Compound for organic optoelectronic diode, organic optoelectronic diode and display device

Abstract

The present invention relates to: a compound for an organic optoelectronic diode represented by chemical formula 1; and an organic optoelectronic diode and a display device comprising the same. The details of the chemical formula 1 are as defined in the specification.

Description

Technical Field

[0001] Disclosed are a compound for an organic optoelectronic device, an organic optoelectronic device, and a display device. Background Art

[0002] Organic optoelectronic devices (organic optoelectronic diodes) are devices that can convert electrical energy into light and vice versa.

[0003] Organic optoelectronic devices can be mainly divided into two types according to the operating principle. One is a photoelectric device that generates electrical energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively, 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 photoelectric devices, organic light emitting diodes, organic solar cells, and organic photoconductors.

[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 organic materials between electrodes. Summary of the invention

[0006] Technical issues

[0007] One embodiment provides a compound for an organic optoelectronic device, which can realize an organic optoelectronic device with high efficiency and long lifetime.

[0008] Another embodiment provides an organic optoelectronic device including the compound for an organic optoelectronic device.

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

[0010] Technical Solution

[0011] According to one embodiment, a compound for an organic optoelectronic device represented by Chemical Formula 1 is provided.

[0012] [Chemical formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0016] Ar3 is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0017] R 1 To R 6 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C6 to C30 heterocyclic,

[0018] n1, n3, n5 and n6 are each independently an integer from 1 to 4,

[0019] n2 is an integer from 1 to 3, and

[0020] n4 is an integer from 1 to 5.

[0021] According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other and at least one organic layer between the anode and the cathode, wherein the organic layer includes a light emitting layer and the light emitting layer includes the above-mentioned compound for an organic optoelectronic device.

[0022] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0023] Beneficial Effects

[0024] High-efficiency and long-life organic optoelectronic devices can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0026] <Description of Reference Numerals>

[0027] 100: Organic light-emitting diode

[0028] 105: Organic layer

[0029] 110: cathode

[0030] 120: Anode

[0031] 130: Luminous layer

[0032] 140: Hole transport zone

[0033] 150: Electron transport region DETAILED DESCRIPTION

[0034] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

[0035] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

[0036] In one example of the present invention, "substituted" means that at least one hydrogen 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 a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl or cyano. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, cyano. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl or naphthyl.

[0037] In the present specification, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0038] In the present specification, "hydrogen substitution (-H)" may include "deuterium substitution (-D)" or "tritium substitution (-T)".

[0039] In the present specification, when a definition is not otherwise provided, "hetero" means including one to three hetero atoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0040] In the present specification, "aryl" refers to a group including at least one hydrocarbon aromatic portion, and all elements of the hydrocarbon aromatic portion have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic portions may be connected by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic portions are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl.

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

[0042] As used herein, "heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si in place of carbon (C) in cyclic compounds such as aryl, cycloalkyl, their condensed rings or combinations thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms.

[0043] For example, "heteroaryl" may refer to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl includes two or more rings, the two or more rings may be fused. When the heteroaryl is a fused ring, each ring may include 1 to 3 heteroatoms.

[0044] 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 pyrene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted para-terphenyl group, a substituted or unsubstituted meta-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 peryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

[0045] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl, 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 invention may include quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted benzofuranofluorenyl, substituted or unsubstituted benzothienofluorenyl, or a combination thereof, but is not limited thereto.

[0046] 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.

[0047] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied, and electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive property according to the lowest unoccupied molecular orbital (LUMO) energy level.

[0048] Hereinafter, a compound for an organic optoelectronic device according to one embodiment is described.

[0049] The compound for an organic optoelectronic device according to one embodiment is represented by Chemical Formula 1.

[0050] [Chemical formula 1]

[0051]

[0052] In Chemical Formula 1,

[0053] Ar 1 and Ar 2are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0054] Ar 3 is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

[0055] R 1 To R 6 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C6 to C30 heterocyclic,

[0056] n1, n3, n5 and n6 are each independently an integer from 1 to 4,

[0057] n2 is an integer from 1 to 3, and

[0058] n4 is an integer from 1 to 5.

[0059] The compound represented by Chemical Formula 1 has a structure in which an amine core is substituted with dibenzosilole, diphenylfluorene, and an aryl group (or heteroaryl group), and the planarity of the molecule is increased, thereby improving lattice packing and increasing glass transition temperature and hole mobility.

[0060] Since dibenzosilole has high heat resistance and fast hole transport capability, it is desirable in realizing a device that reduces operating voltage to improve power efficiency and has excellent lifespan characteristics.

[0061] Because diphenylfluorene has little electrical and electronic interaction with neighboring molecules due to its molecular size, it can reduce electrical and electronic interaction with neighboring layers, thereby enabling devices with improved device lifetime and efficiency.

[0062] Furthermore, because dibenzosilole and diphenylfluorene are included simultaneously, molecular motion is restricted, resulting in a high glass transition temperature, which can prevent degradation of device performance due to heat generation during operation.

[0063] In particular, when amine is substituted at the 3-position of dibenzosilole, dibenzosilole is oriented in the para configuration and, in this case, is in the HOMO position in the entire dibenzosilole structure compared to the meta configuration, which facilitates hole transport between molecules, thereby reducing the operating voltage of the device and improving its lifetime.

[0064] For example, as described below, the optimized molecular structures and resulting HOMO electron clouds according to the para orientation (where the amine is substituted at the 3-position of the dibenzosilole) and the meta orientation (where the amine is substituted at the 2-position of the dibenzosilole) are compared.

[0065]

[0066] It can be demonstrated that the para-orientation of dibenzosilole significantly improves the hole mobility compared to the meta-orientation of dibenzosilole, resulting in improved operating voltage, efficiency and lifetime.

[0067] Chemical Formula 1 may be represented by any one of Chemical Formula 1-I to Chemical Formula 1-III depending on the connection point between the amine and the diphenylfluorene.

[0068]

[0069] In Chemical Formula 1-I to Chemical Formula 1-III,

[0070] Ar 1 To Ar 3 , R 1 To R 6 And n1 to n6 are the same as above.

[0071] For example, Ar 3 It may 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 chrysene group, a substituted or unsubstituted fluorenyl 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.

[0072] As a specific example, Ar 3 It may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted dibenzosilyl group.

[0073] For example, Ar 3 The substituents may be selected from the substituents listed in Group I, but are not limited thereto.

[0074] [Group I]

[0075]

[0076]

[0077] For example, Ar 1 and Ar 2 Each may independently be a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.

[0078] For example, Ar 1and Ar 2 Each may independently be a substituted or unsubstituted methyl group or a substituted or unsubstituted phenyl group.

[0079] For example, R 1 To R 6 Each may independently be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl.

[0080] For example, R 1 To R 6 They may each independently be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C5 alkyl, or substituted or unsubstituted C6 to C12 aryl.

[0081] As a more specific example, R 1 To R 6 and may each independently be hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, or substituted or unsubstituted phenyl.

[0082] For example, Chemical Formula 1 may be selected from Chemical Formula 1-1 to Chemical Formula 1-6, but is not limited thereto.

[0083]

[0084]

[0085] In Chemical Formula 1-1 to Chemical Formula 1-6,

[0086] Ar 1 To Ar 3 , R 1 To R 6 and n2 to n6 are the same as described above, and n1′, n3′, n5′ and n6′ are each independently an integer of 1 or 2.

[0087] For example, Chemical Formula 1 may be selected from Chemical Formula 2-1 to Chemical Formula 2-9, but is not limited thereto.

[0088]

[0089] In Chemical Formulae 2-1 to 2-9, Ar 1 To Ar 3 Same as above.

[0090] For example, the compound for an organic optoelectronic device represented by Chemical Formula 1 may include compounds listed in Group 1, but is not limited thereto.

[0091] [Group 1]

[0092] [Table 1]

[0093]

[0094] [Table 2]

[0095]

[0096]

[0097] [Table 3]

[0098]

[0099] [Table 4]

[0100]

[0101]

[0102] [Table 5]

[0103]

[0104] [Table 6]

[0105]

[0106]

[0107] [Table 7]

[0108]

[0109] [Table 8]

[0110]

[0111]

[0112] [Table 9]

[0113]

[0114] 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 photoconductor.

[0115] Herein, an organic light emitting diode as one example of an organic optoelectronic device is described with reference to the accompanying drawings.

[0116] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0117] Reference Figure 1 , an organic light emitting diode 100 according to one embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110 .

[0118] The anode 120 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 120 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or the like, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0119] The cathode 110 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 110 may include a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca, but is not limited thereto.

[0120] The organic layer 105 includes a light emitting layer 130 , and the light emitting layer 130 may include a known host and a known dopant.

[0121] The host may be a single compound as a known host material or a composition in which two or more known host materials are mixed, and may contain them in a weight ratio of, for example, 1:99 to 99:1.

[0122] Within the above range, they can be included in a weight ratio of, for example, about 10:90 to 90:10, about 20:80 to 80:20, and can be included in a weight ratio of, for example, about 20:80 to about 70:30, about 20:80 to about 60:40, and about 30:70 to about 60:40. As a specific example, they can be included in a weight ratio of 40:60, 50:50, or 60:40.

[0123] The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a red or green phosphorescent dopant.

[0124] A dopant is a material mixed in a small amount with a compound or composition for an organic optoelectronic device to cause light emission, and generally may be a material such as a metal complex that emits light by multiple excitations to a triplet state or more. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types thereof may be used.

[0125] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0126] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0127] The charge transport region may be, for example, a hole transport region 140 .

[0128] The hole transport region 140 may further increase hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.

[0129] The hole transport region 140 may include the above-described compound for an organic optoelectronic device.

[0130] Specifically, the hole transport region 140 may include a hole transport layer between the anode 120 and the light emitting layer 130 and a hole transport auxiliary layer between the light emitting layer 130 and the hole transport layer, and the hole transport auxiliary layer may include the above-mentioned compound for an organic optoelectronic device.

[0131] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0132] The electron transport region 150 may further increase electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0133] Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light emitting layer 130 and an electron transport auxiliary layer between the light emitting layer 130 and the electron transport layer, and at least one of the electron transport layer and the electron transport auxiliary layer may contain at least one of the compounds of group A.

[0134] [Group A]

[0135]

[0136]

[0137]

[0138]

[0139] One embodiment of the present invention may provide an organic light emitting diode including a light emitting layer as an organic layer.

[0140] Another embodiment of the present invention may provide an organic light emitting diode including a light emitting layer and a hole transport region as an organic layer.

[0141] Another embodiment of the present invention may provide an organic light emitting diode including a light emitting layer and an electron transport region as an organic layer.

[0142] Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region 140 and an electron transport region 105 as an organic layer 105 in addition to the light emitting layer 130, such as Figure 1 shown.

[0143] On the other hand, the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), etc. as an organic layer in addition to the light emitting layer.

[0144] The organic light emitting diode 100 may be manufactured by forming an anode or a cathode on a substrate, then forming an organic layer by a dry film method such as vacuum deposition, sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0145] The organic light emitting diode may be applied to an organic light emitting display device.

[0146] Invention Mode

[0147] 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.

[0148] Hereinafter, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc. or Tokyo Chemical Industry or synthesized by known methods unless otherwise specified.

[0149] (Preparation of Compounds for Organic Optoelectronic Devices)

[0150] Synthesis Example 1: Synthesis of Compound 1-40

[0151] [Reaction 1]

[0152]

[0153] In a round-bottom flask, 7.6 g (31 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 15 g (31 mmol) of N-(3-(9-phenyl-9H-fluorene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 2305719-96-2), 1.4 g (1.5 mmol) of tris(dibenzylideneacetone)dipalladium(0), 0.94 g (4.6 mmol) of tri-tert-butylphosphine and 4.5 g (46 mmol) of sodium tert-butoxide and 90 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was subjected to column purification using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 16 g of compound 1-40 (yield: 74.7%). (LC / MS [+H] = 694.63)

[0154] Synthesis Example 2: Synthesis of Compound 1-76

[0155] [Reaction 2]

[0156]

[0157] In a round-bottom flask, 10 g (34.6 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 16.8 g (34.6 mmol) of N-(4-(9-phenyl-9H-fluorene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 1853122-02-7), 1.58 g (1.7 mmol) of tris(dibenzylideneacetone)dipalladium(0), 1.05 g (5.2 mmol) of tri-tert-butylphosphine and 5 g (51.9 mmol) of sodium tert-butoxide and 100 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was subjected to column purification using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 15 g of compound 1-76 (yield: 63%). (LC / MS [+H] = 694.63)

[0158] Synthesis Example 3: Synthesis of Compound 1-292

[0159] [Reaction 3]

[0160]

[0161] Step 1: Synthesis of Int-1

[0162] In a round-bottom flask, 30 g (93.3 mmol) of N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine (CAS No.: 1372775-52-4), 24.1 g (93.3 mmol) of 9-phenyl-9H-fluorene-9-ol (CAS No.: 25603-67-2) and 19.9 g (140 mmol) of boron trifluoride diethyl etherate and 100 mL of dichloromethane were added, and then stirred at room temperature for 12 hours under a nitrogen atmosphere. After the reaction was completed by adding excess water thereto, extraction was performed by using dichloromethane. The organic layer thus obtained was dried under reduced pressure to obtain 34 g of Int-1 (yield: 65%). (LC / MS[+H]=563.00)

[0163] Step 2: Synthesis of Compound 1-292

[0164] In a round-bottom flask, 8.7 g (35.6 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 20 g (35.6 mmol) of Int-1, 1.6 g (1.8 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.72 g (3.6 mmol) of tri-tert-butylphosphine and 4.5 g (46.3 mmol) of sodium tert-butoxide and 100 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was column purified using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 17 g of compound 1-292 (yield: 69%). (LC / MS[+H]=694.63)

[0165] Synthesis Example 4: Synthesis of Compound 1-51

[0166] [Reaction 4]

[0167]

[0168] Step 1: Synthesis of Int-2

[0169] In a round-bottom flask, 10 g (40.5 mmol) of 1-bromodibenzo [b, d] furan (CAS No.: 50548-45-3), 17.5 g (52.6 mmol) of 3- (9-phenyl-9H-fluorene-9-yl) aniline (CAS No.: 2452270-61-8), 2.22 g (2.4 mmol) of tris (dibenzylideneacetone) dipalladium (0), 2.95 g (7.3 mmol) of tri-tert-butylphosphine and 5 g (53 mmol) of sodium tert-butoxide and 120 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was subjected to column purification using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 18 g of Int-2 (yield: 89%). (LC / MS [+H] = 500.47)

[0170] Step 2: Synthesis of Compound 1-51

[0171] In a round-bottom flask, 8.8 g (36 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 18 g (36 mmol) of Int-2, 1 g (1.1 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.44 g (2.2 mmol) of tri-tert-butylphosphine, 4.5 g (47 mmol) of sodium tert-butoxide and 100 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was column purified using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 16 g of compound 1-51 (yield: 63%). (LC / MS[+H]=708.59)

[0172] Synthesis Example 5: Synthesis of Compound 1-87

[0173] [Reaction 5]

[0174]

[0175] Step 1: Synthesis of Int-3

[0176] In a round-bottom flask, 11 g (44.5 mmol) of 1-bromodibenzo [b, d] furan (CAS No.: 50548-45-3), 20.78 g (62.3 mmol) of 4- (9-phenyl-9H-fluorene-9-yl) aniline (CAS No.: 851343-45-8), 2.45 g (2.7 mmol) of tris (dibenzylideneacetone) dipalladium (0), 3.24 g (8 mmol) of tri-tert-butylphosphine and 5.6 g (58 mmol) of sodium tert-butoxide and 130 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was subjected to column purification using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 19 g of Int-3 (yield: 85%). (LC / MS [+H] = 500.50)

[0177] Step 2: Synthesis of compound 1-87

[0178] In a round-bottom flask, 9.15 g (37.4 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 18.7 g (37.4 mmol) of Int-3, 1 g (1.1 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.44 g (2.2 mmol) of tri-tert-butylphosphine, 4.5 g (47 mmol) of sodium tert-butoxide and 100 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was column purified using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 18 g of compound 1-87 (yield: 68%). (LC / MS[+H]=708.56)

[0179] Comparative Synthesis Example 1: Synthesis of Compound C-1

[0180] [Reaction formula 6]

[0181]

[0182] In a round-bottom flask, 10 g (34.6 mmol) of 2-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1801753-03-6), 16.8 g (34.6 mmol) of N-(4-(9-phenyl-9H-fluorene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 1853122-02-7), 1.58 g (1.7 mmol) of tris(dibenzylideneacetone)dipalladium(0), 1.05 g (5.2 mmol) of tri-tert-butylphosphine and 5 g (51.9 mmol) of sodium tert-butoxide and 100 mL of toluene were added, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled and then extracted with water and ethyl acetate. The organic layer thus obtained was dried under reduced pressure. The solid thus obtained was subjected to column purification using dichloromethane and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 14 g of Compound C-1 (yield: 59%).

[0183] (Manufacturing of organic light-emitting diodes)

[0184] Example 1

[0185] A glass substrate coated with an ITO (indium tin oxide) thin film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, and then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus prepared was used as an anode, and Compound A (Novaled GmbH) doped with 3% NDP-9 was vacuum deposited on the ITO substrate to form A thick hole injection layer is formed, and compound A is deposited on the hole injection layer to form Compound 1-40 obtained in Synthesis Example 1 is deposited on the hole transport layer to form A thick hole transport auxiliary layer is formed by vacuum deposition using a first host and a second host at the same time on the hole transport auxiliary layer and doping 10 wt % of GD as a dopant. Subsequently, compound B is deposited on the light-emitting layer to form A thick electron transport auxiliary layer is formed, and compound C and LiQ are simultaneously vacuum deposited at a weight ratio of 1:1 to form On the electron transport layer, vacuum deposition is performed in sequence. LiQ and Al is used to form a cathode to manufacture an organic light emitting diode.

[0186] Organic light emitting diodes were fabricated to have ITO / compound A (3% NDP-9 doping, ) / Compound A / Compound 1-40 / EML[host (first host: second host = 35:65): GD = 90wt%: 10wt%] / Compound B / Compound C:LiQ / LiQ / Al structure.

[0187] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0188] Compound B: 2-{3-[3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine

[0189] Compound C: 4-(4-{4-[4-(diphenyl-1,3,5-triazine-2-yl)phenyl]naphthalen-1-yl}phenyl)benzonitrile

[0190]

[0191] Examples 2-5 and Comparative Example 1

[0192] Each organic light emitting diode was manufactured in the same manner as in Example 1, except that the hole transport auxiliary layer was changed as shown in Table 10.

[0193] evaluate

[0194] Lifespan characteristics of the organic light emitting diodes according to Examples 1 to 5 and Comparative Example 1 were evaluated.

[0195] By using a polaronics lifetime measurement system at 24,000 cd / m 2 Initial brightness (cd / m 2 ) irradiated the organic light emitting diodes manufactured in Examples 1 to 5 and Comparative Example 1 to measure the decrease in luminance over time, wherein the time for the luminance to decrease to 97% from the initial luminance was measured as the T97 lifetime.

[0196] Based on the T97 life of Comparative Example 1, the T97 life of the example was calculated as a relative value, and the results are shown in Table 10.

[0197] [Table 10]

[0198] Grouping Hole transport auxiliary layer T97 lifespan (%) Example 1 1-40 135 Example 2 1-51 160 Example 3 1-76 143 Example 4 1-87 160 Example 5 1-292 140 Comparative Example 1 C-1 100

[0199] Referring to Table 10, the compounds according to the present invention showed significantly improved lifespans compared to the comparative compounds.

[0200] While the invention has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic optoelectronic device, the compound being represented by Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, Ar 3 is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, R 1 To R 6 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C6 to C30 heterocyclic, n1, n3, n5 and n6 are each independently an integer from 1 to 4, n2 is an integer from 1 to 3, and n4 is an integer from 1 to 5.

2. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-I to Chemical Formula 1-III: In Chemical Formula 1-I to Chemical Formula 1-III, Ar 1 To Ar 3 , R 1 To R 6 and n1 to n6 as defined in claim 1.

3. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-6: In Chemical Formula 1-1 to Chemical Formula 1-6, Ar 1 To Ar 3 , R 1 To R 6 and n2 to n6 as defined in claim 1, and n1', n3', n5' and n6' are each independently an integer of 1 or 2.

4. The compound for an organic optoelectronic device according to claim 1, wherein Ar 3 is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted chrysene, substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl or substituted or unsubstituted dibenzosilyl.

5. The compound for an organic optoelectronic device according to claim 1, wherein Ar 3 is one of the substituents listed in Group I: [Group I] 6. The compound for an organic optoelectronic device according to claim 1, wherein Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.

7. The compound for an organic optoelectronic device according to claim 1, wherein The compound is selected from the compounds listed in Group 1: [Group 1] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] 8. An organic optoelectronic device, comprising: an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, The organic layer comprises the compound for an organic optoelectronic device according to any one of claims 1 to 7.

9. The organic optoelectronic device according to claim 8, wherein: The organic layer includes a light-emitting layer, and in a hole transport region between the anode and the light-emitting layer, The hole transport region comprises the compound for an organic optoelectronic device. 10 . A display device comprising the organic optoelectronic device according to claim 8 .

Images