Organic optoelectronic device and display device

Abstract

It includes an anode and a cathode facing each other, a light-emitting layer located between the anode and the cathode, a hole transport layer located between the anode and the light-emitting layer, and a hole transport assist layer located between the hole transport layer and the light-emitting layer. The above hole transport assist layer includes a first hole transport assist layer adjacent to the hole transport layer and a second hole transport assist layer adjacent to the light-emitting layer, and The first hole transport assisting layer comprises a first compound represented by a combination of Formula 1 and Formula 2, and The above second hole transport assisting layer relates to an organic optoelectronic device and a display device comprising a second compound represented by Chemical Formula 3. The contents of the above chemical formulas 1 to 3 are as defined in the specification.

Description

Technology Field

[0001] This relates to organic optoelectronic devices and display devices. Background Technology

[0002] An organic optoelectronic diode is a device capable of converting electrical energy and light energy.

[0003] Organic optoelectronic devices can be broadly divided into two types based on their operating principles. One is a photovoltaic device that generates electrical energy as excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to different electrodes, and the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0004] Examples of organic optoelectronic devices include organic photovoltaic devices, organic light-emitting diodes, organic solar cells, and organic photoconductor drums.

[0005] Among these, organic light-emitting diodes (OLEDs) have recently been receiving significant attention due to the increasing demand for flat panel display devices. As an organic light-emitting diode is a device that converts electrical energy into light, its performance is greatly influenced by the organic material located between the electrodes. The problem to be solved

[0006] One embodiment provides a high-efficiency, low-drive voltage, and long-life organic optoelectronic device.

[0007] Another embodiment provides a display device including the organic optoelectronic element. means of solving the problem

[0008] According to one embodiment, an organic optoelectronic device is provided comprising an anode and a cathode facing each other, a light-emitting layer located between the anode and the cathode, a hole transport layer located between the anode and the light-emitting layer, and a hole transport assist layer located between the hole transport layer and the light-emitting layer, wherein the hole transport assist layer comprises a first hole transport assist layer adjacent to the hole transport layer and a second hole transport assist layer adjacent to the light-emitting layer, wherein the first hole transport assist layer comprises a first compound represented by a combination of the following chemical formulas 1 and 2, and the second hole transport assist layer comprises a second compound represented by the following chemical formula 3.

[0009] [Chemical Formula 1] [Chemical Formula 2]

[0010]

[0011] In the above Chemical Formulas 1 and 2,

[0012] a1* to a4* of Chemical Formula 1 are each independently connected carbon (C) or CR a And,

[0013] Among a1* to a4* of Chemical Formula 1, two adjacent ones are each connected to * of Chemical Formula 2, and

[0014] Among a1* to a4* of Chemical Formula 1, the remaining two that are not connected to * of Chemical Formula 2 are CR a And,

[0015] X 1 and X 2 is independently O, S, or CR 3 R 4 And,

[0016] L 1 to L 3 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0017] R a , and R 1 to R 4Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0018] R 3 and R 4 Each exists independently or is connected to form a substituted or unsubstituted C3 to C10 cycloalkyl group, and

[0019] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a substituted or unsubstituted C6 to C30 arylamine group, and

[0020] m1 is one of integers from 1 to 4, and

[0021] m2 is one of integers from 1 to 3;

[0022] [Chemical Formula 3]

[0023]

[0024] In the above chemical formula 3,

[0025] X 3 is O, S, or CR 7 R 8 And,

[0026] L 4 to L 6 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0027] R 5 to R 8 Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0028] R7 and R 8 Each exists independently or is connected to form a substituted or unsubstituted C3 to C10 cycloalkyl group, and

[0029] Ar 3 and Ar 4 Each is independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0030] m3 is one of integers from 1 to 4, and

[0031] m4 is one of the integers 1 to 3. Effects of the invention

[0032] It is possible to realize high-efficiency, low-drive voltage, and long-life organic optoelectronic devices. Brief explanation of the drawing

[0033] FIG. 1 is a cross-sectional view illustrating an organic light-emitting device according to one embodiment. Specific details for implementing the invention

[0034] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0035] In this specification, "substitution" means that, unless otherwise defined, at least one hydrogen of a substituent or compound is substituted with a deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof.

[0036] In one example of the present invention, "substitution" means that at least one hydrogen in the substituent or compound is substituted with deuterium, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. Furthermore, in a specific example of the present invention, "substitution" means that at least one hydrogen in the substituent or compound is substituted with deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a cyano group. Furthermore, in a specific example of the present invention, "substitution" means that at least one hydrogen in the substituent or compound is substituted with deuterium, a C1 to C5 alkyl group, a C6 to C18 aryl group, or a cyano group. In addition, in a specific example of the present invention, "substitution" means that at least one hydrogen of a substituent or compound is substituted with a deuterium, cyano group, methyl group, ethyl group, propyl group, butyl group, phenyl group, biphenyl group, terphenyl group, or naphthyl group.

[0037] In this specification, “non-substituted” means that a hydrogen atom remains a hydrogen atom without being substituted by another substituent.

[0038] In this specification, “hydrogen substitution (-H)” may include “deuterium substitution (-D) or “tritium substitution (-T).”

[0039] In this specification, "hetero" means, unless otherwise defined, that one functional group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, P and Si, and the remainder is carbon.

[0040] In this specification, "aryl group" is a collective concept for a group having one or more hydrocarbon aromatic moietys, including a form in which all elements of the hydrocarbon aromatic moiety have p-orbitals and these p-orbitals form a conjugation, such as a phenyl group, a naphthyl group, etc., and a form in which two or more hydrocarbon aromatic moietys are connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quarterphenyl group, etc., and a non-aromatic fused ring in which two or more hydrocarbon aromatic moietys are directly or indirectly fused, such as a fluorenyl group, etc.

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

[0042] In this specification, "heterocyclic group" is a superordinate concept including heteroaryl groups, meaning that a cyclic compound, such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof, contains at least one heteroatom selected from the group consisting of N, O, S, P, and Si instead of carbon (C). If the heterocyclic group is a fused ring, it may contain one or more heteroatoms in the entire heterocyclic group or in each ring.

[0043] For example, a "heteroaryl group" means containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si within the aryl group. Two or more heteroaryl groups may be directly connected through sigma bonds, or if the heteroaryl group comprises two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may contain one to three heteroatoms.

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

[0045] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic groups are a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazoleyl group, a substituted or unsubstituted triazoleyl group, a substituted or unsubstituted oxazoleyl group, a substituted or unsubstituted thiazoleyl group, a substituted or unsubstituted oxadiazoleyl group, a substituted or unsubstituted thiadiazoleyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazoleyl group, a substituted or unsubstituted indoleyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted It may be an isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthiridinyl group, a substituted or unsubstituted benzoxazine dil group, a substituted or unsubstituted benzothiazine dil group, a substituted or unsubstituted acrridinyl group, a substituted or unsubstituted phenazine dil group, a substituted or unsubstituted phenothiazine dil group, a substituted or unsubstituted phenoxazine dil group, a substituted or unsubstituted carbazole dil group, a substituted or unsubstituted dibenzofuran dil group, a substituted or unsubstituted dibenzothiophen dil group, a substituted or unsubstituted benzonaphtyufuran dil group, a substituted or unsubstituted benzonaphthiophen dil group, a substituted or unsubstituted benzofuranofluorenyl group, a substituted or unsubstituted benzothiophenfluorenyl group, or a combination thereof, but is not limited thereto.

[0046] In this specification, the term "hole characteristic" refers to a characteristic that can form holes by donating electrons when an electric field is applied, and means a characteristic that facilitates the injection of holes formed at the anode into the light-emitting layer, the movement of holes formed in the light-emitting layer to the anode, and movement within the light-emitting layer by having a conduction characteristic along the HOMO level.

[0047] In addition, electronic properties refer to the ability to receive electrons when an electric field is applied, and they refer to properties that facilitate the injection of electrons formed at the cathode into the light-emitting layer, the movement of electrons formed at the light-emitting layer to the cathode, and the movement of electrons within the light-emitting layer by having conduction properties along the LUMO level.

[0048] Organic optoelectronic devices are not particularly limited as long as they are devices capable of mutually converting electrical energy and light energy, and examples include organic photovoltaic devices, organic light-emitting devices, organic solar cells, and organic photosensitive drums.

[0049] Here, an organic light-emitting diode is described as an example of an organic optoelectronic device, but is not limited thereto and can be applied in the same way to other organic optoelectronic devices.

[0050] In the drawings, thicknesses have been enlarged to clearly represent various layers and regions. Throughout the specification, the same reference numerals have been used for similar parts. When a part such as a layer, film, region, or plate is described as being "on" another part, this includes not only cases where it is "immediately on" another part, but also cases where there is another part in between. Conversely, when a part is described as being "immediately on" another part, it means that there is no other part in between.

[0051] FIG. 1 is a cross-sectional view illustrating an organic light-emitting device according to one embodiment.

[0052] An organic light-emitting device according to one embodiment will be described below with reference to FIG. 1.

[0053] Referring to FIG. 1, an organic light-emitting device according to one embodiment includes an anode (10) and a cathode (20) facing each other, and an organic layer (30) located between the anode (10) and the cathode (20).

[0054] The anode (10) may be made of a conductor with a high work function to facilitate hole injection, for example, and may be made of a metal, a metal oxide and / or a conductive polymer. The anode (10) may be a metal or an alloy thereof, such as nickel, platinum, vanadium, chromium, copper, zinc, gold; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), or indium zinc oxide (IZO); 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) (polyethylenedioxythiophene: PEDOT), polypyrrole and polyaniline, but is not limited thereto.

[0055] The cathode (20) may be made of a conductor with a low work function to facilitate electron injection, for example, and may be made of a metal, a metal oxide and / or a conductive polymer. The cathode (20) may be a metal or an alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc.; or a multilayer material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0056] The organic layer (30) includes a light-emitting layer (31), a hole transport layer (32), and a hole transport auxiliary layer (33) located between the hole transport layer (32) and the light-emitting layer (31).

[0057] The light-emitting layer (31) includes at least two types of host and dopant, and the host may be, for example, a phosphorescent host.

[0058] The dopant can be, for example, a phosphorescent dopant, for example, a red, green, or blue phosphorescent dopant, for example, a red or green phosphorescent dopant.

[0059] A dopant is a substance that is mixed in trace amounts into a host to produce luminescence, and generally, substances such as metal complexes that emit light through multiple excitation, which excites the host to a triplet state or higher, may be used. The dopant may be, for example, inorganic, organic, or organic-inorganic compounds, and may include one or more types.

[0060] Phosphorescent dopants are an example of a dopant, and examples of phosphorescent dopants include organometallic compounds containing Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof. Phosphorescent dopants may include, for example, compounds represented by the following chemical formula Z, but are not limited thereto.

[0061] [Chemical Formula Z]

[0062] L 7 MX 4

[0063] In the above chemical formula Z, M is a metal, and L 7 and X 4 is a ligand that is the same or different from each other and forms a complex with M.

[0064] The above M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and the above L 7 and X 4 It can be, for example, a bidentate ligand.

[0065] L 7 and X 4 Examples of ligands represented by may be selected from the chemical formulas listed in Group A below, but are not limited thereto.

[0066] [Group A]

[0067]

[0068] In the above group A,

[0069] R 300 to R 302 Each is independently hydrogen, deuterium, a C1 to C30 alkyl group substituted or unsubstituted with a halogen, a C6 to C30 aryl group substituted or unsubstituted with a C1 to C30 alkyl group, or a halogen, and

[0070] R 303 to R 324 Each is independently hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 amino group, a substituted or unsubstituted C6 to C30 arylamino group, 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.

[0071] For example, it may include a dopant represented by the following chemical formula V.

[0072] [Chemical Formula V]

[0073]

[0074] In the above chemical formula V,

[0075] R 101 to R 116 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or -SiR 132 R 133 R 134 And,

[0076] The above R132 to R 134 Each is independently a C1 to C6 alkyl group, and

[0077] R 101 to R 116 At least one of them is a functional group represented by the following chemical formula V-1, and

[0078] L 100 It is a bidentate ligand of a monovalent anion that coordinates to iridium through lone pairs of electrons on carbon or heteroatoms, and

[0079] m14 and m15 are independently any one of integers from 0 to 3, and m14 + m15 is any one of integers from 1 to 3, and

[0080] [Chemical Formula V-1]

[0081]

[0082] In the above chemical formula V-1,

[0083] R 135 to R 139 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or -SiR 132 R 133 R 134 And,

[0084] * represents the part connected to the carbon atom.

[0085] For example, it may include a dopant represented by the following chemical formula Z-1.

[0086] [Chemical Formula Z-1]

[0087]

[0088] In the above chemical formula Z-1, rings A, B, C, and D each independently represent a pentagonal or hexagonal carbocyclic or heterocyclic ring;

[0089] R A , R B , RC , and R D Each independently represents a uniform, bisubstitution, trisubstitution, or quadruple substitution, or no substitution;

[0090] L B , L C , and L D Each is independently selected from the group consisting of direct bonding, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', and combinations thereof;

[0091] If nA is 1, L E is selected from the group consisting of direct bonding, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', and combinations thereof; and when nA is 0, L E is not present;

[0092] R A , R B , R C , R D , R, and R' are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl group, cycloalkyl group, heteroalkyl group, arylalkyl group, alkoxy group, aryloxy group, amino group, silyl group, alkenyl group, cycloalkenyl group, heteroalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxylic acid group, ester group, nitrile group, isonitrile group, sulfanyl group, sulfinyl group, sulfonyl group, phosphino group, and combinations thereof; any adjacent R A , R B , R C , R D , R, and R' are arbitrarily connected to form a ring; X B , X C , X D , and X E are each independently selected from the group consisting of carbon and nitrogen; Q 1 , Q 2 , Q 3 , and Q 4Each represents oxygen or direct bonding.

[0093] The dopant according to one embodiment may be a platinum complex, for example, represented by the following chemical formula VI.

[0094] [Chemical Formula VI]

[0095]

[0096] In the above chemical formula VI,

[0097] X 100 It contains O, S, and NR 131 Selected from among,

[0098] R 117 to R 131 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or -SiR 132 R 133 R 134 And,

[0099] The above R 132 to R 134 Each is independently a C1 to C6 alkyl group, and

[0100] R 117 to R 131 At least one of them is -SiR 132 R 133 R 134 or is a tert-butyl group, and

[0101] The above R 132 to R 134 Each is independently a C1 to C6 alkyl group.

[0102] A composition further comprising a dopant may be, for example, a green light-emitting composition.

[0103] The hole transport layer (32) is a layer for facilitating hole transfer from the anode (10) to the light-emitting layer (31) and blocking electrons, and may be, for example, an amine compound, but is not limited thereto.

[0104] The above amine compound may include, for example, at least one aryl group and / or heteroaryl group. The above amine compound may be represented, for example, by the following formula a or formula b, but is not limited thereto.

[0105] [Chemical formula a] [Chemical formula b]

[0106]

[0107] In the above chemical formula a or b,

[0108] Ar a or Ar g Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and

[0109] Ar a or Ar c At least one of and Ar d or Ar g At least one of them is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and

[0110] 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.

[0111] The above organic light-emitting device may additionally include a hole injection layer (34) in addition to the light-emitting layer.

[0112] The hole injection layer (34) is a layer for facilitating hole injection from the anode (10) to the light-emitting layer (31) and blocking electrons, and can be located between the anode (10) and the hole transport layer (32).

[0113] For example, at least one of the above hole transport layer (32) and hole injection layer (34) may contain at least one of the compounds listed in Group B below, and is different from the first hole transport assist layer and second hole transport assist layer materials described later.

[0114] [Group B]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] In addition to the aforementioned compounds, known compounds and compounds with similar structures described in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. may also be used in the hole transport layer (32) and hole injection layer (34).

[0139] The above hole transport assist layer (33) includes a first hole transport assist layer (33a) adjacent to the hole transport layer and a second hole transport assist layer (33b) adjacent to the light-emitting layer.

[0140] The first hole transport assist layer comprises a first compound represented by a combination of the following chemical formulas 1 and 2, and the second hole transport assist layer comprises a second compound represented by the following chemical formula 3.

[0141] [Chemical Formula 1] [Chemical Formula 2]

[0142]

[0143] In the above Chemical Formulas 1 and 2,

[0144] a1* to a4* of Chemical Formula 1 are each independently connected carbon (C) or CR a And,

[0145] Among a1* to a4* of Chemical Formula 1, two adjacent ones are each connected to * of Chemical Formula 2, and

[0146] Among a1* to a4* of Chemical Formula 1, the remaining two that are not connected to * of Chemical Formula 2 are CR a And,

[0147] X 1 and X 2 is independently O, S, or CR 3 R 4 And,

[0148] L 1 to L 3Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0149] R a , and R 1 to R 4 Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0150] R 3 and R 4 Each exists independently or is connected to form a substituted or unsubstituted C3 to C10 cycloalkyl group, and

[0151] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a substituted or unsubstituted C6 to C30 arylamine group, and

[0152] m1 is one of integers from 1 to 4, and

[0153] m2 is one of integers from 1 to 3;

[0154] [Chemical Formula 3]

[0155]

[0156] In the above chemical formula 3,

[0157] X 3 is O, S, or CR 7 R 8 And,

[0158] L 4 to L 6 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0159] R 5 to R8 Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C2 to C30 heterocyclic group, and

[0160] R 7 and R 8 Each exists independently or is connected to form a substituted or unsubstituted C3 to C10 cycloalkyl group, and

[0161] Ar 3 and Ar 4 Each is independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0162] m3 is one of integers from 1 to 4, and

[0163] m4 is one of the integers 1 to 3.

[0164] An organic light-emitting device according to one embodiment can have low driving voltage, high efficiency, and improved lifespan characteristics by applying a combination of two hole transport assisting layers at the interface between a hole transport layer and a light-emitting layer, thereby balancing the charge within the light-emitting layer by controlling the hole injection capability in the first hole transport assisting layer and balancing the hole and electron densities by blocking electrons in the second hole transport assisting layer.

[0165] If the above m1 is 2 or more, each R 1 They may be the same or different from each other.

[0166] In the case where the above m2 is 2 or more, each R 2 They may be identical or different from each other.

[0167] For example, the above Ar 1 and Ar 2Each 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 spirofluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazoleyl group, a substituted or unsubstituted diphenylamine group, or a substituted or unsubstituted spirofluoren-xanthenyl group.

[0168] As a specific example, the aforementioned Ar 1 and Ar 2 Each 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 dibenzothiophenyl group, or a substituted or unsubstituted diphenylamine group.

[0169] For example, the above L 1 to L 3 Each may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0170] As a specific example, the above L 1 is a single bond, and L 2 and L 3 Each may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0171] For example, the above R 1 and R 2 Each may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0172] For example, the above R 3 and R 4Each may be an independently substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0173] For example, the above L 2 -Ar 1 and L 3 -Ar 2 Each can be independently selected from the substituents listed in Group I below.

[0174] [Group I]

[0175]

[0176] In the above Group I,

[0177] R 9 to R 13 Each is independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, and

[0178] m9 is one of integers from 1 to 4, and

[0179] m10 is one of integers from 1 to 7, and

[0180] m11 is one of integers from 1 to 3, and

[0181] m12 is an integer of 1 or 2, and

[0182] m13 is one of integers from 1 to 5, and

[0183] * is a connection point.

[0184] If the above m9 is 2 or more, each R 9 They may be identical or different from each other.

[0185] If the above m10 is 2 or greater, each R 10 They may be the same or different from each other.

[0186] If the above m11 is 2 or more, each R 11 They may be the same or different from each other.

[0187] If the above m12 is 2 or more, each R 12 They may be identical or different from each other.

[0188] If the above m13 is 2 or more, each R 13 They may be the same or different from each other.

[0189] The first compound may be represented by any one of the following formulas 1A to 1F, for example, depending on the fusion positions of formulas 1 and 2.

[0190] [Chemical Formula 1A] [Chemical Formula 1B]

[0191]

[0192] [Chemical Formula 1C] [Chemical Formula 1D]

[0193]

[0194] [Chemical Formula 1E] [Chemical Formula 1F]

[0195]

[0196] In the above chemical formulas 1A to 1F,

[0197] X 1 , X 2 , R 1 , R 2 , L 1 to L 3 , Ar 1 , Ar 2 The definitions of , m1 and m2 are as previously stated, and R a1 to R a4 is R a It is the same as the definition of.

[0198] For example, the first compound can be represented by the above chemical formula 1A or chemical formula 1F.

[0199] The above chemical formula 1A can be expressed as any one of the following chemical formulas 1A-1 to 1A-4.

[0200] [Chemical Formula 1A-1] [Chemical Formula 1A-2]

[0201]

[0202] [Chemical Formula 1A-3] [Chemical Formula 1A-4]

[0203]

[0204] In the above chemical formulas 1A-1 to 1A-4, X 1 , X 2 , R 1 , R 2 , R a1 , R a4 , L 1 to L 3 , Ar 1 , Ar 2 The definitions of , m1 and m2 are as described above.

[0205] The above chemical formula 1F can be expressed as any one of the following chemical formulas 1F-1 to 1F-4.

[0206] [Chemical Formula 1F-1] [Chemical Formula 1F-2]

[0207]

[0208] [Chemical Formula 1F-3] [Chemical Formula 1F-4]

[0209]

[0210] In the above chemical formulas 1A-1 to 1A-4 and chemical formulas 1F-1 to 1F-4, X 1 , X 2 , R 1 , R 2 , R a1 , R a2 , L 1 to L 3 , Ar 1 , Ar 2 The definitions of , m1 and m2 are as described above.

[0211] In one embodiment, the X 1 and X 2 At least one of them can be O.

[0212] In one embodiment, the R 3 and R 4Each can exist independently or be connected to form substituted or unsubstituted cyclopentyl groups.

[0213] For example, the first compound may be one selected from the compounds listed in Group 1 below, but is not limited thereto.

[0214] [Group 1]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407]

[0408]

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418]

[0419]

[0420]

[0421]

[0422]

[0423]

[0424]

[0425]

[0426]

[0427]

[0428]

[0429]

[0430]

[0431]

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443]

[0444]

[0445]

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452] If the above m3 is 2 or greater, each R 5 They may be identical or different from each other.

[0453] If the above m4 is 2 or more, each R 6 They may be the same or different from each other.

[0454] For example, the above Ar 3 and Ar 4 Each 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 spirofluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilolyl group.

[0455] As a specific example, the aforementioned Ar 3 and Ar 4Each 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 dibenzothiophenyl group.

[0456] For example, the above L 4 to L 6 Each may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0457] As a specific example, the above L 4 is a single bond, and L 5 and L 6 Each may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0458] For example, the above R 5 and R 6 Each may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0459] For example, the above R 7 and R 8 Each may be an independently substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0460] For example, the above L 5 -Ar 3 and L 6 -Ar 4 Each can be independently selected from the substituents listed in Group II below.

[0461] [Group II]

[0462]

[0463] In the above Group II,

[0464] R 14 to R 18Each is independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, and

[0465] m14 is one of integers from 1 to 4, and

[0466] m15 is one of integers from 1 to 7, and

[0467] m16 is one of integers from 1 to 3, and

[0468] m17 is an integer of 1 or 2, and

[0469] m18 is one of integers from 1 to 5, and

[0470] * is a connection point.

[0471] The second compound can be represented by any one of the following chemical formulas 3-1 to 3-4, depending on the substitution position of the amine group.

[0472] [Chemical Formula 3-1] [Chemical Formula 3-2]

[0473]

[0474] [Chemical Formula 3-3] [Chemical Formula 3-4]

[0475]

[0476] In the above chemical formulas 3-1 to 3-4,

[0477] X 3 , L 4 to L 6 , R 5 , R 6 , Ar 3 , Ar 4 The definitions of , m3 and m4 are as described above.

[0478] For example, the second compound can be represented by the above chemical formula 3-1 or chemical formula 3-3.

[0479] For example, the above R 7 and R 8Each can exist independently or be connected to form substituted or unsubstituted cyclopentyl groups.

[0480] For example, the second compound may be one selected from the compounds listed in Group 2 below, but is not limited thereto.

[0481] [Group 2]

[0482]

[0483] [G-1] [G-2] [G-3] [G-4] [G-5]

[0484]

[0485] [G-6] [G-7] [G-8] [G-9] [G-10]

[0486]

[0487] [G-11] [G-12] [G-13] [G-14] [G-15]

[0488]

[0489] [G-16] [G-17] [G-18] [G-19] [G-20]

[0490]

[0491] [G-21] [G-22] [G-23] [G-24] [G-25]

[0492]

[0493] [G-26] [G-27] [G-28] [G-29] [G-30]

[0494]

[0495] [G-31] [G-32] [G-33] [G-34] [G-35]

[0496]

[0497] [G-36] [G-37] [G-38] [G-39] [G-40]

[0498]

[0499] [G-41] [G-42] [G-43] [G-44] [G-45]

[0500]

[0501] [G-46] [G-47] [G-48] [G-49] [G-50]

[0502]

[0503] [G-51] [G-52] [G-53] [G-54] [G-55]

[0504]

[0505] [G-56] [G-57] [G-58] [G-59] [G-60]

[0506]

[0507] [G-61] [G-62] [G-63] [G-64] [G-65]

[0508]

[0509] [G-66] [G-67] [G-68] [G-69] [G-70]

[0510]

[0511] [G-71] [G-72] [G-73] [G-74] [G-75]

[0512]

[0513] [G-76] [G-77] [G-78] [G-79] [G-80]

[0514]

[0515] [G-81] [G-82] [G-83] [G-84] [G-85]

[0516]

[0517] [G-86] [G-87] [G-88] [G-89] [G-90]

[0518]

[0519] [G-91] [G-92] [G-93] [G-94] [G-95]

[0520]

[0521] [G-96] [G-97] [G-98] [G-99] [G-100]

[0522]

[0523] [G-101] [G-102] [G-103] [G-104] [G-105]

[0524]

[0525] [G-106] [G-107] [G-108] [G-109] [G-110]

[0526]

[0527] [G-111] [G-112] [G-113] [G-114] [G-115]

[0528]

[0529] [G-116] [G-117] [G-118] [G-119] [G-120]

[0530]

[0531] [G-121] [G-122] [G-123] [G-124] [G-125]

[0532]

[0533] [G-126] [G-127] [G-128] [G-129] [G-130]

[0534]

[0535] [G-131] [G-132] [G-133] [G-134] [G-135]

[0536]

[0537] [G-136] [G-137] [G-138] [G-139] [G-140]

[0538]

[0539] [G-141] [G-142] [G-143] [G-144] [G-145]

[0540]

[0541] [G-146] [G-147] [G-148] [G-149] [G-150]

[0542]

[0543] [G-151] [G-152] [G-153] [G-154] [G-155]

[0544]

[0545] [G-156] [G-157] [G-158] [G-159] [G-160]

[0546]

[0547] [G-161] [G-162] [G-163] [G-164] [G-165]

[0548]

[0549] [G-166] [G-167] [G-168] [G-169] [G-170]

[0550]

[0551] [G-171] [G-172] [G-173] [G-174] [G-175]

[0552]

[0553] [G-176] [G-177] [G-178] [G-179] [G-180]

[0554]

[0555] [G-181] [G-182] [G-183] [G-184] [G-185]

[0556]

[0557] [G-186] [G-187] [G-188] [G-189] [G-190]

[0558]

[0559] [G-191] [G-192] [G-193] [G-194] [G-195]

[0560]

[0561] [G-196] [G-197] [G-198] [G-199] [G-200]

[0562]

[0563] [G-201] [G-202] [G-203] [G-204] [G-205]

[0564]

[0565] [G-206] [G-207] [G-208] [G-209] [G-210]

[0566]

[0567] [G-211] [G-212] [G-213] [G-214] [G-215]

[0568]

[0569] [G-216] [G-217] [G-218] [G-219] [G-220]

[0570]

[0571] [G-221] [G-222] [G-223] [G-224] [G-225]

[0572]

[0573] [G-226] [G-227] [G-228] [G-229] [G-230]

[0574]

[0575] [G-231] [G-232] [G-233] [G-234] [G-235]

[0576]

[0577] [G-236] [G-237] [G-238] [G-239] [G-240]

[0578]

[0579] [G-241] [G-242] [G-243] [G-244] [G-245]

[0580]

[0581] [G-246] [G-247] [G-248] [G-249] [G-250]

[0582]

[0583] [G-251] [G-252] [G-253] [G-254] [G-255]

[0584]

[0585] [G-256] [G-257] [G-258] [G-259] [G-260]

[0586]

[0587] [G-261] [G-262] [G-263] [G-264] [G-265]

[0588]

[0589] [G-266] [G-267] [G-268] [G-269] [G-270]

[0590]

[0591] [G-271] [G-272] [G-273] [G-274] [G-275]

[0592]

[0593] [G-276] [G-277] [G-278] [G-279] [G-280]

[0594]

[0595] [G-281] [G-282] [G-283] [G-284] [G-285]

[0596]

[0597] [G-286] [G-287] [G-288 [G-289] [G-290]

[0598]

[0599] [G-291] [G-292] [G-293] [G-294] [G-295]

[0600]

[0601] [G-296] [G-297] [G-298] [G-299] [G-300]

[0602]

[0603] [G-301] [G-302] [G-303] [G-304] [G-305]

[0604]

[0605] [G-306] [G-307] [G-308] [G-309] [G-310]

[0606]

[0607] [G-311] [G-312] [G-313] [G-314] [G-315]

[0608]

[0609] [G-316] [G-317] [G-318] [G-319] [G-320]

[0610]

[0611] [G-321] [G-322] [G-323] [G-324] [G-325]

[0612]

[0613] [G-326] [G-327] [G-328] [G-329] [G-330]

[0614]

[0615] [G-331] [G-332] [G-333] [G-334] [G-335]

[0616]

[0617] [G-336] [G-337] [G-338] [G-339] [G-340]

[0618]

[0619] [G-341] [G-342] [G-343] [G-344] [G-345]

[0620]

[0621] [G-346] [G-347] [G-348] [G-349] [G-350]

[0622]

[0623] [G-351] [G-352] [G-353] [G-354] [G-355]

[0624]

[0625] [G-356] [G-357] [G-358] [G-359] [G-360]

[0626]

[0627] [G-361] [G-362] [G-363] [G-364] [G-365]

[0628]

[0629] [G-366] [G-367] [G-368] [G-369] [G-370]

[0630]

[0631] [G-371] [G-372] [G-373] [G-374] [G-375]

[0632]

[0633] [G-376] [G-377] [G-378] [G-379] [G-380]

[0634]

[0635] [G-381] [G-382] [G-383] [G-384] [G-385]

[0636]

[0637] [G-386] [G-387] [G-388] [G-389] [G-390]

[0638]

[0639] [G-391] [G-392] [G-393] [G-394] [G-395]

[0640]

[0641] [G-396] [G-397] [G-398] [G-399] [G-400]

[0642]

[0643] [G-401] [G-402] [G-403] [G-404] [G-405]

[0644]

[0645] [G-406] [G-407] [G-408] [G-409] [G-410]

[0646]

[0647] [G-411] [G-412] [G-413] [G-414] [G-415]

[0648]

[0649] [G-416] [G-417] [G-418] [G-419] [G-420]

[0650]

[0651] [G-421] [G-422] [G-423] [G-424] [G-425]

[0652] In a specific embodiment, the first compound is represented by any one of the following formulas 1A-2 to 1A-4 and formulas 1F-2 to 1F-4, and

[0653] The above second compound can be represented by the following chemical formula 3-1 or chemical formula 3-3.

[0654] The above organic layer (30) may include an electron transport region.

[0655] The above electron transport region (150) can further increase electron injection and / or electron mobility between the cathode (20) and the light-emitting layer (31) and block holes.

[0656] 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 below may be included in at least one of the electron transport layer (35) and the electron transport auxiliary layer.

[0657] [Group C]

[0658]

[0659]

[0660]

[0661]

[0662]

[0663]

[0664]

[0665]

[0666]

[0667]

[0668]

[0669]

[0670]

[0671]

[0672]

[0673]

[0674]

[0675] One embodiment may be an organic light-emitting device comprising a light-emitting layer (31), a hole transport layer (32), a first hole transport layer (33a), and a second hole transport layer (33b) as organic layers.

[0676] Another embodiment may be an organic light-emitting device that additionally includes a hole injection layer as an organic layer.

[0677] Another embodiment may be an organic light-emitting device that additionally includes an electron transport region as an organic layer.

[0678] Meanwhile, the organic light-emitting device may additionally include an electron injection layer (not shown), etc., in addition to the light-emitting layer as the aforementioned organic layer.

[0679] An organic light-emitting diode can be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film deposition method such as vacuum evaporation, sputtering, plasma plating, and ion plating, and then forming a cathode or anode thereon.

[0680] The above-described organic light-emitting element can be applied to an organic light-emitting display device.

[0682] The above-described embodiment will be explained in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0683] Unless otherwise noted, the starting materials and reactants used in the following examples and synthesis examples were purchased from Sigma-Aldrich, TCI, Tokyo Chemical Industry, or P&H Tech, or synthesized using known methods.

[0685] (Preparation of the first compound)

[0686] Synthesis Example 1: Synthesis of Compound A-85

[0687]

[0688] Sub-1a (5 g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2a (5.95 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 6.84 g of compound A-85 (yield 68%).

[0690] Synthesis Example 2: Synthesis of Compound F-10

[0691]

[0692] Sub-1b (5g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2a (5.95 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 7.21 g of compound F-10 (yield 71%).

[0694] Synthesis Example 3: Synthesis of Compound F-22

[0695]

[0696] Sub-1b (5g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2b (5.29 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 6.95 g of compound F-22 (yield 73%).

[0698] Synthesis Example 4: Synthesis of Compound F-160

[0699]

[0700] Sub-1b (5 g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2c (6.79 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 7.45 g of compound F-160 (yield 68%).

[0702] Synthesis Example 5: Synthesis of Compound F-25

[0703]

[0704] Sub-1b (5 g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2d (6.79 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 6.91 g of compound F-25 (yield 63%).

[0706] Synthesis Example 6: Synthesis of Compound F-215

[0707]

[0708] Sub-1c (5 g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2e (6.18 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 6.41 g of compound F-215 (yield 62%).

[0710] Synthesis Example 7: Synthesis of Compound F-246

[0711]

[0712] Sub-1d (5 g, 15.7 mmol) was dissolved in toluene (80 mL), then sub-2f (5.52 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 7.13 g of compound F-246 (yield 74%).

[0714] Synthesis Example 8: Synthesis of Compound F-275

[0715]

[0716] Sub-1e (5 g, 17.1 mmol) was dissolved in toluene (85 mL), then sub-2a (6.48 g, 17.9 mmol), NaOtBu (2.46 g, 25.6 mmol), Pd2(dba)3 (0.78 g, 0.9 mmol), and P(tBu)3 (1.23 mL, 2.54 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 6.96 g of compound F-275 (yield 66%).

[0718] Synthesis Example 9: Synthesis of Compound F-276

[0719]

[0720] Sub-1c (5 g, 15.7 mmol) was dissolved in toluene (78 mL), then sub-2a (5.93 g, 16.5 mmol), NaOtBu (2.26 g, 23.5 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol), and P(tBu)3 (1.13 mL, 2.4 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 8.12 g of compound F-276 (yield 80%).

[0722] Synthesis Example 10: Synthesis of Compound PA-1

[0723]

[0724] Sub-1f (5 g, 21.5 mmol) was dissolved in toluene (107 mL), then sub-2g (9.04 g, 22.5 mmol), NaOtBu (3.09 g, 32.2 mmol), Pd2(dba)3 (0.98 g, 1.1 mmol), and P(tBu)3 (1.55 mL, 3.2 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 8.93 g of compound PA-1 (yield 75%).

[0726] (Preparation of the second compound)

[0727] Synthesis Example 11: Synthesis of Compound G-19

[0728]

[0729] Sub-1g (5 g, 24.7 mmol) was dissolved in toluene (123 mL), then sub-2h (13.6 g, 25.9 mmol), NaOtBu (3.56 g, 37.0 mmol), Pd2(dba)3 (1.13 g, 1.2 mmol), and P(tBu)3 (1.78 mL, 3.7 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 7.88 g of compound G-19 (yield 46%).

[0731] Synthesis Example 12: Synthesis of Compound G-139

[0732]

[0733] Sub-1g (5g, 17.9 mmol) was dissolved in toluene (89 mL), then sub-1b (6.81 g, 18.8 mmol), NaOtBu (2.58 g, 26.9 mmol), Pd2(dba)3 (0.82 g, 0.9 mmol), and P(tBu)3 (1.30 mL, 2.7 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 7.57 g of compound G-139 (yield 70%).

[0735] Synthesis Example 13: Synthesis of Compound G-410

[0736]

[0737] Sub-1f (5 g, 21.6 mmol) was dissolved in toluene (107 mL), then sub-1b (11.89 g, 22.6 mmol), NaOtBu (3.11 g, 32.3 mmol), Pd2(dba)3 (0.99 g, 1.1 mmol), and P(tBu)3 (1.56 mL, 3.2 mmol) were added, and the mixture was refluxed for 3 hours. After the reaction was complete, the mixture was extracted with CH2Cl2 and water, the organic layer was dried with MgSO4 and concentrated, and the resulting compound was separated using a silica gel column and recrystallized to obtain 10.53 g of compound G-410 (yield 72%).

[0739] Example 1

[0740] A glass substrate coated with a thin film of ITO / Ag / ITO was cleaned with distilled water ultrasonics. After the distilled water cleaning was finished, the substrate was ultrasonically cleaned with a solvent such as acetone or isopropyl alcohol, dried, transferred to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and then transferred to a vacuum deposition machine. Using the prepared ITO / Ag / ITO (reflective electrode) as the anode, a 100 Å thick hole injection layer was formed by vacuum depositing compound A doped with 3% NDP-9 (commercially available from Novaled) on the ITO / Ag / ITO substrate, and a hole transport layer was formed by depositing compound A to a thickness of 1350 Å on top of the hole injection layer. A first hole transport auxiliary layer was formed by depositing compound F-22 of Synthesis Example 3 to a thickness of 285 Å on the above hole transport layer, and a second hole transport auxiliary layer was formed by depositing compound G-410 of Synthesis Example 13 to a thickness of 50 Å on the above first hole transport auxiliary layer. Host H1 (40%) and host H2 (60%) were used as hosts, and a 380 Å thick emissive layer was formed by vacuum deposition using 15 wt% PtGD as a dopant. Subsequently, an electron transport auxiliary layer was formed by depositing compound C to a thickness of 50 Å on the above emissive layer, and an electron transport layer to a thickness of 310 Å was formed by vacuum deposition of compound D and Liq simultaneously in a weight ratio of 1:1. An organic light-emitting diode was fabricated by forming a cathode by sequentially vacuum depositing Yb and AgMg on the above electron transport layer.

[0741] It was fabricated with the structure ITO / Ag / ITO / Compound A (3% NDP-9 doping, 100Å) / Compound A (1350Å) / First hole transport assist layer (285Å) / Second hole transport assist layer (50Å) / Emitting layer [Host (85wt%, Host H1, Host H2): PtGD (15wt%)] (380Å) / Compound C (50Å) / Compound D : Liq (310Å) / Yb / AgMg.

[0742] Compound A: N-(9,9-diphenyl-9H-fluoren-2-yl)-N,9-diphenyl-9H-carbazol-2-amine

[0743] Compound C: 4-{4-[3-(9,9-dimethyl-9H-fluoren-4-yl)phenyl]phenyl}-2-phenyl-6-(4-phenylphenyl)pyrimidine

[0744] Compound D: 2-(4-{2-[4-(diphenyl-1,3,5-triazin-2-yl)phenyl]naphthalen-1-yl}phenyl)-4,6-diphenyl-1,3,5-triazine

[0745] [Host H1] [Host H2] [PtGD]

[0746]

[0748] Examples 2 to 13 and Comparative Examples 1 to 5

[0749] An organic light-emitting diode was fabricated using the same method as in Example 1, except that the composition was changed to the one listed in Table 1 below.

[0751] evaluation

[0752] The driving voltage, luminous efficiency, and lifespan characteristics of organic light-emitting diodes according to Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated.

[0753] The specific measurement method is as follows, and the results are shown in Table 1.

[0754] (1) Measurement of change in current density according to voltage change

[0755] For the fabricated organic light-emitting diode, the current flowing through the unit element was measured using a current-voltage meter (Keithley 2400) while increasing the voltage from 0V to 10V, and the result was obtained by dividing the measured current value by the area.

[0756] (2) Measurement of change in brightness according to voltage change

[0757] For the fabricated organic light-emitting diode, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0V to 10V, and the results were obtained.

[0758] (3) Measurement of luminous efficiency

[0759] Using the luminance, current density, and voltage measured from (1) and (2) above, the same current density (10 mA / cm²) 2 The current efficiency (cd / A) of ) was calculated.

[0760] (4) Life measurement

[0761] Luminance (cd / m²) 2 ) 24,000 cd / m 2 The result was obtained by maintaining it and measuring the time it took for the current efficiency (cd / A) to decrease to 97%.

[0762] The lifespan measurements of Examples 1 to 13 and Comparative Examples 1 to 5 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1 below.

[0763] (5) Driving voltage measurement

[0764] Using a current-voltage meter (Keithley 2400), 15 mA / cm 2 The driving voltage of each component was measured to obtain the results.

[0765] The driving voltages of Examples 1 to 13 and Comparative Examples 1 to 5 were calculated as relative values ​​based on Comparative Example 1 and are listed in Table 1 below.

[0766] No. 1st air transport auxiliary layer Second air transport auxiliary layer Driving voltage (%) Color (ELcolor) life(%) Example 1 F-22 G-410 98 Green 141 Example 2 F-276 G-410 99 Green 122 Example 3 F-215 G-410 98 Green 130 Example 4 F-275 G-410 99 Green 135 Example 5 F-246 G-410 98 Green 115 Example 6 F-10 G-410 98 Green 125 Example 7 F-160 G-410 95 Green 130 Example 8 F-25 G-410 95 Green 138 Example 9 A-85 G-19 98 Green 120 Example 10 F-22 G-19 99 Green 141 Example 11 F-215 G-19 98 Green 120 Example 12 F-275 G-19 99 Green 133 Example 13 F-22 G-139 98 Green 132 Comparative Example 1 PA-1 G-410 100 Green 100 Comparative Example 2 F-22 - 100 Green 52 Comparative Example 3 F-160 - 96 Green 40 Comparative Example 4 F-25 - 97 Green 72 Comparative Example 5 F-246 - 98 Green 76

[0767] Referring to Table 1, it can be seen that the organic light-emitting diodes according to Examples 1 to 13 have significantly improved driving voltage, luminous efficiency, and lifespan characteristics compared to the organic light-emitting diodes according to Comparative Examples 1 to 5. Explanation of the symbols

[0768] 10: Anode 20: Cathode 30: Organic layer 31: Emissive layer 32: Precision Transport Layer 33: Precision Transport Auxiliary Layer 33a: 1st Auxiliary Air Transport Layer 33b: 2nd Auxiliary Air Transport Layer 34: Hole injection layer 35: Electron transport layer

Claims

Claim 1 An organic optoelectronic device comprising an anode and a cathode facing each other, a light-emitting layer located between the anode and the cathode, a hole transport layer located between the anode and the light-emitting layer, and a hole transport assist layer located between the hole transport layer and the light-emitting layer, wherein the hole transport assist layer comprises a first hole transport assist layer adjacent to the hole transport layer and a second hole transport assist layer adjacent to the light-emitting layer, wherein the first hole transport assist layer comprises a first compound represented by the following chemical formula 1F, and the second hole transport assist layer comprises a second compound represented by the following chemical formula 3: [Chemical Formula 1F] In the above chemical formula 1F, X 1 is O or S, and X 2 is O, S, CR 3 R 4 and,L 1 is a single bond, and L 2 and L 3 Each is independently a single bond or a substituted or unsubstituted phenylene group, and R a1 , R a2 , R 1 and R 2 are each independently hydrogen or deuterium, and R 3 and R 4 is a substituted or unsubstituted C1 to C10 alkyl group, and Ar 1 and Ar 2 Each is independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group or a substituted or unsubstituted diphenylamine group, m1 is one of integers 1 to 4, and m2 is one of integers 1 to 3; [Chemical Formula 3] In the above chemical formula 3, X 3 is CR 7 R 8 and, R 7 and R 8 is each independently a substituted or unsubstituted C1 to C10 alkyl group, and L 4 to L 6 Each is independently a single bond or a substituted or unsubstituted phenylene group, and R 5 and R 6 Each is independently hydrogen, deuterium, a substituted or unsubstituted tert-butyl group, or a substituted or unsubstituted phenyl group, and Ar 3 and Ar 4 Each is independently a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group, m3 is one of integers from 1 to 4, and m4 is one of integers from 1 to 3. Claim 2 delete Claim 3 In claim 1, the first compound is an organic optoelectronic device represented by any one of the following chemical formulas 1F-1 to 1F-4: [Chemical Formula 1F-1] [Chemical Formula 1F-2] [Chemical Formula 1F-3] [Chemical Formula 1F-4] In the above chemical formulas 1F-1 to 1F-4, X 1 , X 2 , R 1 , R 2 , R a1 , R a2 , L 1 to L 3 , Ar 1 , Ar 2 , m1 and m2 are as defined in Paragraph 1. Claim 4 delete Claim 5 delete Claim 6 In paragraph 1, the above L 2 -Ar 1 and L 3 -Ar 2 Organic optoelectronic device in which each is independently selected from the substituents listed in Group I below: [Group I] In the above Group I, R 9 , R 11 and R 13 Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C12 aryl group, m9 is one of integers from 1 to 4, m11 is one of integers from 1 to 3, m13 is one of integers from 1 to 5, and * is a connecting point. Claim 7 In claim 1, the organic optoelectronic device wherein the first compound is one selected from the compounds listed in Group 1 below: [Group 1] . Claim 8 In claim 1, the second compound is an organic optoelectronic device represented by any one of the following chemical formulas 3-1 to 3-4: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] In the above chemical formulas 3-1 to 3-4, X 3 , L 4 to L 6 , R 5 , R 6 , Ar 3 , Ar 4 The definitions of , m3 and m4 are the same as the definitions of Chemical Formula 3. Claim 9 delete Claim 10 In paragraph 1, the above L 5 -Ar 3 and L 6 -Ar 4 Organic optoelectronic device in which each is independently selected from the substituents listed in Group II below: [Group II] In the above Group II, R 14 , R 16 and R 18 Each is independently hydrogen, deuterium, cyano group, substituted or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C12 aryl group, m14 is one of integers 1 to 4, m16 is one of integers 1 to 3, m18 is one of integers 1 to 5, and * is a connecting point. Claim 11 In claim 1, the second compound is an organic optoelectronic device selected from the compounds listed in Group 2 below: [Group 2] [G-1] [G-4] [G-7] [G-10] [G-13] [G-15] [G-16] [G-17] [G-18] [G-19] [G-20] [G-23] [G-27] [G-29] [G-31] [G-38] [G-43] [G-44] [G-47] [G-49] [G-50] [G-51] [G-52] [G-57] [G-59] [G-61] [G-63] [G-66] [G-69] [G-72] [G-74] [G-79] [G-80] [G-81] [G-82] [G-85] [G-87] [G-89] [G-90] [G-94] [G-95] [G-98] [G-101] [G-104] [G-107] [G-108] [G-114] [G-115] [G-117] [G-119] [G-120] [G-121] [G-124] [G-125] [G-128] [G-129] [G-133] [G-136] [G-139] [G-141] [G-142] [G-147] [G-148] [G-150] [G-151] [G-152] [G-153] [G-156] [G-159] [G-160] [G-161] [G-165] [G-166] [G-168] [G-170] [G-177] [G-178] [G-179] [G-180] [G-182] [G-183] [G-186] [G-187] [G-188] [G-190] [G-191] [G-194] [G-197] [G-201] [G-203] [G-205] [G-212] [G-214] [G-216] [G-217] [G-219] [G-221] [G-223] [G-229] [G-231] [G-233] [G-237] [G-240] [G-244] [G-245] [G-246] [G-247] [G-249] [G-254] [G-256] [G-258] [G-261] [G-266] [G-267] [G-269] [G-271] [G-272] [G-274] [G-275] [G-277] [G-282] [G-285] [G-286] [G-288] [G-292] [G-294] [G-299] [G-300] [G-302] [G-303] [G-305] [G-306] [G-313] [G-316] [G-318] [G-324] [G-327] [G-329] [G-330] [G-332] [G-333] [G-334] [G-337] [G-340] [G-341] [G-355] [G-356] [G-357] [G-358] [G-359] [G-360] [G-361] [G-362] [G-363] [G-364] [G-365] [G-366] [G-367] [G-368] [G-369] [G-370] [G-371] [G-372] [G-373] [G-374] [G-375] [G-376] [G-377] [G-379] [G-380] [G-381] [G-383] [G-384] [G-385] [G-386] [G-387] [G-388] [G-389] [G-390] [G-391] [G-392] [G-393] [G-394] [G-395] [G-396] [G-397] [G-398] [G-399] [G-400] [G-402] [G-403] [G-404] [G-405] [G-406] [G-407] [G-408] [G-409] [G-410] [G-412] [G-413] [G-414] [G-415] [G-416] [G-417] [G-418] [G-419] [G-420] [G-421] [G-422] [G-423] [G-424]. Claim 12 An organic optoelectronic device according to claim 1, wherein the first compound is represented by any one of the following chemical formulas 1F-2 to 1F-4, and the second compound is represented by the following chemical formula 3-1 or chemical formula 3-3: [Chemical formula 1F-2] [Chemical Formula 1F-3] [Chemical Formula 1F-4] In the above chemical formulas 1F-2 to 1F-4, X 1 , X 2 , R 1 , R 2 , R a1 , R a2 , L 1 to L 3 , Ar 1 , Ar 2 , m1 and m2 are as defined in Clause 1; [Chemical Formula 3-1] [Chemical Formula 3-3] In the above chemical formulas 3-1 and 3-3, X 3 , L 4 to L 6 , R 5 , R 6 , Ar 3 , Ar 4 , m3 and m4 are as defined in Paragraph 1. Claim 13 A display device comprising an organic optoelectronic element according to any one of claims 1, 3, 6 through 8, and 10 through 12.

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