 6 and Ar 7The substituents may be each independently selected from group III.

[0163] [Group III]

[0164]

[0165]

[0166] For example, Ar 6 and Ar 7 At least one of can be represented by Chemical Formula A1 to Chemical Formula A3.

[0167]

[0168] In Chemical Formulae A1 to A3,

[0169] * is the connection point,

[0170] X 2 O, S, or CR 27 CR 28 ,

[0171] R 27 and R 28 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

[0172] R c , R d , R e , R f , R g , R h and R i are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0173] Ar 8 and Ar 9 Each is independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0174] For example, R 27 and R 28 Each independently may be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0175] For example, R c , R d , R e , R f , R g , Rh and R i Each may independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0176] 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 terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0177] For example, Ar 8 and Ar 9 The substituents may be each independently selected from Group IV.

[0178] [Group IV]

[0179]

[0180] In one embodiment, Ar 6 To Ar 9 Each is independently 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 dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0181] As a specific example, the third compound may be represented by one of Chemical Formula 4-1 to Chemical Formula 4-3.

[0182]

[0183]

[0184] [Chemical formula 4-3]

[0185]

[0186] In Chemical Formula 4-1 to Chemical Formula 4-3,

[0187] X 2 , R 19 To R 26 , L 6 To L 8 ,Ar 6 and Ar 7 Same as above,

[0188] X 3 O, S or CR t Ru ,

[0189] Ar 8 is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0190] R j , R k , R l , R m , R n , R o , R p , R q , R r and R s are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl, and

[0191] R t and R u Each is independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0192] For example, R 19 To R 26 Each independently may be hydrogen, or a substituted or unsubstituted phenyl group.

[0193] For example, L 6 To L 8 Each independently may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0194] In the specific example, L 6 may be substituted or unsubstituted phenylene, and

[0195] L 7 and L 8 Each independently may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0196] For example, Ar 5 The phenyl group may be substituted or unsubstituted.

[0197] For example, Ar 7 and Ar 8Each 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 dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0198] For example, R j , R k , R l , R m , R n , R o , R p , R q , R r and R s Each independently may be hydrogen, or a substituted or unsubstituted phenyl group.

[0199] The third compound may be, for example, one of the compounds selected from Group 3, but is not limited thereto.

[0200] [Group 3]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212] 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 4-1.

[0213] 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.

[0214] The hole transport layer 141 may include, for example, an amine derivative.

[0215] The hole transport layer 141 may include, for example, a compound represented by Chemical Formula 5, but is not limited thereto.

[0216] [Chemical formula 5]

[0217]

[0218] In Chemical Formula 5,

[0219] R 29 To R 32 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 29 and R 30 Each exists independently or combines with each other to form a ring,

[0221] R 31 and R 32 Each exists independently or combines with each other to form a ring,

[0222] Ar 10 To Ar 12 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 9 To L 12 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 10 may be a substituted or unsubstituted C6 to C30 aryl group, and for example, R 31 It may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

[0225] For example, Ar 11 and Ar 12Each is independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted bifluorenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl, or a combination thereof.

[0226] The compound represented by Chemical Formula 5 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 methyl (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 at high temperature. After removing moisture from it with MgSO4, the organic solvent was filtered with a silica gel pad and the filtrate was stirred. The solid produced was filtered and dried in vacuo 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 in 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. At the end of the reaction, after removing the water layer, the organic solvent was removed under reduced pressure to obtain a solid. The obtained solid was dissolved in MCB at high temperature. After removing water from it with MgSO4, the organic solvent was filtered through a silica gel pad and the filtrate obtained was stirred.

[0260] Herein, 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 thereto, and then stirred for 1 hour. The solid was filtered out and then dissolved in MCB at high temperature. MgSO4 was used to remove moisture therefrom, and then the organic solvent was filtered through a silica gel pad, and the filtrate obtained therefrom was stirred. The solid produced therein was filtered out and dried in vacuo to obtain 23.7 g (90%) of compound 1-7.

[0265] According to the same method as Synthesis Example 4 except that the intermediates were changed as shown in Table 1, the following compounds were synthesized.

[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 3-1

[0278]

[0279] Compound 3-1 was synthesized according to the method known from KR 10-1931250 B1.

[0280] Synthesis Example 22: Synthesis of Compound 3-2

[0281]

[0282] Compound 3-2 was synthesized according to the method known from KR 10-1931250 B1.

[0283] Synthesis Example 23: Synthesis of Intermediate Int-13

[0284] [Reaction Scheme 5]

[0285]

[0286] Under nitrogen, 4-benzidine (18.78 g, 111.08 mmol), 2-chlorodibenzothiophene (18.63 g, 85.44 mmol), NaOtBu (24.636 g, 256.33 mmol), Pd2(dba)3 (3.91 g, 4.27 mmol) and P(t-Bu)3 (3.46 ml, 8.54 mmol) were placed in a round-bottom flask, dissolved in xylene (560 ml), and then refluxed for 12 hours. When the reaction was complete, excess distilled water was poured into it and the organic layer was separated using a separatory funnel. The product thus obtained was dried using MgSO4, and then 11.4 g (38%) of intermediate Int-13 was obtained by column chromatography (hexane: DCM (20%)).

[0287] Synthesis Example 24: Synthesis of Compound 3-199

[0288] [Reaction Scheme 6]

[0289]

[0290] Intermediate Int-14 was synthesized with reference to the method known from KR 10-1931250 B1. Intermediate Int-13 (11.4 g, 32.47 mmol), intermediate Int-14 (12.25 g, 30.92 mmol), NaOtBu (4.46 g, 46.38 mmol), Pd2(dba)3 (1.7 g, 1.86 mmol) and Sphos (2.29 g, 5.57 mmol) were placed in a round bottom flask under nitrogen, dissolved in toluene (160 ml), and then refluxed for 4 hours. When the reaction was complete, an excess of distilled water was poured in, and the organic layer was separated using a separatory funnel. The product thus obtained was dried over MgSO4 and then 12.9 g (63%) of compound 3-199 was obtained by column chromatography (hexane: DCM (30%)).

[0291] Synthesis Example 25: Synthesis of Compound 3-220

[0292] [Reaction Scheme 7]

[0293]

[0294] Compound 3-220 was synthesized according to the method known from KR 10-2019-0038303 A.

[0295] Synthesis Example 26: Synthesis of Compound 3-212

[0296] [Reaction Scheme 8]

[0297]

[0298] Compound 3-212 was synthesized according to the method known in KR 10-2019-0038303 A.

[0299] Synthesis Example 27: Synthesis of Compound 3-216

[0300] [Reaction Scheme 9]

[0301]

[0302] Synthesis Example 28: Synthesis of Compound 3-224

[0303] [Reaction Scheme 10]

[0304]

[0305] Compound 3-224 was synthesized according to the method known in KR 10-2019-0038303 A.

[0306] Comparative Synthesis Example 1: Synthesis of Compound P-1

[0307]

[0308] Compound P-1 was synthesized according to the method known from KR 10-1476231 B1.

[0309] Comparative Synthesis Example 2: Synthesis of Compound P-2

[0310] [Reaction Scheme 11]

[0311]

[0312] Under nitrogen, 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 separatory funnel. The product thus obtained was dried using MgSO4, and then 10.5 g (56%) of compound P-2 was obtained by column chromatography (hexane: DCM (20%)).

[0313] Comparative Synthesis Example 3: Synthesis of Intermediate Int-15

[0314] [Reaction Scheme 12]

[0315]

[0316] Under nitrogen, 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 was filtered with a silica gel pad, and the filtrate obtained therefrom was stirred. The solid produced therein was filtered and dried in vacuo to obtain 14.77 g (62%) of intermediate Int-15.

[0317] Comparative Synthesis Example 4: Synthesis of Compound H-1

[0318] [Reaction Scheme 13]

[0319]

[0320] Under nitrogen conditions, intermediate Int-15 (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 then stirred for 1 hour. The solid was filtered and then dissolved in MCB at high temperature. After removing the moisture therein with MgSO4, the organic solvent was filtered with a silica gel pad and the filtrate obtained therefrom was stirred. The solid produced therein was filtered and vacuum dried to obtain 20 g (72%) of compound H-1.

[0321] (Manufacturing of organic light-emitting diodes)

[0322] Example 1

[0323] 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 resulting 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 the compound 3-199 obtained in Synthesis Example 24 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 host and doped with 10 wt% PhGD as a dopant, and vacuum deposited to form -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 in 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 make organic light-emitting diodes.

[0324] ITO / Compound A (1% NDP-9 doping, ) / Compound 3-199 / EML[Compound 1-7: Synthetic Compound 2-142:PhGD=4:6:10wt%] / Compound / Compound D:LiQ / LiQ / Al

[0325] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0326] Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-diphenyl-1,3,5-triazine

[0327] Compound D: 8-(4-(4,6-di(naphthalene-2-yl)-1,3,5-triazine-2-yl)phenyl)quinolone

[0328] [PhGD]

[0329]

[0330] Examples 2 to 4, and Comparative Examples 1 to 3

[0331] Diodes according to Examples 2 to 4 and Comparative Examples 1 to 3 were manufactured in the same method as in Example 1, except that the host or the hole transport auxiliary layer was changed as shown in Tables 2 and 3.

[0332] evaluate

[0333] 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.

[0334] (1) Measuring the change in current density based on the change in voltage

[0335] 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.

[0336] (2) Measuring brightness changes based on voltage changes

[0337] 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).

[0338] (3) Measurement life

[0339] At 24,000cd / m 2 As the initial brightness (cd / m 2 ) was used to emit light, and the decrease in brightness over time was measured using the Polanonix lifetime measurement system. The T97 lifetime of the organic light emitting diodes according to Example 4 and Comparative Example 3 was measured as the time when the brightness was relative to the initial brightness (cd / m 2 ) drops to 97%.

[0340] (4) Measure the driving voltage

[0341] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 Measure the driving voltage of each diode.

[0342] (5) Calculation of T97 life ratio (%)

[0343] Table 3 shows the relative comparison values ​​of T97(h) between Example 4 and Comparative Example 3.

[0344] T97 life ratio (%) = {T97 (h) of Example 4 / T97 (h) of Comparative Example 3} × 100

[0345] (6) Calculation of driving voltage ratio (%)

[0346] Table 2 shows relative comparison values ​​of driving voltages of Example 1, Examples 2 and 3, and Comparative Examples 1 and 2.

[0347] Driving voltage ratio (%) = {driving voltage of Example 1 (V) / (driving voltage of Comparative Examples 1 and 2 or Examples 2 and 3) (V)} × 100

[0348] (Table 2)

[0349]

[0350] (Table 3)

[0351]

[0352] Referring to Table 2, the organic light emitting diodes according to Examples 1 to 3 exhibited lower driving voltages than the organic light emitting diodes according to Comparative Examples 1 and 2. This result indicates that since the compound represented by Chemical Formula 4 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.

[0353] In addition, referring to Table 3, the organic light emitting diode according to Example 4 exhibited improved life characteristics compared with 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 with the organic light emitting diode according to Comparative Example 3. Since benzofuran or benzothiophene is partially fused with carbazole, the compound represented by the combination of Chemical Formula 1 and Chemical Formula 2 expands the HOMO electron cloud and thus exhibits smooth hole injection and transport characteristics, and thus the life characteristics of the organic light emitting diode manufactured by applying the same are improved due to the stability caused by the balance of holes and electrons.

[0354] In other words, the combination of compound derivatives according to the present invention can control the characteristics of the hole transport auxiliary layer and the light-emitting layer in the organic light-emitting diode, thereby establishing a balance between holes and electrons in the light-emitting layer of the organic light-emitting diode, thereby providing improved driving voltage and lifespan.

[0355] 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 is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0356] <Description of Reference Numerals>

[0357] 300: Organic light-emitting diode

[0358] 110: Anode

[0359] 120: cathode

[0360] 130: Luminous layer

[0361] 141: Hole transport layer

[0362] 142: Hole transport auxiliary layer

[0363] 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, wherein the light emitting layer comprises 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: in, 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 , * is the connection point, 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] Among them, 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; [Chemical formula 4] Among them, in chemical formula 4, L 6 is a single bond, or a substituted or unsubstituted phenylene group, L 7 and L 8 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group, R 19 To R 26 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted phenyl, Ar 5 is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, Ar 6 and Ar 7 each independently represents a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenylyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothienyl, or an amine substituted with a biphenylyl, a fluorenyl, a dibenzofuranyl or a dibenzothienyl, Wherein Ar 6 and Ar 7 At least one of is represented by Chemical Formula A1 or Chemical Formula A3: Among them, in Chemical Formula A1 and Chemical Formula A3, * is the connection point, X 2 is O or S, R c , R d and R e are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and Ar 8 and Ar 9 are each independently a biphenyl group, a fluorenyl group, a dibenzofuranyl group, or a dibenzothienyl group, 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 substituent is independently 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] Where, in Group II, * is the connection point.

6. The organic optoelectronic device according to claim 1, wherein the third compound is represented by one of Chemical Formula 4-1 to Chemical Formula 4-3: [Chemical formula 4-3] in, In Chemical Formula 4-1 to Chemical Formula 4-3, R 19 To R 26 , L 6 To L 8 ,Ar 5 and Ar 7 Same as claim 1, and X 2 O, S or CR 27 R 28 , X 3 O, S or CR t R u , Ar 8 is a biphenyl group, a fluorenyl group, a dibenzofuranyl group, or a dibenzothienyl group, R j , R k , R l , R m , R n , R o , R p , R q , R r and R s are each independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl, R t and R u are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and R 27 and R 28 Each is independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

7. The organic optoelectronic device according to claim 1, wherein the third compound is selected from the group consisting of compounds of Group 3: [Group 3] [3-25]8 [3-53] [3-81] 8. 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 4-1: [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 4-1] Among them, in chemical formula 4-1, X 2 is O, S or CR 27 CR 28 , R 27 and R 28 are each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, Ar 5 is a substituted or unsubstituted phenyl group, Ar 7 is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothienyl, L 6 is a substituted or unsubstituted phenylene group, L 7 and L 8 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group, and R j , R k , R l and R 19 To R 26 Each is independently hydrogen or substituted or unsubstituted phenyl. 9 . A display device comprising the organic optoelectronic device according to claim 1 .

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