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

Abstract

The present application discloses a compound for an organic optoelectronic device, an organic optoelectronic device, and a display device. Specifically, the present application discloses a compound for an organic optoelectronic device represented by Chemical Formula 1, an organic optoelectronic device including the compound, and a display device. The details of Chemical Formula 1 are as defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0181066 filed on December 22, 2020, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

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

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

[0005] Organic optoelectronic devices can be broadly divided into two types based on their operating principles: 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; the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0006] Examples of the organic optoelectronic device include an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photoconductor.

[0007] Among them, organic light emitting diodes (OLEDs) have recently attracted attention due to the increasing demand for flat panel displays. OLEDs are devices that convert electrical energy into light energy, and the performance of OLEDs is greatly affected by the organic material between electrodes. Summary of the Invention

[0008] One embodiment provides a compound for an organic photoelectric device, which can realize an organic photoelectric device having high efficiency and a long lifespan.

[0009] Another embodiment provides an organic photoelectric device including the compound.

[0010] Another embodiment provides a display device including the organic photoelectric device.

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

[0012] [Chemical Formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] Z 1 to Z 3Each independently is N or CR a ,

[0016] Z 1 to Z 3 At least two of them are N,

[0017] X is O, S, Si or NR b ,

[0018] L 1 is a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0019] L 2 is a substituted or unsubstituted C6 to C12 arylene group,

[0020] Ar is a substituted or unsubstituted C6 to C20 aryl group,

[0021] R b 、R 1 and R 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and

[0022] R a and R 3 to R 14 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0023] According to another embodiment, an organic photoelectric 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 compound for an organic photoelectric device.

[0024] According to another embodiment, a display apparatus including an organic photoelectric device is provided.

[0025] Organic optoelectronic devices with high efficiency and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figures 1 to 4 are cross-sectional views each showing an organic light emitting diode according to an embodiment. DETAILED DESCRIPTION

[0027] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and is defined by the scope of the claims.

[0028] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of a substituent or compound is replaced with deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

[0029] In one embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound with 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 embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound with deuterium, C1 to C20 alkyl, C6 to C30 aryl, or cyano. In a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound with deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. In a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound with deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

[0030] As used herein, when no definition is otherwise provided, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, P and Si and the remainder carbon in one functional group.

[0031] As used herein, "aryl" refers to a group containing at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic moieties may be linked by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic moieties may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl.

[0032] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0033] As used herein, "heterocyclyl" is a general concept of heteroaryl and may contain at least one heteroatom selected from N, O, S, P and Si to replace carbon (C) in a cyclic compound, such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. When the heterocyclyl is a fused ring, the entire ring or each ring of the heterocyclyl may contain one or more heteroatoms.

[0034] For example, "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by a sigma bond, or, when the heteroaryl group comprises two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0035] 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 naphthyl 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 chrysenyl 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, a substituted or unsubstituted furanyl group, or a combination thereof, but is not limited thereto.

[0036] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl 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 The present invention may include, but is not limited to, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

[0037] As used herein, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, and due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) level, holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0038] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) level, electrons formed in the cathode can be easily injected into the light emitting layer and transported in the light emitting layer.

[0039] Hereinafter, compounds for an organic photoelectric device according to embodiments are described.

[0040] The compound for an organic photoelectric device according to an embodiment is represented by Chemical Formula 1.

[0041] [Chemical Formula 1]

[0042]

[0043] In Chemical Formula 1,

[0044] Z 1 to Z 3 Each independently is N or CR a ,

[0045] Z1 to Z 3 At least two of them are N,

[0046] X is O, S, Si or NR b ,

[0047] L 1 is a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

[0048] L 2 is a substituted or unsubstituted C6 to C12 arylene group,

[0049] Ar is a substituted or unsubstituted C6 to C20 aryl group,

[0050] R b 、R 1 and R 2 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and

[0051] R a and R 3 to R 14 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0052] In the compound represented by Chemical Formula 1, dibenzosilacyclopentadiene is substituted with triazine at the 4th position thereof, and triazine is substituted with dibenzofuran (or dibenzothiophene, dibenzosilacyclopentadiene, or carbazolyl) and an aryl group having 12 or more carbon atoms.

[0053] Since dibenzosilane is replaced with triazine, it achieves charge balance between holes and electrons, and improves intermolecular film properties by increasing the tendency to maintain the planarity of the molecular structure. Consequently, the refractive index is increased, and when applied, it is possible to realize organic light-emitting diodes with low drive efficiency, high efficiency, and long life.

[0054] In particular, since dibenzosilylene is substituted with triazine at the 4-position thereof, the efficiency characteristics of an organic light emitting diode including the same can be further improved.

[0055] At the same time, triazine is substituted by dibenzofuran (or dibenzothiophene, dibenzosilyl or carbazolyl) and an aromatic group having 12 or more carbon atoms, thereby not only increasing Tg but also accelerating electron movement, thereby further improving the life of the organic light-emitting diode including it.

[0056] In particular, by including an aromatic group having 12 or more carbon atoms, T1 energy and LUMO energy can be controlled, and thus an easy energy transfer effect to a dopant can be expected.

[0057] Chemical Formula 1 may be represented, for example, by any one of Chemical Formulas 1-1 to 1-4 depending on the substitution position of the dibenzofuran (or dibenzothiophene, dibenzosilyl, or carbazolyl) substituted with triazine.

[0058]

[0059] In Chemical Formulas 1-1 to 1-4, Z 1 to Z 3 , X, L 1 、L 2 , Ar and R 1 to R 14 The definition of is the same as described above.

[0060] For example, L in Chemical Formula 1 2 It may be a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group, and Ar may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.

[0061] As a specific embodiment, when L 2 When Ar is substituted, *-L 2 -Ar may contain 12 to 16 carbon atoms, and L 2 The carbon atoms of the additional substituents of and the carbon atoms of the additional substituents of Ar are not included in the number of carbons.

[0062] As a specific example, *-L in Chemical Formula 1 2-Ar may be selected from the substituted or unsubstituted groups of Group I.

[0063] [Group I]

[0064]

[0065] In group I, * is the connection point.

[0066] For example, R in Formula 1 1 and R 2 Each independently may be an unsubstituted methyl group, an unsubstituted ethyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted biphenyl group.

[0067] As a specific example, R in Chemical Formula 1 1 and R 2 Each independently may be an unsubstituted methyl group, an unsubstituted ethyl group or an unsubstituted phenyl group.

[0068] For example, R 3 to R 14 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0069] As a specific example, R 3 to R 14 Each may be hydrogen, but is not limited thereto.

[0070] For example, X may be O, S, or Si.

[0071] As a specific example, X may be O or S.

[0072] For example, the compound for an organic photoelectric device represented by Chemical Formula 1 may be one selected from the compounds of Group 1, but is not limited thereto.

[0073] [Group 1]

[0074]

[0075]

[0076]

[0077]

[0078] As a more specific example, the compound for an organic photoelectric device according to the present invention may be represented by Chemical Formula 1-1 or Chemical Formula 1-3,

[0079] X can be O or S, L 1 Can be a single key,

[0080] L 2 may be unsubstituted phenylene, Ar may be unsubstituted naphthyl, or

[0081] L 2 may be unsubstituted naphthylene and Ar may be unsubstituted phenyl, and

[0082] R 1 and R 2 may each independently be an unsubstituted methyl group, and R 3 to R 14 may each independently be hydrogen.

[0083] In addition to the above-mentioned compounds for organic photoelectric devices, one or more compounds may be included.

[0084] For example, the above-mentioned compound for an organic optoelectronic device may be used in the form of a composition further comprising a known host material.

[0085] For example, the compound for an organic photoelectric device may further include a dopant.

[0086] The dopant may be, for example, a phosphorescent dopant and may be, for example, a red, green or blue phosphorescent dopant, for example a red phosphorescent dopant.

[0087] A dopant is a material that is mixed in trace amounts with a compound or composition used in an organic optoelectronic device to induce light emission. It is typically a material such as a metal complex that emits triplet or higher levels of light through multiple excitation. The dopant can be, for example, an inorganic, organic, or organic-inorganic compound, and one or more of these can be used.

[0088] Examples of the dopant may include phosphorescent dopants. Examples of the phosphorescent dopant may include organometallic compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof. The phosphorescent dopant may be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0089] [Chemical formula Z]

[0090] L 3 MX 1

[0091] In the chemical formula Z, M is a metal, L 3 and X 1 They are the same as or different from each other and are ligands that form a complex with M.

[0092] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L 3 and X 1 This may be, for example, a bidentate ligand.

[0093] Hereinafter, an organic photoelectric device including the above-mentioned compound for an organic photoelectric device is described.

[0094] The organic optoelectronic device may be any device that converts electrical energy into light energy or vice versa, without particular limitation, and may be, for example, an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photoconductor.

[0095] Herein, an organic light emitting diode is described as an example of an organic photoelectric device with reference to the accompanying drawings.

[0096] Figures 1 to 4 are cross-sectional views each showing an organic light emitting diode according to an embodiment.

[0097] Reference Figure 1 , the organic light emitting diode 100 according to the 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 .

[0098] 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 an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; or a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0099] 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 be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; or a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0100] The organic layer 105 may include the above-mentioned compound for an organic photoelectric device.

[0101] The organic layer 105 may include a light emitting layer 130 , and the light emitting layer 130 may include the above-described compound for an organic photoelectric device.

[0102] The composition for an organic optoelectronic device further including a dopant may be, for example, a red-light-emitting composition.

[0103] The light emitting layer 130 may include, for example, the above-described first compound for an organic photoelectric device as a phosphorescent host.

[0104] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0105] The charge transport region may be, for example, a hole transport region 140 .

[0106] Reference Figure 2 In addition to the light emitting layer 130 , the organic light emitting diode 200 further includes a hole transport region 140 . The hole transport region 140 may further increase hole injection and / or hole mobility and block electrons between the anode 120 and the light emitting layer 130 .

[0107] 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 at least one of the group E compounds may be included in at least one of the hole transport layer and the hole transport auxiliary layer.

[0108] [Group E]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] In the hole transport region, in addition to the compounds described above, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds having similar structures can also be used.

[0115] In addition, the charge transport region may be, for example, a hole transport region 150 .

[0116] Reference Figure 3In addition to the light emitting layer 130 , the organic light emitting diode 300 further includes an electron transport region 150 . The electron transport region 150 can further increase electron injection and / or electron mobility and block holes between the cathode 110 and the light emitting layer 130 .

[0117] 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 group F compounds may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[0118] [Group F]

[0119]

[0120]

[0121]

[0122] One embodiment of the present invention may provide an organic light emitting diode including a light emitting layer 130 as an organic layer 105, such as Figure 1 shown.

[0123] Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region 140 in addition to the light emitting layer 130 as the organic layer 105, such as Figure 2 shown.

[0124] Another embodiment of the present invention may provide an organic light emitting diode including an electron transport region 150 in addition to the light emitting layer 130 as the organic layer 105, such as Figure 3 shown.

[0125] Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region 140 and an electron transport region 150 in addition to the light emitting layer 130 as the organic layer 105, such as Figure 4 shown.

[0126] In another embodiment of the present invention, in addition to Figures 1 to 4 In addition to the light emitting layer 130 as the organic layer 105 , the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), and the like.

[0127] The organic light emitting diodes 100 , 200 , 300 and 400 may be manufactured by forming an anode or cathode on a substrate and then forming an organic layer by a dry film method such as vacuum deposition, sputtering, plasma plating and ion plating and forming the cathode or anode thereon.

[0128] Organic light emitting diodes can be applied to organic light emitting display devices.

[0129] Hereinafter, the embodiments will be described in more detail with reference to Examples. However, these Examples are exemplary, and the scope of the claims is not limited thereto.

[0130] Hereinafter, unless otherwise specified or synthesized by known methods, the starting materials and reactants used in the Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd, TCI Corporation, Tokyo Chemical Industry Co., Ltd. or P&H tech.

[0131] (Preparation of Compounds for Organic Photoelectric Devices)

[0132] A compound which is a more specific example of the compound of the present invention was synthesized by the following steps.

[0133] Synthesis Example 1: Synthesis of Compound A-15

[0134] [Reaction Scheme 1]

[0135]

[0136] Step 1: Synthesis of Int-3

[0137] Int-1 (100 g, 315.11 mmol) was dissolved in 1.0 L of tetrahydrofuran (THF), and then Int-2 (63.28 g, 315.11 mmol) and tetrakis(triphenylphosphine)palladium (10.92 g, 9.45 mmol) were added thereto, followed by stirring. Subsequently, potassium carbonate (108.88 g, 787.77 mmol) saturated in 500 ml of water was added thereto, and then heated under reflux at 80°C for 12 hours. After the reaction was complete, water was added to the reaction solution, which was then extracted with ethyl acetate (EA), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained was separated and purified by flash column chromatography to obtain 84.02 g (76.9%) of Int-3.

[0138] Step 2: Synthesis of Int-4

[0139] Int-3 (86 g, 242.45 mmol) was dissolved in 600 mL of tetrahydrofuran (THF), and the internal temperature was lowered to -78°C. Subsequently, n-BuLi (288.75 mL, 721.88 mmol) was slowly added dropwise thereto while maintaining the internal temperature at -78°C, and then stirred at the same temperature for 1 hour.

[0140] Then, dichlorodimethylsilane (104.31 ml, 871.24 mmol) was added dropwise at -78°C, followed by stirring at room temperature for 12 hours. After completion of the reaction, water was added to the reaction solution, which was then extracted with ethyl acetate (EA), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The resulting residue was separated and purified by flash column chromatography to obtain 39.03 g (64.3%) of Int-4.

[0141] Step 3: Synthesis of Int-5

[0142] The intermediate of Int-4 (39.0 g, 159.32 mmol) was dissolved in 500 ml of dimethylformamide (DMF) under nitrogen, and bis(pinacolato)diboron (65.35 g, 257.36 mmol), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) (7.01 g, 8.58 mmol) and potassium acetate (33.68 g, 343.15 mmol) were added thereto, and then heated under reflux at 150 ° C for 24 hours. After the reaction was completed, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified by flash column chromatography to obtain 41.5 g (72%) of Int-5.

[0143] Step 4: Synthesis of Int-7

[0144] Int-5 (5.00 g, 14.87 mmol) was dissolved in 50 mL of tetrahydrofuran (THF), and Int-6 (2,4-dichloro-6-[4-(naphthalene-2-yl)phenyl]-1,3,5-triazine, 6.27 g, 14.87 mmol) and tetrakis(triphenylphosphine)palladium (0.52 g, 0.45 mmol) were added thereto, and then stirred. Subsequently, potassium carbonate (5.14 g, 37.17 mmol) saturated in 25 ml of water was added thereto, and then heated under reflux at 80 ° C for 12 hours. When the reaction was complete, the organic layer was separated therefrom and concentrated. Subsequently, 150 mL of methanol was added to the resulting mixture to crystallize the solid, which was filtered and dissolved in monochlorobenzene, then filtered again with silica gel / diatomaceous earth, and after removing an appropriate amount of organic solvent, recrystallized with methanol and purified by sublimation to obtain 4.07 g (52%) of Int-7.

[0145] Step 5: Synthesis of Compound A-15

[0146] Int-7 (4.00 g, 7.6 mmol) was dissolved in 30 mL of tetrahydrofuran (THF), and Int-8 (2.56 g, 7.6 mmol) and tetrakis (triphenylphosphine) palladium (0.26 g, 0.23 mmol) were added thereto and stirred. Subsequently, potassium carbonate (2.63 g, 19.01 mmol) saturated in 15 ml of water was added thereto, and the mixture was refluxed at 80 ° C for 12 hours. When the reaction was complete, the organic layer was separated and concentrated. Subsequently, the resulting mixture was added to 150 mL of methanol to crystallize the solid, which was filtered and dissolved in monochlorobenzene, then filtered with silica gel / diatomaceous earth, and after removing an appropriate amount of organic solvent, recrystallized from methanol to obtain 3.85 g (77%) of compound A-15.

[0147] Calculated for C45H31N3OSi: C, 82.16; H, 4.75; N, 6.39; O, 2.43; Si, 4.27; Found: C, 82.17; H, 4.75; N, 6.39; O, 2.43; Si, 4.26

[0148] Synthesis Examples 2-16 and Comparative Synthesis Examples 1-4

[0149] Each compound was synthesized according to the same method as in Step 5 of Synthesis Example 1, except that Int A and / or Int B were used instead of Int-7 and / or Int-8.

[0150] (Table 1)

[0151]

[0152]

[0153]

[0154]

[0155] <Int A>

[0156]

[0157] <Int B>

[0158]

[0159]

[0160] (Manufacturing of organic light-emitting diodes)

[0161] Example 1

[0162] A glass substrate coated with 1,500A thick indium tin oxide (ITO) was washed with distilled water. After washing the glass substrate with distilled water, it was ultrasonically cleaned and dried with solvents such as isopropyl alcohol, acetone, and methanol, then moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and moved to a vacuum precipitator. The obtained ITO transparent electrode was used as an anode, and compound A was vacuum deposited on the ITO substrate to form a 700A thick hole injection layer. After depositing 50A thick compound B on the injection layer, compound C was deposited with a thickness of 1,020A to form a hole transport layer. On the hole transport layer, compound A-15 of Synthesis Example 1 was used as the main body, doped with 2wt% of [Ir(piq)2acac] as a dopant to form a 400A thick light-emitting layer by vacuum deposition. Subsequently, compound D and Liq were simultaneously vacuum deposited on the light-emitting layer in a 1:1 ratio to form a 300A thick electron transport layer, and 15A of Liq and 1200A of Al electron transport layers were vacuum deposited in sequence to form a cathode to manufacture an organic light-emitting diode.

[0163] The organic light emitting diode has a structure having five organic thin film layers, as follows.

[0164] ITO / Compound A (700A) / Compound B (50A) / Compound C (1,020A) / EML [Compound A-15: [Ir(piq)2acac] (2 wt%)] (400A) / Compound D: Liq (300A) / Liq (15A) / Al (1,200A).

[0165] Compound A: N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4'-diamine

[0166] Compound B: 2,3,6,7,10,11-Hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN)

[0167] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0168] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

[0169] Examples 2 to 16 and Comparative Examples 1 to 4

[0170] The diodes of Examples 2 to 16 and Comparative Examples 1 to 4 were manufactured in the same manner as in Example 1, except that the main body was changed as shown in Table 2.

[0171] Evaluation: Confirmation of life extension effect

[0172] (1) Measuring current density changes based on voltage changes

[0173] The obtained organic light emitting diode was measured for a current value flowing in a unit device while increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by the area to provide a result.

[0174] (2) Measuring brightness changes based on voltage changes

[0175] The luminance was measured using a luminance meter (Minolta CS-1000A) while increasing the voltage of the organic light emitting diode from 0 V to 10 V.

[0176] (3) Measure luminous efficiency

[0177] By using the luminance and current density from items (1) and (2) to calculate the current density at the same current density (10 mA / cm 2 ) under luminous efficiency (cd / A).

[0178] (4) Measurement life

[0179] The brightness (cd / m 2 ) maintained at 6,000cd / m 2 , and measured the time when the luminous efficiency (cd / A) dropped to 90% to obtain the results.

[0180] (5) Measure the driving voltage

[0181] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 Measure the driving voltage of each diode.

[0182] The values ​​shown in Table 2 are relative values ​​based on the values ​​of Comparative Example 1, respectively.

[0183] (Table 2)

[0184]

[0185]

[0186] 2, the organic light emitting diode according to the embodiment of the present invention has improved driving voltage, luminous efficiency, and lifespan characteristics compared to the organic light emitting diode according to the comparative example.

[0187] While the invention has been described in connection with what are presently considered to be practical embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary is intended to cover various modifications and equivalent arrangements within the spirit and scope of the appended claims.

[0188] <Description of Reference Numerals>

[0189] 100, 200, 300, 400: organic light-emitting diodes

[0190] 105: Organic layer

[0191] 110: cathode

[0192] 120: Anode

[0193] 130: Luminous layer

[0194] 140: Hole transport zone

[0195] 150: Electron transport region.

Claims

1. A compound for an organic photoelectric device, the compound being represented by Chemical Formula 1: [Chemical Formula 1] in, In Chemical Formula 1, Z 1 to Z 3 Each independently is N or CR a , Z 1 to Z 3 At least two of them are N, X is O or S, L 1 is a single bond, or a substituted or unsubstituted C6 to C20 arylene group, *-L 2 -Ar is one of the substituted or unsubstituted groups of Group I: [Group I] Among them, in group I, * is the connection point R 1 and R 2 are each independently an unsubstituted methyl group or an unsubstituted ethyl group, R a and R 3 to R 14 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, and Here, "substituted" means that at least one hydrogen of the substituent is replaced by deuterium, a C1 to C5 alkyl group, a C6 to C18 aryl group, or a cyano group.

2. The compound according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-4: Among them, in Chemical Formula 1-1 to Chemical Formula 1-4, Z 1 to Z 3 , X, L 1 , L 2 , Ar and R 1 to R 14 The definition is the same as in claim 1.

3. The compound according to claim 1, wherein *-L 2 -Ar contains 16 carbon atoms. 2 When L is substituted with Ar, 2 The carbon atoms of the additional substituents of and the carbon atoms of the additional substituents of Ar are not included in the number of carbon atoms.

4. The compound according to claim 1, which is one of the compounds of Group 1: [Group 1] 5. An organic optoelectronic device comprising an anode and a cathode facing each other, and at least one organic layer, wherein the at least one organic layer is located between the anode and the cathode, in, The organic layer comprises the compound for an organic photoelectric device according to any one of claims 1 to 4 .

6. The organic photoelectric device according to claim 5, wherein The organic layer includes a light-emitting layer, and The light-emitting layer includes the compound for an organic photoelectric device. A display device comprising the organic photoelectric device according to claim 5 .

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