Organic optoelectronic device and display device

Abstract

The invention relates to an organic optoelectronic device and a display device. The 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 hole transport layer and the light emitting layer, wherein the hole transport auxiliary layer includes a first hole transport auxiliary layer adjacent to the hole transport layer and a second hole transport auxiliary layer adjacent to the light emitting layer, the first hole transport auxiliary layer including a first compound represented by Chemical Formula 1, and the second hole transport auxiliary layer including a second compound represented by Chemical Formula 2, and the first compound and the second compound are different from each other. Details of the chemical formula 1 and the chemical formula 2 are defined in the specification.

Description

Technical Field

[0001] An organic optoelectronic device and a display device are disclosed. Background Art

[0002] An organic optoelectronic device (organic optoelectronic diode) is a device that can convert electrical energy into light energy and vice versa.

[0003] Organic optoelectronic devices can be broadly divided into two categories based on their operating principles: photovoltaic devices that generate electrical energy by separating excitons formed from light energy into electrons and holes and transferring these electrons and holes to different electrodes; and light-emitting devices that generate light energy from electrical energy by applying voltage or current to electrodes.

[0004] Examples of the organic optoelectronic device include an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0005] Among them, organic light emitting diodes (OLEDs) have attracted much attention in recent years due to the increasing demand for flat panel display devices. Organic light emitting diodes are devices that convert electrical energy into light, and the performance of organic light emitting diodes is greatly affected by the organic material between electrodes. Summary of the Invention

[0006] Technical issues

[0007] One embodiment provides an organic optoelectronic device with high efficiency, low driving voltage, and long lifespan.

[0008] Another embodiment provides a display device including an organic optoelectronic device.

[0009] Technical Solution

[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 hole transport layer and the light-emitting layer, wherein the hole transport auxiliary layer includes a first hole transport auxiliary layer adjacent to the hole transport layer and a second hole transport auxiliary layer adjacent to the light-emitting layer, the first hole transport auxiliary layer includes a first compound represented by Chemical Formula 1, the second hole transport auxiliary layer includes a second compound represented by Chemical Formula 2, and the first compound and the second compound are different from each other.

[0011] [Chemical Formula 1]

[0012]

[0013] In Chemical Formula 1,

[0014] X 1 It is O or S,

[0015] 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 C30 heterocyclic group,

[0016] R 1 and R 2 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0017] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0018] m1 is an integer from 1 to 4, and

[0019] m2 is an integer from 1 to 3;

[0020] [Chemical Formula 2]

[0021]

[0022] In Chemical Formula 2,

[0023] X 2 It is O or S,

[0024] L 7 To L 9 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0025] R 5 and R 6 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0026] Ar 6 and Ar 7 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0027] m5 is an integer from 1 to 4, and

[0028] m6 is one of integers from 1 to 3.

[0029] According to one embodiment, a display device including the above-mentioned organic optoelectronic device is provided.

[0030] Beneficial effects

[0031] An organic optoelectronic device with high efficiency, low driving voltage, and long lifespan can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0033] <Description of Reference Numerals>

[0034] 10: Anode 20: Cathode

[0035] 30: Organic layer 31: Light-emitting layer

[0036] 32: Hole transport layer 33: Hole transport auxiliary layer

[0037] 33a: First hole transport auxiliary layer

[0038] 33b: Second hole transport auxiliary layer

[0039] 34: Hole injection layer 35: Electron transport layer DETAILED DESCRIPTION

[0040] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

[0041] As used herein, when no definition is otherwise provided, "substituted" refers to a substituent or a compound in which at least one hydrogen is replaced by deuterium, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

[0042] In one embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, or cyano. In one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl, or cyano. In one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. In one specific embodiment of the present invention, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0043] As used herein, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0044] As used herein, "hydrogen substitution (—H)" may include "deuterium substitution (—D)" or "tritium substitution (—T)".

[0045] As used herein, when no definition is otherwise provided, "hetero" means containing one to three heteroatoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0046] As used herein, "aryl" refers to a group including at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic moieties may be connected by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic moieties may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl.

[0047] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0048] As used herein, "heterocyclyl" is a general concept of heteroaryl and may include at least one heteroatom selected from N, O, S, P and Si in place of carbon (C) in a cyclic compound such as an aryl, a cycloalkyl, a fused ring thereof or a combination thereof. When the heterocyclyl is a fused ring, the entire ring or each ring of the heterocyclyl may include one or more heteroatoms.

[0049] For example, "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by a sigma bond, or when the heteroaryl group comprises two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0050] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted tetraphenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

[0051] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted The present invention also includes, but is not limited to, a substituted or unsubstituted quinolinyl, a substituted or unsubstituted isoquinolinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted naphthyridinyl, a substituted or unsubstituted benzoxazinyl, a substituted or unsubstituted benzothiazinyl, a substituted or unsubstituted acridinyl, a substituted or unsubstituted phenazinyl, a substituted or unsubstituted phenothiazinyl, a substituted or unsubstituted phenoxazinyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted benzonaphthofuranyl, a substituted or unsubstituted benzonaphthothiophenyl, a substituted or unsubstituted benzofuranofluorenyl, a substituted or unsubstituted benzothienofluorenyl, or a combination thereof, but is not limited thereto.

[0052] As used herein, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductive 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.

[0053] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0054] The organic optoelectronic device may be a suitable device that converts electrical energy into light energy and vice versa, such as an organic photovoltaic device, an organic light emitting diode, an organic solar cell, or an organic photosensitive drum.

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

[0056] In the accompanying drawings, the thickness of layers, films, panels, regions, etc. is exaggerated for clarity. Like reference numerals denote like elements throughout the specification. It will 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 intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

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

[0058] refer to Figure 1 , an organic light emitting diode according to one embodiment is described.

[0059] refer to Figure 1 , an organic light emitting diode according to one embodiment includes an anode 10 and a cathode 20 facing each other and an organic layer 30 between the anode 10 and the cathode 20 .

[0060] The anode 10 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 10 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; or 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.

[0061] The cathode 20 may be made of a conductor having a small work function to facilitate electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 20 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; or a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0062] The organic layer 30 includes a light emitting layer 31 , a hole transport layer 32 , and a hole transport auxiliary layer 33 between the hole transport layer 32 and the light emitting layer 31 .

[0063] The light emitting layer 31 includes at least two types of hosts and a dopant, and the host may be, for example, a phosphorescent host.

[0064] The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, such as a red or green phosphorescent dopant.

[0065] The dopant is a material mixed with a host in a small amount to cause luminescence, and can generally be a material such as a metal complex that emits light by being excited multiple times to a triplet state or more. The dopant can be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types thereof can be used.

[0066] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organometallic 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.

[0067] [Chemical formula Z]

[0068] L 10 MX 3

[0069] In the chemical formula Z, M is a metal, and L 10 and X 3 are the same or different and are ligands that form a complex with M.

[0070] 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 10 and X 3 This may be, for example, a bidentate ligand.

[0071] By L 10 and X 3 Examples of the ligand represented by may be selected from the chemical formulae listed in Group A, but are not limited thereto.

[0072] [Group A]

[0073]

[0074] In Group A,

[0075] R 300 to R 302 are each independently hydrogen, deuterium, C1 to C30 alkyl which may be substituted by halogen, C6 to C30 aryl which may be substituted by C1 to C30 alkyl, or halogen, and

[0076] R 303 to R 324 Each is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroaryl, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C6 to C30 arylamino, SF5, a trialkylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group, a dialkylarylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group and a C6 to C30 aryl group, or a triarylsilyl group having a substituted or unsubstituted C6 to C30 aryl group.

[0077] For example, a dopant represented by Chemical Formula V may further be included.

[0078] [Chemical Formula V]

[0079]

[0080] In Chemical Formula V,

[0081] R 101 to R 116 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0082] R 132 to R 134 are each independently C1 to C6 alkyl,

[0083] R 101 to R 116 At least one of them is a functional group represented by Chemical Formula V-1,

[0084] L 100is a bidentate ligand for a monovalent anion and is coordinated to iridium via a lone pair of electrons of a carbon or heteroatom, and

[0085] m14 and m15 are each independently any one of integers from 0 to 3, and m14+m15 is any one of integers from 1 to 3,

[0086] [Chemical Formula V-1]

[0087]

[0088] In Chemical Formula V-1,

[0089] R 135 to R 139 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,and

[0090] * refers to the moiety attached to the carbon atom.

[0091] For example, a dopant represented by Chemical Formula Z-1 may be included.

[0092] [Chemical Formula Z-1]

[0093]

[0094] In formula Z-1, rings A, B, C, and D are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0095] R A 、R B 、R C and R D each independently mono-, di-, tri- or tetra-substituted or unsubstituted;

[0096] L B , L C and L D are each independently a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof,

[0097] When nA is 1, L E It can be a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof; and when nA is 0, L E does not exist;

[0098] R A 、RB 、R C 、R D R and R' are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, or a combination thereof; any adjacent R A 、R B 、R C 、R D , R and R' are optionally linked to each other to provide a ring; X B 、X C 、X D and X E are each independently selected from carbon and nitrogen; and Q 1 , Q 2 , Q 3 and Q 4 Each represents oxygen or a direct bond.

[0099] According to one embodiment, the dopant may be a platinum complex, and may be represented by, for example, Chemical Formula VI.

[0100] [Chemical Formula VI]

[0101]

[0102] In Chemical Formula VI,

[0103] X 100 Selected from O, S and NR 131 ,

[0104] R 117 to R 131 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0105] R 132 to R 134 are each independently C1 to C6 alkyl,

[0106] R 117 to R 131 At least one of them is -SiR 132 R 133 R 134 or tert-butyl, and

[0107] R 132 to R 134 Each is independently a C1 to C6 alkyl group.

[0108] The composition further comprising a dopant may be, for example, a green light emitting composition.

[0109] The hole transport layer 32 is a layer that facilitates the transfer of holes from the anode 10 to the light emitting layer 31 and blocks electrons, and may be, for example, an amine compound, but is not limited thereto.

[0110] The amine compound may include, for example, at least one aryl group and / or heteroaryl group. The amine compound may be represented by, for example, Chemical Formula a or Chemical Formula b, but is not limited thereto.

[0111]

[0112] In chemical formula a or b,

[0113] Ar a to Ar g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof,

[0114] Ar a to Ar c At least one of Ar d to Ar g At least one of may be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and

[0115] Ar h is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

[0116] In addition to the light emitting layer, the organic light emitting diode may further include a hole injection layer 34 .

[0117] The hole injection layer 34 is a layer for promoting injection of holes from the anode 10 to the light emitting layer 31 and blocking electrons, and may be located between the anode 10 and the hole transport layer 32 .

[0118] For example, at least one of the hole transport layer 32 and the hole injection layer 34 may include at least one of the compounds listed in Group B and be different from materials of the first and second hole transport auxiliary layers described later.

[0119] [Group B]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] In the hole transport layer 32 and the hole injection layer 34 , in addition to the compounds described above, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds having similar structures can be used.

[0126] The hole transport auxiliary layer 33 includes a first hole transport auxiliary layer 33 a adjacent to the hole transport layer and a second hole transport auxiliary layer 33 b adjacent to the light emitting layer.

[0127] The first hole transport auxiliary layer includes a first compound represented by Chemical Formula 1, and the second hole transport auxiliary layer includes a second compound represented by Chemical Formula 2, and the first compound and the second compound are different from each other.

[0128] [Chemical Formula 1]

[0129]

[0130] In Chemical Formula 1,

[0131] X 1 It is O or S,

[0132] 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 C30 heterocyclic group,

[0133] R 1 and R 2 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0134] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0135] m1 is an integer from 1 to 4, and

[0136] m2 is an integer from 1 to 3;

[0137] [Chemical Formula 2]

[0138]

[0139] In Chemical Formula 2,

[0140] X 2 It is O or S,

[0141] L 7 To L 9 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0142] R 5 and R 6 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group,

[0143] Ar 6 and Ar 7 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0144] m5 is an integer from 1 to 4, and

[0145] m6 is one of integers from 1 to 3.

[0146] An organic light emitting diode according to one embodiment includes a combination of two hole transport auxiliary layers at the interface between a hole transport layer and a light emitting layer, whereby hole injection capability is adjusted in the first hole transport auxiliary layer to balance charges in the light emitting layer, and hole and electron densities are balanced by blocking electrons in the second hole transport auxiliary layer, resulting in low driving voltage, high efficiency, and improved lifespan characteristics.

[0147] When m1 is 2 or greater, R 1 Each may be the same as or different from each other.

[0148] When m2 is 2 or greater, R 2 Each may be the same as or different from each other.

[0149] For example, Chemical Formula 1 may be represented by one of Chemical Formula 1-1 to Chemical Formula 1-4.

[0150]

[0151] In Chemical Formula 1-1 to Chemical Formula 1-4,

[0152] X 1 , L 1 To L 3 、R 1 、R 2 、Ar 1 、Ar 2 , m1 and m2 are as defined in Chemical Formula 1.

[0153] As a specific example, in Chemical Formula 1, Ar 1 and Ar 2 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 triphenylene group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilyl group.

[0154] For example, in Chemical Formula 1, 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 fluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted dibenzosilyl group.

[0155] For example, in Chemical Formula 1, R 1 and R 2 and may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0156] For example, in Chemical Formula 1, L 1 To L 3 Each independently may be a single bond or a substituted or unsubstituted phenylene group.

[0157] For example, L 2 -Ar 1 and L 3 -Ar 2 The substituents listed in Group I may be each independently selected.

[0158] [Group I]

[0159]

[0160] In Group I,

[0161] R 8 to R 12are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl,

[0162] m8 is an integer from 1 to 5,

[0163] m9 is an integer from 1 to 4,

[0164] m10 is an integer from 1 to 7,

[0165] m11 is an integer from 1 to 3,

[0166] m12 is an integer of 1 or 2, and

[0167] * is the connection point.

[0168] When m8 is 2 or greater, R 8 Each may be the same as or different from each other.

[0169] When m9 is 2 or greater, R 9 Each may be the same as or different from each other.

[0170] When m10 is 2 or greater, R 10 Each may be the same as or different from each other.

[0171] When m11 is 2 or greater, R 11 Each may be the same as or different from each other.

[0172] When m12 is 2 or greater, R 12 Each may be the same as or different from each other.

[0173] For example, the first compound may be one selected from the compounds listed in Group 1, but is not limited thereto.

[0174] [Group 1]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188] When m5 is 2 or greater, R 5 Each may be the same as or different from each other.

[0189] When m6 is 2 or greater, R 6 Each may be the same as or different from each other.

[0190] For example, in Chemical Formula 2, 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 phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilyl group.

[0191] As a specific example, in Chemical Formula 2, Ar 6 and Ar 7 Each of the 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 spirofluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0192] For example, L 7 To L 9 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0193] As a specific example, L 7 can be a single bond, and

[0194] L 8 and L 9 At least one of the groups may be a substituted or unsubstituted phenylene group.

[0195] For example, R 5 and R 6and may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0196] For example, L 8 -Ar 6 and L 9 -Ar 7 The substituents listed in Group I may be each independently selected.

[0197] In a specific embodiment, Ar 6 and Ar 7 At least one of may be represented by Chemical Formula I-1.

[0198] [Chemical Formula I-1]

[0199]

[0200] In Chemical Formula I-1,

[0201] R 8 、R 9 、R 11 , m8, m9 and m11 are the same as above.

[0202] For example, the second compound may be one selected from the compounds listed in Group 2, but is not limited thereto.

[0203] [Group 2]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212] The organic layer 30 may include an electron transport region.

[0213] The electron transport region may further increase electron injection and / or electron mobility between the cathode 20 and the light emitting layer 31 , and block holes.

[0214] Specifically, the electron transport region may include an electron transport layer 35 between the cathode 20 and the light-emitting layer 31 and an electron transport auxiliary layer (not shown) between the light-emitting layer 31 and the electron transport layer 35, and at least one of the compounds listed in group C may be included in at least one layer of the electron transport layer 35 and the electron transport auxiliary layer.

[0215] [Group C]

[0216]

[0217]

[0218]

[0219]

[0220] One embodiment may provide an organic light emitting diode including a light emitting layer 31 , a hole transport layer 32 , a first hole transport layer 33 a , and a second hole transport layer 33 b as organic layers.

[0221] Another embodiment may be an organic light emitting diode including a hole injection layer as an organic layer.

[0222] Another embodiment may be an organic light emitting diode including an electron transport region as an organic layer.

[0223] Meanwhile, the organic light emitting diode may further include an electron injection layer (not shown) and the like as the above-mentioned organic layer in addition to the light emitting layer.

[0224] The organic light emitting diode may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film method such as evaporation, sputtering, plasma plating, and ion plating, and then forming a cathode or an anode thereon.

[0225] The organic light emitting diode may be applied to an organic light emitting display device.

[0226] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the scope of the present invention is not limited thereto.

[0227] Invention Mode

[0228] Hereinafter, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo chemical industry, or P&H tech, or synthesized by known methods unless otherwise specified.

[0229] (Preparation of the First Compound)

[0230] Synthesis Example 1: Synthesis of Compound 1-136

[0231]

[0232] 20.0g (49.8mmol) of the intermediate bis (9,9-dimethyl-9H-fluoren-2-yl) amine, 16.67g (59.76mmol) of the intermediate 1-chloro-8-phenyldibenzo [b, d] furan, 9.57g (99.61mmol) of sodium tert-butoxide and 1.2g (2.98mmol) of tri-tert-butylphosphine were dissolved in 498ml of toluene, and 1.36g (1.49mmol) of Pd2 (dba) 3 was added thereto, and then stirred and refluxed for 12 hours under a nitrogen atmosphere. When the reaction was complete, the organic layer was extracted therefrom with ethyl acetate and distilled water, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio 3: 1) to obtain 26.2g (yield: 82%) of white solid compound 1-136 as the target compound.

[0233] Calculated values: C, 89.55; H, 5.79; N, 2.18; O, 2.48;

[0234] Analytical values: C, 89.55; H, 5.79; N, 2.18; O, 2.48.

[0235] Synthesis Example 2: Synthesis of Compound 1-139

[0236]

[0237] Compound 1-139 (20.1 g, yield: 80%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine and 13.88 g of the intermediate 1-chloro-8-phenyldibenzo[b,d]furan were used in an equivalent ratio of 1:1.2.

[0238] Calculated values: C, 89.52; H, 5.51; N, 2.32; O, 2.65;

[0239] Analytical values: C, 89.52; H, 5.51; N, 2.33; O, 2.65.

[0240] Synthesis Example 3: Synthesis of Compound 1-274

[0241]

[0242] Compound 1-274 (15.2 g, yield: 75%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate 9,9-dimethyl-N-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)-9H-fluoren-2-amine and 7.49 g of the intermediate 2-chlorodibenzo[b,d]thiophene were used in an equivalent ratio of 1:1.2.

[0243] Calculated values: C, 88.22; H, 5.27; N, 1.98; S, 4.53;

[0244] Analytical values: C, 88.22; H, 5.27; N, 1.98; S, 4.53.

[0245] Synthesis Example 4: Synthesis of Compound 1-288

[0246]

[0247] Compound 1-288 (17.4 g, yield: 78%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1-amine and 10.48 g of the intermediate 3-chlorodibenzo[b,d]thiophene were used in an equivalent ratio of 1:1.2.

[0248] Calculated values: C, 83.99; H, 4.88; N, 2.51; O, 2.87; S, 5.75;

[0249] Analytical values: C, 83.99; H, 4.88; N, 2.51; O, 2.87; S, 5.75.

[0250] Comparative Synthesis Example 1: Synthesis of Compound F-1

[0251]

[0252] Compound F-1 (20.4 g, yield: 78%) was synthesized in the same manner as in Synthesis Example 1, except that 17 g of the intermediate N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine and 15.41 g of the intermediate 2-bromo-9,9-dimethyl-9H-fluorene were used in an equivalent ratio of 1:1.2.

[0253] (Preparation of the Second Compound)

[0254] Synthesis Example 5: Synthesis of Compound 2-34

[0255]

[0256] Compound 2-34 (22.4 g, yield: 81%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate N-(9,9-dimethyl-9H-fluorene-2-yl)dibenzo[b,d]furan-1-amine and 19.05 g of the intermediate 9-(4-bromophenyl)-9-phenyl-9H-fluorene were mixed in an equivalent ratio of 1:1.2.

[0257] Calculated values: C, 90.27; H, 5.39; N, 2.02; O, 2.31;

[0258] Analytical values: C, 90.27; H, 5.39; N, 2.02; O, 2.31.

[0259] Synthesis Example 6: Synthesis of Compound 2-76

[0260]

[0261] Compound 2-76 (17.9 g, yield: 82%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate 9,9-dimethyl-N-(3-(9-phenyl-9H-fluorene-9-yl)phenyl)-9H-fluorene-2-amine and 9.54 g of the intermediate 1-chloro-4-phenyldibenzo[b,d]furan were used in an equivalent ratio of 1:1.2.

[0262] Calculated values: C, 90.71; H, 5.38; N, 1.82; O, 2.08;

[0263] Analytical values: C, 90.71; H, 5.38; N, 1.82; O, 2.07.

[0264] Synthesis Example 7: Synthesis of Compound 2-119

[0265]

[0266] Compound 2-119 (16.5 g, yield: 80%) was synthesized in the same manner as in Synthesis Example 1, except that 15 g of the intermediate N-([1,1'-biphenyl]-4-yl)-8-phenyldibenzo[b,d]furan-1-amine and 10.2 g of the intermediate 4-bromo-1,1'-biphenyl were mixed in an equivalent ratio of 1:1.2.

[0267] Calculated values: C, 90.27; H, 5.39; N, 2.02; O, 2.31;

[0268] Analytical values: C, 90.27; H, 5.39; N, 2.02; O, 2.31.

[0269] Synthesis Example 8: Synthesis of Compound 2-175

[0270]

[0271] Compound 2-175 (23.3 g, yield: 77%) was synthesized in the same manner as in Synthesis Example 1, except that 16 g of the intermediate N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophene-1-amine and 21.71 g of the intermediate 9-(4-bromophenyl)-9-phenyl-9H-fluorene were used in an equivalent ratio of 1:1.2.

[0272] Calculated values: C, 88.12; H, 4.98; N, 2.10; S, 4.80;

[0273] Analytical values: C, 88.12; H, 4.98; N, 2.10; S, 4.80.

[0274] Example 1

[0275] A glass substrate coated with an ITO / Ag / ITO thin film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as acetone, isopropyl alcohol, etc. and dried, and then moved to a plasma cleaner, cleaned for 10 minutes using oxygen plasma, and moved to a vacuum depositor. The ITO / Ag / ITO (reflective electrode) electrode thus prepared was used as an anode, and Compound A doped with 3% NDP-9 (Novaled GmbH) was vacuum deposited on the ITO / Ag / ITO substrate to form A hole injection layer is formed, and compound A is deposited on the hole injection layer to The compound 1-136 of Synthesis Example 1 was deposited on the hole transport layer to a thickness of The thickness of the first hole transport auxiliary layer is formed, and the compound 2-34 of Synthesis Example 5 is deposited on the first hole transport auxiliary layer to On the second hole transport auxiliary layer, 85 wt% of the host H1 (40%) and the host H2 (60%) were used as the host, and 15 wt% of PtGD was doped as a dopant to form a second hole transport auxiliary layer by vacuum deposition. Next, compound C is deposited on the light-emitting layer to to form an electron transport auxiliary layer, and simultaneously vacuum depositing compound D and Liq at a ratio of 1:1 to form The organic light-emitting diode is manufactured by sequentially vacuum-depositing Yb and AgMg on the electron transport layer to form a cathode.

[0276] ITO / Ag / ITO / Compound A (3% NDP-9 doping, ) / Compound A / First hole transport auxiliary layer / Second hole transport auxiliary layer / Emitting layer [Host (Host H1, Host H2): PtGD = 85 wt%: 15 wt%] Compound C / Compound D:Liq / Yb / AgMg.

[0277] Compound A: N-(9,9-diphenyl-9H-fluoren-2-yl)-N,9-diphenyl-9H-carbazol-2-amine

[0278] Compound C: 4-{4-[3-(9,9-dimethyl-9H-fluoren-4-yl)phenyl]phenyl}-2-phenyl-6-(4-phenylphenyl)pyrimidine

[0279] Compound D: 2-(4-{2-[4-(diphenyl-1,3,5-triazine-2-yl)phenyl]naphthalen-1-yl}phenyl)-4,6-diphenyl-1,3,5-triazine

[0280] Body H1:

[0281]

[0282] Body H2:

[0283]

[0284] PtGD:

[0285]

[0286] Examples 2 to 12 and Comparative Examples 1 to 5

[0287] An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compositions were changed to those shown in Table 1.

[0288] evaluate

[0289] The driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 12 and Comparative Examples 1 to 5 were evaluated.

[0290] The specific measurement method is as follows, and the results are shown in Table 1.

[0291] (1) Measuring the change in current density according to voltage change

[0292] While increasing the voltage from 0 V to 10 V, the current value flowing through the unit device in the obtained organic light emitting diode was measured using a current-voltage meter (Keithley 2400), and the measured current value was divided by the area to provide a result.

[0293] (2) Measuring brightness changes according to voltage changes

[0294] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured by using a luminance meter (Minolta Cs-1000A).

[0295] (3) Measure luminous efficiency

[0296] By using the luminance and current density and voltage from (1) and (2) above, calculate the 2 ) under the current efficiency (cd / A).

[0297] The luminous efficiency values ​​of Examples 1 to 12 and Comparative Examples 1 to 5 were calculated as relative values ​​based on Comparative Example 3 and are listed in Table 1.

[0298] (4) Measurement life

[0299] In the case of brightness (cd / m 2 ) maintained at 24000cd / m 2 At the same time, the time until each current efficiency (cd / A) dropped to 97% was measured as the lifespan.

[0300] The life measurement values ​​of Examples 1 to 12 and Comparative Examples 1 to 5 were calculated as relative values ​​based on Comparative Example 3 and are listed in Table 1.

[0301] (5) Measure the driving voltage

[0302] The current of each diode was measured at 15 mA / cm by using a current-voltage meter (Keithley 2400). 2 The driving voltage was used to obtain the results.

[0303] The driving voltages of Examples 1 to 12 and Comparative Examples 1 to 5 were calculated as relative values ​​based on Comparative Example 3 and are listed in Table 1.

[0304] [Table 1]

[0305]

[0306]

[0307] Referring to Table 1, the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 12 are significantly improved compared to those of the organic light emitting diodes according to Comparative Examples 1 to 5.

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 hole transport layer and the light emitting layer, in, The hole transport auxiliary layer includes a first hole transport auxiliary layer adjacent to the hole transport layer and a second hole transport auxiliary layer adjacent to the light emitting layer. The first hole transport auxiliary layer includes a first compound represented by Chemical Formula 1, The second hole transport auxiliary layer includes a second compound represented by Chemical Formula 2, and The first compound and the second compound are different from each other: [Chemical Formula 1] In Chemical Formula 1, X 1 It is O or S, 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 C30 heterocyclic group, R 1 and R 2 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, m1 is an integer from 1 to 4, and m2 is an integer from 1 to 3; [Chemical Formula 2] In Chemical Formula 2, X 2 It is O or S, L 7 To L 9 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C30 heterocyclic group, R 5 and R 6 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic group, Ar 6 and Ar 7 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, m5 is an integer from 1 to 4, and m6 is one of integers from 1 to 3.

2. The organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-4: In Chemical Formula 1-1 to Chemical Formula 1-4, X 1 , L 1 To L 3 、R 1 、R 2 、Ar 1 、Ar 2 The definitions of m1, m2 and m3 are as defined in Chemical Formula 1.

3. The organic optoelectronic device according to claim 1, wherein Ar 1 and Ar 2 and 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 naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilyl group. The organic optoelectronic device according to claim 1 , wherein L 2 -Ar 1 , L 3 -Ar 2 , L 5 -Ar 3 and L 6 -Ar 4 Each is independently selected from the substituents listed in Group I: [Group I] In Group I, R 8 to R 12 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl, m8 is an integer from 1 to 5, m9 is an integer from 1 to 4, m10 is an integer from 1 to 7, m11 is an integer from 1 to 3, m12 is an integer of 1 or 2, and * is the connection point. The organic optoelectronic device according to claim 1 , wherein The first compound is selected from the compounds listed in Group 1: [Group 1] The organic optoelectronic device according to claim 1 , wherein Ar 6 and Ar 7 and 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 naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilyl group.

7. The organic optoelectronic device according to claim 1, wherein L 8 -Ar 6 and L 9 -Ar 7 Each is independently selected from the substituents listed in Group I: [Group I] In Group I, R 8 to R 12 are each independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl, m8 is an integer from 1 to 5, m9 is an integer from 1 to 4, m10 is an integer from 1 to 7, m11 is an integer from 1 to 3, m12 is an integer of 1 or 2, and * is the connection point. The organic optoelectronic device according to claim 7 , wherein Ar 6 and Ar 7 At least one of them is represented by Chemical Formula I-1: [Chemical Formula I-1] In Chemical Formula I-1, R 8 、R 9 、R 11 , m8, m9 and m11 are defined in claim 7.

9. The organic optoelectronic device according to claim 1, wherein The second compound is selected from the compounds listed in Group 2: [Group 2] 10 . A display device comprising the organic optoelectronic device according to claim 1 .

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