Compound for organic photoelectric device, composition for organic photoelectric device, organic photoelectric device and display device

Abstract

The present invention relates to a compound for an organic photoelectric device represented by Chemical Formula 1; a composition for an organic photoelectric device comprising the compound; an organic photoelectric device; and a display device. The description of Chemical Formula 1 is the same as defined in the specification.

Description

Technical Field

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

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

[0003] Organic photoelectric devices can be roughly divided into two types according to the operating principle. One is a photoelectric device that generates electric 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 electric energy by supplying voltage or current to electrodes.

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

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

[0006] [Technical issues]

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

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

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

[0010] Another embodiment provides a display device including an organic optoelectronic device.

[0011] [Technical solution]

[0012] According to an embodiment, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] X 1O, S or NR a ,

[0017] L 1 To L 3 are independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0018] R a and R 1 To R 5 are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0019] Ar 1 and Ar 2 are independently a substituted or unsubstituted C6 to C30 aryl group, a C2 to C30 heterocyclic group, a substituted or unsubstituted C6 to C30 arylamine group, or a combination thereof.

[0020] According to another embodiment, a composition for an organic photoelectric device includes the above-mentioned compound for an organic photoelectric device and a second compound for an organic photoelectric device represented by Chemical Formula 2.

[0021] [Chemical formula 2]

[0022]

[0023] In chemical formula 2,

[0024] Z 1 To Z 3 Independently N or CL a -R e ,

[0025] Z 1 To Z 3 At least two of them are N,

[0026] L a and L 4 To L 6 are independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0027] R e and R 15 To R 17 are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0028] R 15To R 17 At least one of the groups is a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted triphenylene group.

[0029] 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 or a composition.

[0030] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0031] [Beneficial Effects]

[0032] High-efficiency and long-life organic photovoltaic devices can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 and Figure 2 Each is a cross-sectional view of an organic light emitting diode according to an embodiment.

[0034] <symbol description>

[0035] 100, 200: Organic light-emitting diodes

[0036] 105: Organic layer

[0037] 110: cathode

[0038] 120: Anode

[0039] 130: Luminous layer

[0040] 140: Hole auxiliary layer DETAILED DESCRIPTION

[0041] Hereinafter, embodiments of the present invention will be 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.

[0042] In the present specification, when no limitation 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 aralkyl, 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.

[0043] In one embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 aralkyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C20 alkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen in a substituent or compound by deuterium, C1 to C5 alkyl, C6 to C18 aryl, pyridyl, quinolyl, isoquinolyl, dibenzofuranyl, dibenzothienyl, or carbazolyl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound by deuterium, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl, or dibenzothiophenyl. In addition, in a specific embodiment of the present invention, "substituted" refers to the replacement of at least one hydrogen of a substituent or compound by deuterium, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, naphthyl, triphenylene, tribenzofuranyl, or dibenzothiophenyl.

[0044] In the present specification, when no definition is otherwise provided, "hetero" means that one functional group contains 1 to 3 hetero atoms selected from N, O, S, P and Si and the rest are carbon.

[0045] In the present specification, "aryl" refers to a group including at least one hydrocarbon aromatic part, and may include a group in which all elements of the hydrocarbon aromatic part have a p-orbital forming a conjugation, such as phenyl, naphthyl, etc., a group in which two or more hydrocarbon aromatic parts may be connected by a σ bond, such as biphenyl, terphenyl, quaterphenyl, etc., and a group in which two or more hydrocarbon aromatic parts are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl, etc. The aryl group may include a group of a monocyclic, polycyclic or fused-ring polycyclic (i.e., a ring sharing adjacent pairs of carbon atoms) functional group.

[0046] In this specification, "heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si instead of carbon (C) in a ring (such as an aryl group, a cycloalkyl group, a condensed ring thereof or a combination thereof). When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may include one or more heterocycles.

[0047] For example, "heteroaryl" refers 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 can be fused. When the heteroaryl is a fused ring, each ring can include one to three heteroatoms.

[0048] Specific examples of the heterocyclic group may be pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl and the like.

[0049] More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heterocyclic 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 substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted indenyl, substituted or unsubstituted furanyl, substituted or unsubstituted phenylthio, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted The invention may include, but is not limited to, a substituted benzothiophenyl group, 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 phenoxazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

[0050] In this specification, hole characteristics refer to the ability to give electrons to form holes when an electric field is applied, based on the highest occupied molecular orbital (HOMO) energy level, and the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive properties.

[0051] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied, and the 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.

[0052] Hereinafter, a compound for an organic photoelectric device according to an embodiment is described.

[0053] The compound for an organic photoelectric device according to an embodiment is represented by Chemical Formula 1.

[0054] [Chemical formula 1]

[0055]

[0056] In Chemical Formula 1,

[0057] X 1 O, S or NR a ,

[0058] L 1 To L 3 are independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0059] R a and R 1 To R 5 are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0060] Ar 1 and Ar 2 are independently a substituted or unsubstituted C6 to C30 aryl group, a C2 to C30 heterocyclic group, a substituted or unsubstituted C6 to C30 arylamine group, or a combination thereof.

[0061] The compound represented by Chemical Formula 1 has a linear structure in which 2,3-positions of dibenzofuran, dibenzothiophene or carbazole are further condensed. Such a structure can realize a device having high efficiency by increasing the refractive index.

[0062] In addition, since the terminal ring to be further fused is substituted with an amine group, a linear structure can be maintained, heat resistance stability can be improved, and a device with an appropriate HOMO energy can be provided, thereby realizing a device with improved life. By maintaining a linear main chain structure, a high Tg can be provided, and when applied to a device, high heat resistance can be provided.

[0063] For example, depending on the specific substitution position of the amine group, the compound may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-4.

[0064]

[0065] In Chemical Formulae 1-1 to 1-4, X 1 , L 1 To L 3 , R 1 To R 5 ,Ar 1 and Ar 2 Same as above.

[0066] According to an embodiment of the present invention, Chemical Formula 1 may be represented by Chemical Formulas 1-3.

[0067] The compounds represented by Chemical Formula 1-3 are closest to a linear structure and are particularly advantageous in terms of efficiency when applied to a device.

[0068] For example, X 1 Can be O or S.

[0069] For example, X 1 YesNR a , where R a It may be a substituted or unsubstituted C6 to C30 aryl group. Specifically, R a It may be a substituted or unsubstituted C6 to C20 aryl group, for example, R a It may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.

[0070] L 1 To L 3 It may be a single bond or a substituted or unsubstituted C6 to C30 arylene group, and specifically, a single bond or a substituted or unsubstituted C6 to C20 arylene group.

[0071] According to an embodiment of the present invention, L 1 To L 3 It may be a single bond or a substituted or unsubstituted phenylene group.

[0072] For example, R 1 To R 5 may independently be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, and specifically, R 1 To R 5 It may be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl.

[0073] According to an embodiment of the present invention, R 1 To R 5Each may be hydrogen, but is not limited thereto.

[0074] For example, Ar 1 and Ar 2 It may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted C6 to C30 aromatic amine group.

[0075] Specifically, Ar 1 and Ar 2 The groups may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted C6 to C30 aromatic amine groups.

[0076] According to an embodiment of the present invention, Ar 1 and Ar 2 The groups may be independently selected from Group I.

[0077] [Group I]

[0078]

[0079] At the same time, for example, depending on Ar 1 and Ar 2 Of the specific types, Chemical Formula 1 can be represented by any one of Chemical Formulas 1a to 1d.

[0080]

[0081]

[0082] In Chemical Formulae 1a to 1d,

[0083] X 1 Can be O, S or NR a ,

[0084] X 2 Can be O, S, CR b R c or NR d ,

[0085] L 1 To L 3may independently be a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0086] R a , R b , R c , R d and R 1 To R 14 may independently be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0087] Ar 2 To Ar 5 and may independently be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0088] For example, Ar in Formula 1a to Formula 1c 2 The C6 to C30 aryl group may be substituted or unsubstituted.

[0089] For example, Ar in formula 1d 2 may be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, and Ar 4 and Ar 5 The C6 to C30 aryl group may be substituted or unsubstituted.

[0090] As a specific example, Ar 4 and Ar 5 The may exist independently or be linked to each other to form a substituted or unsubstituted heteroaromatic polycyclic ring.

[0091] For example, the heteroaromatic polycyclic ring may be a carbazolyl group and may be connected to L of Formula 1d at position 9. 2 .

[0092] For example, Ar in Formula 1a to Formula 1c 2 may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group,

[0093] Ar in Formula 1c and Formula 1d 3 To Ar 5 may independently be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group,

[0094] Ar in chemical formula 1d 2It 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, or a substituted or unsubstituted dibenzothienyl group.

[0095] According to an embodiment of the present invention, Ar of Chemical Formula 1a to Chemical Formula 11c 2 It may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group. Ar in Formula 1d 2 may be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, and Ar 3 To Ar 5 and may independently be substituted or unsubstituted phenyl or substituted or unsubstituted biphenyl.

[0096] According to an embodiment of the present invention, Chemical Formula 1 may be represented by Chemical Formula 1a or Chemical Formula 1d.

[0097] The compound for an organic photoelectric device may be, for example, one of the compounds selected from Group 1, but is not limited thereto.

[0098] [Group 1]

[0099]

[0100]

[0101]

[0102]

[0103] A composition for an organic photoelectric device according to another embodiment includes a compound for an organic photoelectric device (hereinafter referred to as “a first compound for an organic photoelectric device”) and a second compound for an organic photoelectric device represented by Chemical Formula 2.

[0104] [Chemical formula 2]

[0105]

[0106] In chemical formula 2,

[0107] Z 1 To Z 3 Independently N or CL a -R e ,

[0108] Z 1 To Z 3 At least two of them are N,

[0109] L a and L 4 To L 6 are independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0110] R e and R 15 To R 17 are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0111] R 15 To R 17 At least one of the groups is a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted triphenylene group.

[0112] The second compound for an organic optoelectronic device is a compound having a property of being able to receive electrons when an electric field is applied (i.e., electronic properties), and may have a structure that can easily receive electrons when an electric field is applied due to a nitrogen-containing ring (such as pyrimidine, triazine, etc.). Therefore, the driving voltage of the organic optoelectronic device including the second organic optoelectronic device compound can be reduced.

[0113] Furthermore, it may be included together with the first compound for an organic photoelectric device having a hole characteristic to exhibit a bipolar characteristic.

[0114] For example, Z 1 To Z 3 Two of them can be nitrogen (N) and the other can be CR e .

[0115] For example, Z 1 and Z 2 can be nitrogen and Z 3 Can be CR e .

[0116] For example, Z 2 and Z 3 can be nitrogen and Z 1 Can be CR e .

[0117] For example, Z 1 and Z 3 can be nitrogen and Z 2 Can be CR e .

[0118] As an example, Z 1 To Z3 Each may be nitrogen (N).

[0119] For example, L 4 To L 6 and may independently be a single bond or a substituted or unsubstituted C6 to C20 arylene group.

[0120] Specifically, L 4 To L 6 and may independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, or a substituted or unsubstituted naphthylene group.

[0121] According to an embodiment of the present invention, L 4 To L 6 It may be a single bond, a substituted or unsubstituted m-phenylene group, or a substituted or unsubstituted p-phenylene group.

[0122] For example, R 15 may be a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted triphenylene group, and R 16 and R 17 The radicals may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or a combination thereof.

[0123] According to an exemplary embodiment of the present invention, R 15 It may be a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, R 16 and R 17 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or a combination thereof.

[0124] For example, Chemical Formula 2 may be represented by any one of Chemical Formula 2-1 to Chemical Formula 2-3.

[0125]

[0126] In Chemical Formula 2-1 to Chemical Formula 2-3, Z1 To Z 3 , L 4 To L 6 , R 16 and R 17 Same as above,

[0127] X 3 O, S or NR f ,

[0128] R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s and R is independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof.

[0129] For example, R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s are independently hydrogen, cyano, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl.

[0130] For example, R k , R l and R m It may independently be hydrogen, cyano, substituted or unsubstituted C6 to C12 aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted carbazolyl.

[0131] According to an embodiment of the present invention, Chemical Formula 2 may be represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[0132] The second compound for an organic photoelectric device may be, for example, one of the compounds of Group 2, but is not limited thereto.

[0133] [Group 2]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] For example, the first compound and the second compound can be included in a weight ratio of 1:99 to 99:1. Within the above range, bipolar characteristics can be achieved by adjusting the appropriate weight ratio using the hole transport ability of the first compound and the electron transport ability of the second compound to improve efficiency and life. Within the above range, they can be included, for example, in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, about 30:70 to 70:30, about 40:60 to 60:40, or about 50:50. For example, they can be included in a weight ratio of 70:30 to 50:50, such as a weight ratio of 70:30 or 60:40.

[0147] For example, the composition for an organic photoelectric device may include a first compound for an organic photoelectric device represented by any one of Chemical Formula 1-1 to Chemical Formula 1-4 and a second compound for an organic photoelectric device represented by any one of Chemical Formula 2-1 to Chemical Formula 2-3.

[0148] As an example, the composition for an organic photoelectric device may include a first compound for an organic photoelectric device represented by any one of Chemical Formula 1a to Chemical Formula 1d and a second compound for an organic photoelectric device represented by any one of Chemical Formula 2-1 to Chemical Formula 2-3.

[0149] As a specific example, the first compound for an organic photoelectric device may be represented by Chemical Formula 1-3, and the second compound for an organic photoelectric device may be represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[0150] As a specific example, the first compound for an organic photoelectric device may be represented by Chemical Formula 1a or Chemical Formula 1d, and the second compound for an organic photoelectric device may be represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[0151] For example, the composition for an organic photoelectric device may include a first compound for an organic photoelectric device that is one of compounds H-1 to H-129 and a second compound for an organic photoelectric device that is one of compounds A-1 to A-44, B-1 to B-160, C-1 to C20, D-1 to D-28, and E-1 to E-55.

[0152] The composition for an organic photoelectric device may further include at least one compound in addition to the first compound for an organic photoelectric device and the second compound for an organic photoelectric device described above.

[0153] The composition may further comprise a dopant. The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, and may be, for example, a red phosphorescent dopant.

[0154] The dopant is a material that is mixed in a small amount with the first compound for an organic photoelectric device and the second compound for an organic photoelectric device to cause light emission, and may generally be a material such as a metal complex that emits light by multiple excitation to a triplet state or a multiplet state. For example, the dopant may be an inorganic, organic, or organic / inorganic compound, and one or two or more types thereof may be used.

[0155] An embodiment of the dopant may be, for example, a phosphorescent dopant, and an embodiment of the phosphorescent dopant may be an organic metal compound containing 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.

[0156] [Chemical formula Z]

[0157] L 7 MX a

[0158] In the chemical formula Z, M is a metal, L is 7 and X a They are the same as or different from each other and are ligands that form a coordination compound with M.

[0159] 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 7 and X a This may be, for example, a bidentate ligand.

[0160] The composition may be formed by a dry film forming method such as chemical vapor deposition (CVD).

[0161] Hereinafter, an organic photoelectric device including the above composition is described.

[0162] The organic photoelectric device may be any device that converts electrical energy into light energy and 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.

[0163] Herein, an organic light emitting diode as one embodiment of an organic photoelectric device is described with reference to the accompanying drawings.

[0164] Figure 1 and Figure 2 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0165] refer to 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 .

[0166] 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. For example, the anode 120 may be: a metal or an alloy thereof, such as nickel, platinum, vanadium, chromium, copper, zinc, gold, etc.; a metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; a combination of a metal and an oxide, such as ZnO and Al or SnO 2 and Sb; conductive polymers such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDT), polypyrrole, and polyaniline, but not limited thereto.

[0167] 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. For example, the cathode 110 may be: a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc., or an alloy thereof; a multilayer structure material such as LiF / Al, LiO 2 / Al, LiF / Ca, LiF / Al and BaF 2 / Ca, but not limited thereto.

[0168] The organic layer 105 may include the above-described compound for an organic photoelectric device or a composition for an organic photoelectric device.

[0169] The organic layer 105 includes a light emitting layer 130 , which may include the above-mentioned compound for an organic optoelectronic device.

[0170] The composition for an organic optoelectronic device may be, for example, a red light-emitting composition.

[0171] The light emitting layer 130 may include, for example, the above-described first compound for an organic photoelectric device and the second compound for an organic photoelectric device as respective phosphorescent hosts.

[0172] refer to Figure 2 In addition to the light emitting layer 130, the organic light emitting diode 200 further includes a hole auxiliary layer 140. The hole auxiliary layer 140 further increases hole injection and / or hole mobility and blocks electrons between the anode 120 and the light emitting layer 130. The hole auxiliary layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer.

[0173] The hole auxiliary layer 140 may be at least two layers, for example, a hole transport layer between the anode 120 and the light emitting layer 130 and a hole transport auxiliary layer between the hole transport layer and the light emitting layer 130 .

[0174] According to an embodiment of the present invention, the hole transport auxiliary layer may include the above-mentioned compound for an organic photoelectric device or the composition for an organic photoelectric device.

[0175] According to another exemplary embodiment of the present invention, the light emitting layer may include the above compound for an organic photoelectric device or the composition for an organic photoelectric device, and the hole transport layer or the hole transport auxiliary layer may include at least one of Compounds RA-1 to RA-4.

[0176]

[0177] Furthermore, in one embodiment of the present invention, in addition to the organic layer 105 , at least one electron auxiliary layer such as an electron transport layer, an electron injection layer and / or a hole blocking layer may be further included between the cathode 110 and the light emitting layer 130 .

[0178] For example, the electron auxiliary layer may be at least two layers and include, for example, an electron transport layer between the cathode 110 and the light emitting layer 130 and an electron transport auxiliary layer between the electron transport layer and the light emitting layer.

[0179] According to yet another embodiment of the present invention, the electron transport layer or the electron transport auxiliary layer may include at least one of compounds EA-1 and EA-2.

[0180]

[0181] The organic light emitting diodes 100 and 200 may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film forming method such as vacuum deposition (evaporation), sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0182] The organic light emitting diode may be applied to an organic light emitting display device.

[0183] [Implementation Method]

[0184] 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.

[0185] Hereinafter, raw materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo chemical industry or P&Htech unless specifically commented or synthesized by a known method.

[0186] (Preparation of Compounds)

[0187] First compound for organic optoelectronic devices

[0188] Synthesis Example 1: Synthesis of Compound H-1

[0189] [Reaction Scheme 1]

[0190]

[0191] a) Synthesis of intermediate H-1-1

[0192] In a round-bottom flask, 50.00 g (135.41 mmol) of 9-phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9H-carbazole, 29.72 g (135.41 mmol) of 2-bromo-5-chloro-benzaldehyde, 4.69 g (4.06 mmol) of Pd(PPh 3 ) 4 and 37.43 g (270.81 mmol) K 2 CO 3 Suspended in a mixed solvent of 400 mL THF / 220 mL distilled water, then stirred at room temperature for 12 hours. When the reaction is complete, the product is concentrated, extracted with dichloromethane, and the organic layer silica gel column therefrom is used to obtain 45.0 g (yield 87%) of the target compound, intermediate H-1-1.

[0193] b) Synthesis of intermediate H-1-2

[0194] 45.00g (117.9mmol) intermediate H-1-1 and 45.00g (117.9mmol) (methoxymethyl) triphenylphosphonium chloride are suspended in 600ml THF, and 15.87g (141.48mmol) potassium tert-butoxide is added thereto, and then at room temperature stirred for 12 hours. When the reaction is complete, 400ml distilled water is added thereto, and then extraction, then organic layer is concentrated therein and extracted again with methylene dichloride, magnesium sulfate is added thereto, and then stirred 30 minutes, and concentrated filtrate. After adding 100ml methylene dichloride in concentrated filtrate, 15ml methylsulfonic acid is added thereto, and then stirred 1 hour.

[0195] When the reaction was completed, methanol was added thereto to produce a solid. The produced solid was filtered and dried to obtain 30.0 g (yield 67%) of the target compound, intermediate H-1-2.

[0196] c) Synthesis of Compound H-1

[0197] Intermediate H-1-2 (8.85 g, 23.45 mmol), bis-biphenyl-4-yl-amine (7.91 g, 24.62 mmol), sodium tert-butoxide (NaOtBu) (3.38 g, 35.17 mmol), Pd 2 (dba) 3 (1.28 g, 1.41 mmol) and tri-tert-butylphosphine ((P(tBu) 3) (1.71 g, 50% in toluene) was added to xylene (120 mL), and then heated to reflux for 12 hours under a nitrogen stream. After removing xylene, 200 mL of methanol was added to the obtained mixture, and the solid crystallized therein was filtered, dissolved in toluene, and filtered with silica gel / diatomaceous earth, and an appropriate amount of organic solvent was concentrated to obtain 12 g of compound H-1 (77%).

[0198] LC / MS calculated for: C50H34N2 Exact mass: 662.27 Measured 662.32 [M+H]

[0199] Synthesis Example 2: Synthesis of Compound H-7

[0200] [Reaction Scheme 2]

[0201]

[0202] a) Synthesis of intermediate H-7-1

[0203] 15.00 g (39.71 mmol) of intermediate H-1-2, 12.1 g (47.64 mmol) of bis(pinacolato)diboron, 1.62 g (1.98 mmol) of Pd(dppf)Cl 2 and 11.69g (119.09mmol) KOAc were suspended in 150ml toluene, then refluxed and stirred for 12 hours. After concentrating the reaction solvent, the organic layer was extracted therefrom with dichloromethane, and columnized with hexane: EA = 4: 1 (v / v) to obtain 15.0g (yield 81%) of the target compound, intermediate H-7-1.

[0204] b) Synthesis of intermediate H-7-2

[0205] Intermediate H-7-1 (13.30 g, 28.34 mmol), 1-bromo-4-chloro-benzene (6.51 g, 34.00 mmol), K 2 CO 3 (7.83 g, 56.67 mmol) and Pd(PPh 3 ) 4 (0.98 g, 0.85 mmol) was put into a round-bottom flask, and then dissolved in 100 ml of THF and 50 ml of distilled water, and then stirred at 80° C. for 12 hours. When the reaction was completed, the water layer was removed therefrom, and 10.0 g (78%) of Intermediate H-7-2 was obtained by column chromatography.

[0206] c) Synthesis of Compound H-7

[0207] Intermediate H-7-2 (9.21 g, 20.30 mmol), bis-biphenyl-4-yl-amine (6.85 g, 21.32 mmol), sodium tert-butoxide (NaOtBu) (2.97 g, 30.45 mmol), Pd 2 (dba) 3 (1.11 g, 1.22 mmol) and tri-tert-butylphosphine ((P(tBu) 3 ) (1.48 g, 50% in toluene) was added to xylene (120 mL), and then heated to reflux for 12 hours under a nitrogen stream. After removing xylene, 200 mL of methanol was added to the obtained mixture, and the solid crystallized therein was filtered, dissolved in toluene, and filtered with silica gel / diatomaceous earth, and an appropriate amount of organic solvent was concentrated to obtain 12 g of compound H-7 (80%).

[0208] LC / MS calculated for: C56H38N2 Exact mass: 738.30 Measured 738.27 [M+H]

[0209] Synthesis Example 3: Synthesis of Compound H-14

[0210] [Reaction Scheme 3]

[0211]

[0212] Compound A-7 was synthesized according to the same method as in Synthesis Example 1 c) by using intermediate H-1-2 and dibenzofuran-3-yl-phenyl-amine at an equivalent ratio of 1:1.

[0213] LC / MS calculated for: C44H28N2O Exact mass: 600.22 Observed 600.45 [M+H]

[0214] Synthesis Example 4: Synthesis of Compound H-23

[0215] [Reaction Scheme 4]

[0216]

[0217] Compound H-23 was synthesized in the same manner as in Synthesis Example 1 using 2-dibenzothiophene-3-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane instead of the reactant 9-phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-9H-carbazole.

[0218] LC / MS calculated for: C44H29NS Exact mass: 603.20 Observed 603.77 [M+H]

[0219] Synthesis Example 5: Synthesis of Compound H-42

[0220] [Reaction Scheme 5]

[0221]

[0222] Compound H-42 was synthesized in the same manner as in Synthesis Example 1 using 2-dibenzothiophen-3-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane instead of the reactant 9-phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-9H-carbazole.

[0223] LC / MS calculated for: C44H29NO Exact mass: 587.22 Observed 587.71 [M+H]

[0224] Synthesis Example 6: Synthesis of Compound H-43

[0225] [Reaction Scheme 6]

[0226]

[0227] Compound H-43 was synthesized in the same manner as in Synthesis Example 1 c) using intermediate H-42-2 and biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine at an equivalent ratio of 1:1.

[0228] LC / MS calculated for: C47H33NO Exact mass: 627.26 Measured 627.77 [M+H]

[0229] Synthesis Example 7: Synthesis of Compound H-55

[0230] [Reaction Scheme 7]

[0231]

[0232] Compound H-55 was synthesized in the same manner as in Synthesis Example 1 c) using intermediate H-42-2 and (4-naphth-2-yl-phenyl)-phenyl-amine at an equivalent ratio of 1:1.

[0233] LC / MS calculated for: C42H27NO Exact mass: 561.21 Measured 561.67 [M+H]

[0234] Synthesis Example 8: Synthesis of Compound H-49

[0235] [Reaction Scheme 8]

[0236]

[0237] Using intermediate H-42-2 and biphenyl-4-yl-[4-(9-phenyl-9H-fluoren-9-yl)-phenyl]-amine at an equivalent ratio of 1:1, compound H-49 was synthesized in the same manner as in Synthesis Example 1 c).

[0238] LC / MS calculated for: C57H37NO Exact mass: 751.29 Measured 751.91 [M+H]

[0239] Synthesis Example 9: Synthesis of Compound H-56

[0240] [Reaction Scheme 9]

[0241]

[0242] Using intermediate H-1-2 and N1-([1,1'-biphenyl]-4-yl)-N3,N3-diphenylbenzene-1,3-diamine in an equivalent ratio of 1:1, compound H-56 was synthesized in the same manner as in Synthesis Example 1 c).

[0243] LC / MS calculated for: C56H39N3 Exact mass: 753.31 Measured 753.93 [M+H]

[0244] Synthesis Example 10: Synthesis of Compound H-75

[0245] [Reaction Scheme 10]

[0246]

[0247] Using intermediate H-42-2 and N1-([1,1'-biphenyl]-4-yl)-N3,N3-diphenylbenzene-1,3-diamine in an equivalent ratio of 1:1, compound H-75 was synthesized in the same manner as in Synthesis Example 1 c). LC / MS calculated: C50H34N2O Exact mass: 678.27 Measured 678.82 [M+H]

[0248] Synthesis Example 11: Synthesis of Compound H-85

[0249] [Reaction Scheme 11]

[0250]

[0251] Compound H-85 was synthesized in the same manner as in Synthesis Example 1 by using 2-bromo-3-chloro-benzaldehyde instead of the reactant 2-bromo-5-chloro-benzaldehyde.

[0252] LC / MS calculated for: C50H34N2 Exact mass: 662.27 Measured 662.82 [M+H]

[0253] Synthesis Example 12: Synthesis of Compound H-120

[0254] [Reaction Scheme 12]

[0255]

[0256] Compound H-120 was synthesized in the same manner as in Synthesis Example 1 by using 2-dibenzothiophene-3-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane and 2-bromo-4-chloro-benzaldehyde instead of the reactants 9-phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-9H-carbazole and 2-bromo-5-chloro-benzaldehyde.

[0257] LC / MS calculated for: C44H29NO Exact mass: 587.22 Observed 587.71 [M+H]

[0258] Synthesis Example 13: Synthesis of Compound H-125

[0259] [Reaction Scheme 13]

[0260]

[0261] Compound H-125 was synthesized in the same manner as in Synthesis Example 1 by using 2-dibenzothiophene-3-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane and 2-bromo-6-chloro-benzaldehyde instead of the reactants 9-phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-9H-carbazole and 2-bromo-5-chloro-benzaldehyde.

[0262] LC / MS calculated for: C44H29NO Exact mass: 587.22 Measured 587.78 [M+H]

[0263] Comparative Synthesis Example 1: Synthesis of Compound V-1

[0264] [Reaction Scheme 14]

[0265]

[0266] a) Synthesis of intermediate V-1-1

[0267] 50g (146mmol) 3,7-dibromobenzo [b, d] thiophene and 400mL tetrahydrofuran are put into a round-bottomed flask, then cooled to -78°C with dry ice and acetone under a nitrogen atmosphere. Subsequently, while maintaining the temperature, 100.5mL of 1.6M butyl lithium is slowly added dropwise thereto, and then, while still maintaining the temperature, stirred for 2 hours. At the same temperature, 103mL trimethyl borate is slowly added dropwise thereto, then heated to room temperature and stirred for 24 hours. When the reaction is complete, 2N hydrochloric acid is added thereto, then stirred. Then, EA is added to the reaction solution, and then stirred and stirred with EA / H 2 O was extracted, and the obtained EA layer was then neutralized to pH 6 to 7. The organic layer was concentrated and recrystallized with hexane, and the crystals thus obtained were dried to obtain Intermediate V-1-1 (29.4 g, 65.5%).

[0268] b) Synthesis of intermediate V-1-2

[0269] 29.4g (96mmol) of intermediate V-1-1, 32.3g (115mmol) of 2,5-dibromobenzene, 2.2g (1.9mmol) of tetrakis (triphenylphosphine) palladium (0), 26.5g (192mmol) of potassium carbonate, 176.4mL of hydrofuran, 58.8mL of oxane, and 176.4mL of water were placed in a round-bottom flask, and then refluxed. When the reaction was complete, the product was cooled to room temperature and extracted with EA, and the organic layer therefrom was concentrated and column separated. The separated solution was concentrated and recrystallized with MeOH, and the crystals produced therein were dried to obtain intermediate V-1-2 (28g, 63.1%).

[0270] c) Synthesis of Intermediate V-1-3

[0271] 28g (60mmol) intermediate V-1-2, 170mL hydrochloric acid and 560mL ethanol are put into a round-bottomed flask, and then cooled to less than or equal to 0°C, and 17.9g (151mmol) tin powder is added thereto, and then heated until it is completely dissolved. When the reaction is complete, the product is cooled to room temperature, and 40% sodium hydroxide aqueous solution is added thereto to increase pH to 10 or higher. The product is extracted with EA, the organic layer is taken out and concentrated, and then recrystallized with MeOH, the crystals produced therein are dried to obtain intermediate V-1-3 (23g, 87.8%).

[0272] d) Synthesis of Intermediate V-1-4

[0273] 23g (53mmol) of intermediate V-1-3, 9.2g (133mmol) of sodium nitrite, 22g (132.7mmol) of potassium iodide and 228mL of acetonitrile are placed in a round-bottomed flask, and then cooled to less than or equal to 0°C while stirring, and then hydrochloric acid is slowly added dropwise thereto. When the reaction is complete, the temperature is raised to room temperature, and water is added thereto, and then stirred, and after MC is added thereto in addition, it is also stirred. Subsequently, sodium thiosulfate is added thereto until the reaction solution becomes yellow. The product is extracted with MC, then concentrated and column separated, the separated solution is concentrated, and then recrystallized with hexane, and the crystals produced therein are dried to obtain intermediate V-1-4 (25g, 86.6%).

[0274] e) Synthesis of Intermediate V-1-5

[0275] 25g (46mmol) intermediate V-1-4, 1.1g (1mmol) tetrakis (triphenylphosphine) palladium (0), 0.4g (2mmol) copper iodide and 200mL triethylamine are put into a round-bottom flask, and then stirred at room temperature. While stirring the resultant, 4.7mL (46mmol) phenylacetylene is slowly added dropwise thereto. The mixture obtained is stirred for 1 hour, and hexane is poured into to complete the reaction. The reaction solution is concentrated, and then column separation is performed to obtain intermediate V-1-5 (19g, 79.7%).

[0276] f) Synthesis of Intermediate V-1-6

[0277] 19g (37mmol) of intermediate V-1-5, 1.8g (4mmol) of iron (III) trifluoromethanesulfonate and 300mL of 1,2-dichloroethane were placed in a round-bottom flask and then refluxed for 24 hours. When the reaction was complete, the product was cooled to room temperature, then concentrated and column separated, the separated solution was concentrated and recrystallized with MeOH, and the resulting crystals were then dried to obtain intermediate V-1-6 (17g, 89.5%).

[0278] g) Synthesis of Compound V-1

[0279] 17g (33mmol) of intermediate V-1-6, 13.3g (79mmol) of diphenylamine, 0.29g (1.3mmol) of palladium (II) acetate, 12.6g (131mmol) of sodium tert-butoxide and 200mL of toluene were put into a round-bottom flask, and then heated while stirring, and 2.12g (5.2mmol) of tri-tert-butylphosphine was added thereto when the temperature reached 60°C, and then refluxed. When the reaction was completed, the reaction solution was cooled to room temperature, then concentrated and column separated, the separated solution was recrystallized, and the produced crystals were filtered and dried to obtain compound V-1 (8.6g, 37.7%).

[0280] LC / MS calculated for: C50H34N2S Exact mass: 694.24 Measured 694.88 [M+H]

[0281] Comparative Synthesis Example 2: Synthesis of Compound V-2

[0282] [Reaction Scheme 15]

[0283]

[0284] a) Synthesis of intermediate V-2-1

[0285] 7.5g (1.2eq) 2-bromoiodobenzene, 780mg (0.05eq) di (chloro (triphenylphosphine)) palladium (II) and 250mg (0.06eq) CuI are mixed, the mixture is added to 70mL THF, and then stirred under a nitrogen stream, and 13mL (8eq) triethylamine and 6g (1eq) (4-ethynyl-phenyl) -diphenylamine are slowly added thereto in a dropwise manner, and then stirred at room temperature for 2 hours. After removing the sol in the substance obtained therefrom by using a rotary evaporator, 50mL water is added to the reaction solution, and then extracted three times with 50mL ether. The organic layer obtained therefrom is dried using magnesium sulfate, and the residue is separated and purified by evaporating the solvent therefrom to obtain 5g (yield: 55%) of intermediate V-2-1.

[0286] b) Synthesis of intermediate V-2-2

[0287] 5.0 g (1.0 eq) of intermediate V-2-1, 4.2 g (1.2 eq) of 3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-dibenzofuran, 950 mg (0.07 eq) of Pd(PPh 3 ) 4 and 2.8 g (1.7 eq) K 2 CO 3Mix with 30mLTHF and 15mL distilled water, heat to 70 ℃, and stir for 24 hours while refluxing.The mixture obtained is cooled to room temperature, then extracted three times with 100mL water and 100mL ether.The organic layer obtained therefrom is dried using magnesium sulfate, and the residue obtained therefrom by evaporating the solvent is separated and purified by column to obtain 3.6g (yield 60%) of intermediate V-2-2.

[0288] c) Synthesis of Compound V-2

[0289] 3.6g (1eq) intermediate V-2-2 is mixed with 500mL dichloromethane, and 20mL (40eq) trifluoroacetic acid is slowly added thereto in a dropwise manner, and then stirred at room temperature for 1 hour. When the reaction is complete, 100mL water and 100mL ether are added to the reaction solution, and then extracted three times. Subsequently, the organic layer obtained by it is dried using magnesium sulfate, and the residue obtained by evaporating solvent therein is separated and purified by column, to obtain 3.2g (productive rate is 90%) of compound V-2.

[0290] LC / MS calculated for: C38H25NO Exact mass: 511.19 Observed 511.61 [M+H]

[0291] Second compound for organic optoelectronic device

[0292] Synthesis Example 14: Synthesis of Compound A-8

[0293] [Reaction Scheme 16]

[0294]

[0295] a) Synthesis of intermediate A-8-1

[0296] 3-bromocarbazole (35g, 142mmol) is dissolved in 0.5L tetrahydrofuran (THF) in a 1L round-bottom flask, and then phenylboric acid (17.3g, 142mmol) and tetrakis (triphenylphosphine) palladium (8.2g, 7.1mmol) are added thereto, and then stirred. Subsequently, potassium carbonate (49.1g, 356mmol) saturated in water is added thereto, and then heated and refluxed at 80°C for 12 hours. When the reaction is complete, water is added to the reaction solution, the mixture is extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture therein, filtered, and concentrated under reduced pressure. The residue obtained is separated and purified by flash column chromatography to obtain 22.0g of intermediate A-8-1.

[0297] b) Synthesis of intermediate A-8-2

[0298] 2-chloro-4,6-diphenyl-[1,3,5]triazine (40g, 149mmol) is dissolved in 0.5L tetrahydrofuran (THF) in a 1L round-bottom flask, and 4-chlorophenylboric acid (25.7g, 164mmol) and tetrakis (triphenylphosphine) palladium (8.63g, 7.5mmol) are added thereto, and then stirred. Subsequently, potassium carbonate (51.6g, 374mmol) saturated in water is added thereto, and then heated and refluxed at 80°C for 12 hours. When the reaction is complete, water is added to the reaction solution, the mixture is extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained is separated and purified by flash column chromatography to obtain 32.1g of intermediate A-8-2.

[0299] c) Synthesis of Compound A-8

[0300] Intermediate A-8-1 (22.0 g, 90.4 mmol), intermediate A-8-2 (31.1 g, 90.4 mmol), sodium tert-butoxide (NaOtBu) (13.01 g, 135.6 mmol), Pd 2 (dba) 3 (2.48 g, 2.7 mmol) and tri-tert-butylphosphine (P(tBu) 3 ) (5.49 g, 50% in toluene) was added to xylene (300 mL), and then heated to reflux for 12 hours under a nitrogen stream. After removing xylene, the crystallized solid was filtered by adding 200 mL of methanol to the obtained mixture, dissolved in monochlorobenzene (MCB), and filtered through silica gel / diatomaceous earth, and an appropriate amount of organic solvent was concentrated to obtain compound A-8 (32 g, 64.3%).

[0301] LC / MS calculated for: C39H26N4 Exact mass: 550.22 Measured 550.65 [M+H]

[0302] Synthesis Example 15: Synthesis of Compound A-12

[0303] [Reaction Scheme 17]

[0304]

[0305] a) Synthesis of intermediate A-12-1

[0306] Carbazole (35 g, 209.3 mmol), 1-bromo-4-chloro-benzene (60.11 g, 313.98 mmol), CuI (3.99 g, 20.9 mmol), K 2 CO 3The product of the present invention is prepared by mixing 1,1-phenanthroline (43.39g, 313.98mmol) and 1,10-phenanthroline (3.77g, 20.9mmol) in a round-bottomed flask and dissolved in 700ml DMF. The solution obtained is stirred at 180 ℃ for 18 hours. When the reaction is complete, the product obtained after removing the reaction solvent under reduced pressure is dissolved in dichloromethane and filtered on silica gel. After concentrating dichloromethane, the product therein is recrystallized with hexane to obtain 40.0g (68.8%) of intermediate A-12-1.

[0307] b) Synthesis of intermediate A-12-2

[0308] Intermediate A-12-1 (40 g, 144 mmol), bis(pinacol)diboron (54.86 g, 216 mmol), Pd(dppf)Cl 2 (7.1 g, 8.64 mmol), tricyclohexylphosphine (8.08 g, 28.8 mmol) and potassium acetate (42.4 g, 432.04 mmol) were placed in a round bottom flask and then dissolved in 720 ml of dioxane. The mixture was refluxed at 120 ° C and stirred for 12 hours. When the reaction was complete, the mixture was poured into excess distilled water and then stirred for 1 hour. The solid was filtered and dissolved in DCM. After MgSO 4 After removing moisture, the organic solvent was filtered using a silica gel pad and then removed under reduced pressure. The solid therein was recrystallized with EA and hexane to obtain 31.3 g (58.9%) of Intermediate A-12-2.

[0309] c) Synthesis of Compound A-12

[0310] In a 1L round-bottom flask, intermediate A-12-2 (31g, 83.95mmol) was dissolved in 0.3L of tetrahydrofuran (THF), intermediate A-8-2 (28.86g, 83.95mmol) and tetrakis (triphenylphosphine) palladium (4.85g, 4.2mmol) were added thereto, and then stirred. Subsequently, potassium carbonate (29.01g, 209.9mmol) saturated in water was added thereto at 80°C for 12 hours, and then heated and refluxed. When the reaction was complete, water was added to the reaction solution, then stirred for 30 minutes and filtered, the solid thus obtained was dissolved in monochlorobenzene at 133°C, treated with anhydrous magnesium sulfate to remove moisture, and filtered by using silica gel, and the filtrate therefrom was cooled to room temperature and filtered. The solid obtained was repeatedly purified by using monochlorobenzene to obtain 31.0g (67.1%) of compound A-12.

[0311] LC / MS calculated for: C39H26N4 Exact mass: 550.22 Observed 550.75 [M+H]

[0312] Synthesis Example 16: Synthesis of Compound A-25

[0313] [Reaction Scheme 18]

[0314]

[0315] a) Synthesis of intermediate A-25-1

[0316] By using Intermediate A-8-1 (22 g, 90.4 mmol), 18 g (56.3%) of Intermediate A-25-1 was synthesized according to the same method as in Synthesis Example 15 a).

[0317] b) Synthesis of intermediate A-25-2

[0318] By using Intermediate A-25-1 (18 g, 51 mmol), 14.8 g (65.3%) of Intermediate A-25-2 was synthesized according to the same method as b) of Synthesis Example 15.

[0319] c) Synthesis of Compound A-25

[0320] 12.7 g (67.5%) of compound A-25 was synthesized according to the same method as c) of Synthesis Example 15 by using intermediate A-25-2 (10.5 g, 29.3 mmol) and 2-chloro-4-dibenzofuran-3-yl-6-phenyl-[1,3,5]triazine (14.38 g, 32.28 mmol).

[0321] LC / MS calculated for: C45H28N4O Exact mass: 640.23 Measured 640.73 [M+H]

[0322] Synthesis Example 17: Synthesis of Compound B-1

[0323] [Reaction Scheme 19]

[0324]

[0325] a) Synthesis of intermediate B-1-1

[0326] In a 500mL round-bottomed flask, 15g (81.34mmol) cyanuric chloride is dissolved in 200mL anhydrous tetrahydrofuran, 1 equivalent of 3-biphenyl magnesium bromide solution (0.5M tetrahydrofuran) is added dropwise thereto under a nitrogen atmosphere at 0°C, and then heated to room temperature. The reaction solution is stirred at room temperature for 1 hour, then put into 500mL ice water to separate layers. The organic layer is separated from it, and treated with anhydrous magnesium sulfate and concentrated. The concentrated residue is recrystallized with tetrahydrofuran and methanol, to obtain 17.2g intermediate B-1-1.

[0327] b) Synthesis of Compound B-1

[0328] In a 500mL round-bottomed flask, 17.2g (56.9mmol) of intermediate B-1-1 is added to 200mL tetrahydrofuran and 100mL distilled water, and 2 equivalents of dibenzofuran-3-boric acid (cas: 395087-89-5), 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate are added thereto, and then heated to reflux under a nitrogen atmosphere. After 18 hours, the reaction solution is cooled, and the solid precipitated therein is filtered and washed with 500mL water. The solid is recrystallized with 500mL of monochlorobenzene to obtain 12.87g of compound B-1.

[0329] LC / MS calculated for: C39H23N3O2 Exact mass: 565.1790 Measured: 566.18 [M+H]

[0330] Synthesis Example 18: Synthesis of Compound B-3

[0331] [Reaction Scheme 20]

[0332]

[0333] a) Synthesis of intermediate B-3-1

[0334] In nitrogen environment, magnesium (7.86g, 323mmol) and iodine (1.64g, 6.46mmol) are added in 0.1L tetrahydrofuran (THF), and then stirred for 30 minutes, and 1-bromo-3,5-diphenylbenzene (100g, 323mmol) dissolved in 0.3LTHF is slowly added thereto in a dropwise manner at 0 ℃ for 30 minutes. At 0 ℃, through 30 minutes, the mixed solution of this acquisition is slowly added to 64.5g (350mmol) cyanuric chloride dissolved in 0.5L THF in a dropwise manner. When the reaction is complete, water is added to the reaction solution, and then extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under reduced pressure. The residue obtained is separated and purified by flash column chromatography to obtain intermediate B-3-1 (79.4g, 65%).

[0335] b) Synthesis of Compound B-3

[0336] By using the intermediate B-3-1, the compound B-3 was synthesized according to the same method as b) of Synthesis Example 17.

[0337] LC / MS calculated for: C45H27N3O2 Exact mass: 641.2103 Observed 642.21 [M+H]

[0338] Synthesis Example 19: Synthesis of Compound B-17

[0339] [Reaction Scheme 21]

[0340]

[0341] a) Synthesis of intermediate B-17-1

[0342] In a 500mL round-bottom flask, 22.6g (100mmol) of 2,4-dichloro-6-phenyltriazine is added to 100mL of tetrahydrofuran, 100mL of toluene and 100mL of distilled water, and 0.9 equivalent of dibenzofuran-3-boric acid (CAS No.: 395087-89-5), 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate are added thereto, and then heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled, and after removing the water layer, the organic layer is dried under reduced pressure. The solid obtained is washed with water and hexane, then recrystallized from 200mL of toluene, to obtain 21.4g (yield is 60%) of intermediate B-17-1.

[0343] b) Synthesis of Compound B-17

[0344] In a 500mL round-bottomed flask, intermediate B-17-1 (56.9mmol) is added to 200mL of tetrahydrofuran (THF) and 100mL of distilled water, and 1.1 equivalents of 3,5-diphenylphenylboronic acid (CAS: 128388-54-5), 0.03 equivalent of tetrakis triphenylphosphine palladium and 2 equivalents of potassium carbonate are added thereto, and then heated to reflux under a nitrogen atmosphere. After 18 hours, the reaction solution is cooled, and the solid precipitated therein is filtered and washed with 500mL of water. The solid is recrystallized with 500mL of monochlorobenzene. To obtain compound B-17.

[0345] LC / MS calculated for: C39H25N3O Exact mass: 555.1998 Observed 556.21 [M+H]

[0346] Synthesis Example 20: Synthesis of Compound B-23

[0347] [Reaction Scheme 22]

[0348]

[0349] a) Synthesis of intermediate B-23-1

[0350] In a 500mL round-bottomed flask, 15g (81.34mmol) cyanuric chloride is dissolved in 200mL anhydrous tetrahydrofuran, 1 equivalent of 4-biphenyl magnesium bromide solution (0.5M tetrahydrofuran) is added dropwise thereto at 0°C and under a nitrogen atmosphere, and then slowly heated to room temperature. The reaction solution is stirred at room temperature for 1 hour and put into 500mL of ice water to separate layers. The organic layer is separated from it, and then treated with anhydrous magnesium sulfate and concentrated. The concentrated residue is recrystallized with tetrahydrofuran and methanol, to obtain 17.2g intermediate B-23-1.

[0351] b) Synthesis of intermediate B-23-2

[0352] Intermediate B-23-2 was synthesized according to the same method as in Synthesis Example 19 a) by using Intermediate B-23-1.

[0353] c) Synthesis of Compound B-23

[0354] Compound B-23 was synthesized according to the same method as b) of Synthesis Example 19 by using Intermediate B-23-2 and 1.1 equivalents of 3,5-diphenylbenzeneboronic acid.

[0355] LC / MS calculated for: C45H29N3O Exact mass: 627.2311 Observed 628.24 [M+H]

[0356] Synthesis Example 21: Synthesis of Compound B-129

[0357] [Reaction Scheme 23]

[0358]

[0359] a) Synthesis of intermediate B-129-1

[0360] Intermediate B-129-1 was synthesized according to the same method as b) of Synthesis Example 19 by using 1.0 equivalent of 1-bromo-4-chloro-benzene and 3-dibenzofuranylboronic acid, respectively.

[0361] b) Synthesis of intermediate B-129-2

[0362] Intermediate B-129-2 was synthesized according to the same method as Synthesis Example 15 by using Intermediate B-129-1 and bispinacol diboron at an equivalent ratio of 1:1.2.

[0363] c) Synthesis of Compound B-129

[0364] Compound B-129 was synthesized according to the same method as Synthesis Example 19 by using 1.0 equivalent of Intermediate B-129-2 and 2-chloro-4-(biphenyl-4-yl)6-phenyl-1,3,5-triazine, respectively.

[0365] LC / MS calculated for: C39H25N3O Exact mass: 551.20 Observed 551.24 [M+H]

[0366] Synthesis Example 22: Synthesis of Compound B-133

[0367] [Reaction Scheme 24]

[0368]

[0369] Compound B-133 was synthesized according to the same method as Synthesis Example 19 by using Intermediate B-17-1 and Intermediate B-129-2.

[0370] LC / MS calculated for: C39H23N3O2 Exact mass: 565.18 Observed 565.22 [M+H]

[0371] Synthesis Example 23: Synthesis of Compound B-135

[0372] [Reaction Scheme 25]

[0373]

[0374] a) Synthesis of intermediate B-135-1

[0375] Intermediate B-135-1 was synthesized according to the same method as b) of Synthesis Example 19 by using 1.0 equivalent of 1-bromo-4-chloro-benzene and 2-naphthaleneboronic acid, respectively.

[0376] b) Synthesis of intermediate B-135-2

[0377] Intermediate B-135-2 was synthesized according to the same method as Synthesis Example 19 by using Intermediate B-135-1 and bispinacol diboron at an equivalent ratio of 1:1.2.

[0378] c) Synthesis of Compound B-135

[0379] Compound B-135 was synthesized according to the same method as Synthesis Example 19 by using 1.0 equivalent of Intermediate B-135-2 and Intermediate B-17-1, respectively.

[0380] LC / MS calculated for: C37H23N3O Exact mass: 525.18 Observed 525.22 [M+H]

[0381] Synthesis Example 24: Synthesis of Compound D-25

[0382] [Reaction Scheme 26]

[0383]

[0384] a) Synthesis of intermediate Int-1

[0385] 1-Bromo-4-chloro-2-fluorobenzene (61 g, 291 mmol), 2,6-dimethoxyphenylboronic acid (50.4 g, 277 mmol), K 2 CO 3 (60.4 g, 437 mmol) and Pd(PPh 3 ) 4 (10.1 g, 8.7 mmol) was put into a round-bottom flask, and then dissolved in 500 ml of THF and 200 ml of distilled water, and then refluxed and stirred at 60° C. for 12 hours. When the reaction was completed, the aqueous layer was removed therefrom, and 38 g (51%) of Intermediate Int-1 was obtained by column chromatography (hexane: DCM (20%)).

[0386] b) Synthesis of intermediate Int-2

[0387] Intermediate Int-1 (38 g, 142 mmol) and pyridine hydrochloride (165 g, 1425 mmol) were placed in a round-bottom flask, and then refluxed and stirred at 200° C. for 24 hours. When the reaction was complete, the product was cooled to room temperature and slowly poured into distilled water, and then stirred for 1 hour. The solid was filtered to obtain 23 g of intermediate Int-2 (68%).

[0388] c) Synthesis of intermediate Int-3

[0389] Intermediate Int-2 (23 g, 96 mmol) and K 2 CO 3 (20 g, 144 mmol) was placed in a round-bottom flask and then dissolved in 100 ml of NMP, then refluxed at 180° C. and stirred for 12 hours. When the reaction was complete, the mixture was poured into an excess of distilled water. The solid was filtered and then dissolved in ethyl acetate and MgSO 4 After drying, the organic layer was removed therefrom under reduced pressure. 16 g (76%) of Intermediate Int-3 was obtained by column chromatography (hexane:EA (30%)).

[0390] d) Synthesis of intermediate Int-4

[0391] Intermediate Int-3 (16g, 73mmol) and pyridine (12ml, 146mmol) are put into a round-bottom flask and dissolved in 200ml DCM. The temperature is reduced to 0 ° C, and trifluoromethanesulfonic anhydride (14.7ml, 88mmol) is slowly added thereto in a dropwise manner. After the mixture is stirred for 6 hours, when the reaction is complete, excessive distilled water is added thereto, then stirred for 30 minutes and extracted with DCM. After removing the organic solvent under reduced pressure, 22.5g (88%) of intermediate Int-4 is obtained by vacuum drying.

[0392] e) Synthesis of intermediate Int-5

[0393] By using intermediate Int-4 (22.5 g, 64 mmol), phenylboronic acid (7.8 g, 64 mmol), K 2 CO 3 (13.3 g, 96 mmol) and Pd(PPh 3 ) 4 (3.7 g, 3.2 mmol), and 14.4 g (81%) of the intermediate Int-5 was synthesized according to the same method as b) of Synthesis Example 19.

[0394] f) Synthesis of intermediate Int-6

[0395] Intermediate Int-5 (22.5 g, 80 mmol), bis(pinacol)diboron (24.6 g, 97 mmol), Pd(dppf)Cl 2 (2g, 2.4mmol), tricyclohexylphosphine (3.9g, 16mmol) and potassium acetate (16g, 161mmol) were placed in a round bottom flask and then dissolved in 320ml DMF. The mixture was refluxed at 120°C and stirred for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and then stirred for 1 hour. The solid was filtered and dissolved in DCM. After MgSO 4 After removing moisture, the mixture was filtered through a silica gel pad and the organic solvent was removed under reduced pressure. Then, the solid was recrystallized with EA and hexane to obtain 26.9 g (90%) of Intermediate Int-6.

[0396] g) Synthesis of Compound D-25

[0397] By using intermediate B-23-2 (15 g, 35 mmol), intermediate Int-6 (12.8 g, 35 mmol), K 2 CO 3 (7.2 g, 52 mmol) and Pd(PPh 3 ) 4(2 g, 1.7 mmol), and 15.5 g (70%) of compound D-25 were synthesized in a round-bottom flask under nitrogen conditions according to the same method as b) of Synthesis Example 19.

[0398] LC / MS calculated for: C45H27N3O2 Exact mass: 641.21 Measured 641.25 [M+H]

[0399] Synthesis Example 25: Synthesis of Compound D-3

[0400] [Reaction Scheme 27]

[0401]

[0402] a) Synthesis of intermediate D-3-1

[0403] Intermediate D-3-1 was synthesized according to the same method as synthesis of 24 by using 1.0 equivalent of 2-bromo-1-chloro-3-fluoro-benzene and 2-hydroxyphenylboronic acid, respectively.

[0404] b) Synthesis of intermediate D-3-2

[0405] By using intermediate D-3-1 and K in an equivalent ratio of 1:1.5 2 CO 3 , intermediate D-3-2 was synthesized according to the same method as Synthesis Example 24.

[0406] c) Synthesis of intermediate D-3-3

[0407] Intermediate D-3-3 was synthesized according to the same method as Synthesis Example 24 by using Intermediate D-3-2 and bis(pinacolato)diboron at an equivalent ratio of 1:1.2.

[0408] d) Synthesis of Compound D-3

[0409] Compound D-3 was synthesized according to the same method as b) of Synthesis Example 19 by using 1.0 equivalent of Intermediate D-3-3 and 2,4-bis([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine, respectively.

[0410] LC / MS calculated for: C39H25N3O Exact mass: 551.20 Observed 551.24 [M+H]

[0411] Synthesis Example 26 to Synthesis Example 29

[0412] Referring to the synthesis method disclosed in Korean Patent Application Publication No. 10-2014-0135524, compounds E-31, E-33, E-35 and E-37 were synthesized using the following starting material 1 and starting material 2, respectively.

[0413] [Table 1]

[0414]

[0415]

[0416] (Manufacturing of Organic Light Emitting Diode I)

[0417] Example 1

[0418] The coating will have a thickness of The glass substrate of ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent (such as isopropyl alcohol, acetone, methanol, etc.) and dried, and then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus obtained was used as an anode, and compound A was vacuum-deposited on the ITO substrate to form The hole injection layer is formed into a hole injection layer having a thickness of thick, and then compound C is deposited as On the hole transport layer, a hole transport layer is formed by depositing compound H-1 On the hole transport layer, by using compound E as the host and doping 2 wt% of [Ir(piq) 2 acac] as a dopant to form Subsequently, on the light-emitting layer, a thin film of compound D and Liq was formed by simultaneously vacuum depositing the compound D and Liq at a ratio of 1:1. A thick electron transport layer is formed, and Liq and Al are vacuum deposited sequentially on the electron transport layer. Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0419] The organic light emitting diode has five organic thin layers, and specifically has the following structure.

[0420] ITO / Compound A / Compound B / Compound C / Compound H-1 / EML[Compound E:[Ir(piq)2acac](2wt%)] / Compound D: Liq / Liq / Al

[0421] Compound A: N4, N4'-diphenyl-N4, N4'-bis(9-phenyl-9H-carbazole-3-yl)biphenyl-4, 4'-diamine

[0422] Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN),

[0423] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0424] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

[0425] Compound E: 9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-dicarbazole

[0426] Examples 2 to 6 and Comparative Examples 1 and 2

[0427] As shown in Table 2, devices of Examples 2 to 6 and Comparative Examples 1 and 2 were manufactured in the same manner as in Example 1 using the hole transport auxiliary layer of the present invention.

[0428] (Manufacturing of Organic Light Emitting Diode II)

[0429] Example 7

[0430] The coating will have a thickness of The glass substrate of ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent (such as isopropyl alcohol, acetone, methanol, etc.) and dried, and then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The ITO transparent electrode thus obtained was used as an anode, and compound A was vacuum-deposited on the ITO substrate to form The hole injection layer is formed into a hole injection layer having a thickness of thick, and then compound C is deposited as On the hole transport layer, a hole transport layer is formed by depositing compound C-1 On the hole transport layer, by using compound H-1 and compound E-35 as the host at the same time and doping 2wt% of [Ir(piq) 2 acac] as a dopant to form Herein, compound H-1 and compound E-35 were used in a weight ratio of 7:3, and the ratios are described in the following examples, respectively. Subsequently, on the light-emitting layer, a film was formed by simultaneously vacuum depositing compound D and Liq in a ratio of 1:1. A thick electron transport layer is formed, and Liq and Al are vacuum deposited sequentially on the electron transport layer. Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0431] The organic light emitting diode has five organic thin layers, and specifically has the following structure.

[0432] ITO / Compound A / Compound B / Compound / Compound C-1 / EML[Compound H-1:E-35:[Ir(piq) 2 acac](2wt%)] / Compound D: Liq / Liq / Al

[0433] Compound C-1: N,N-di([1,1'-biphenyl]-4-yl)-7,7-dimethyl-7H-fluoren[4,3-b]benzofuran-10-amine

[0434] Examples 8 to 18, Reference Examples 1 and 2

[0435] Each organic light emitting diode was manufactured in the same manner as in Example 7, except that the composition was changed to the composition shown in Table 3.

[0436] Evaluate

[0437] The power efficiency of the organic light emitting diodes according to Examples 1 to 18, Comparative Examples 1 and 2, and Reference Examples 1 and 2 was evaluated.

[0438] The specific measurement method is as follows, and the results are shown in Tables 2 and 3.

[0439] (1) Measurement of current density changes depending on voltage changes

[0440] The obtained organic light emitting diode was measured with respect to a current value flowing in a unit device while increasing a voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by an area to provide a result.

[0441] (2) Measurement of brightness changes depending on voltage changes

[0442] While increasing the voltage of the organic light emitting diode from 0 V to 10 V, the luminance was measured using a luminance meter (Minolta Cs-1000A).

[0443] (3) Measurement of luminous efficiency

[0444] By using the luminance and current density from items (1) and (2), the luminance at the same current density (10 mA / cm 2 ) under power efficiency (lm / W).

[0445] (4) Lifespan measurement

[0446] The T97 lifespan of the organic light emitting diodes of Examples 1 to 18, Comparative Examples 1, 2, Reference Examples 1 and 2 was measured at 6000 cd / m 2 The initial brightness of the light emitted after their brightness relative to the initial brightness (cd / m 2 ) to 97% and their time-dependent brightness reduction was measured using the Polanonix lifetime measurement system.

[0447] [Table 2]

[0448]

[0449]

[0450] [Table 3]

[0451]

[0452] Referring to Table 2, the lifespan of the organic light emitting diodes according to Examples 1 to 6 is significantly improved compared to the organic light emitting diodes according to Comparative Examples 1 and 2.

[0453] In addition, referring to Table 3, compared with the organic light emitting diodes according to Reference Examples 1 and 2, the organic light emitting diodes according to Examples 7 to 18 have greatly improved efficiency and lifespan.

[0454] While the invention has been described in connection 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 on the contrary is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A composition for an organic optoelectronic device, comprising a first compound for an organic photoelectric device represented by one of Chemical Formula 1-1 to Chemical Formula 1-4, and The second compound for an organic photoelectric device represented by Chemical Formula 2: in, In Chemical Formula 1-1 to Chemical Formula 1-4, X 1 is O or S, L 1 is a single bond or unsubstituted phenylene, L 2 and L 3 is a single key, R 1 To R 5 are independently hydrogen or deuterium, Ar 1 and Ar 2 are independently a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted C6 to C12 arylamine group, [Chemical formula 2] Wherein, in Chemical Formula 2, Z 1 To Z 3 It is N, L 4 To L 6 are independently a single bond, or a substituted or unsubstituted phenylene group, R 15 To R 17 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, carbazolyl substituted with phenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted triphenylene, R 15 To R 17 At least one of the following is a carbazolyl group substituted with a phenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted triphenylene group, and Herein, "substituted" means that at least one hydrogen of the substituted group is replaced by deuterium or C1 to C5 alkyl.

2. The composition according to claim 1, wherein Ar 1 is a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group, and Ar 2 is a substituted or unsubstituted biphenyl group.

3. The composition according to claim 1, wherein Ar 1 and Ar 2 A group independently selected from Group I: [Group I] Where, in group I, * is the connection point.

4. The composition according to claim 1, wherein the first compound is selected from the group consisting of: [Group 1] 5. The composition according to claim 1, wherein Chemical Formula 2 is represented by one of Chemical Formula 2-1 to Chemical Formula 2-3: Among them, in Chemical Formula 2-1 to Chemical Formula 2-3, Z 1 To Z 3 It is N, X 3 It's O. L 4 To L 6 are independently a single bond, or a substituted or unsubstituted phenylene group, R g , R h , R i and R j One of them is phenyl, and the other three are R k , R l , R m , R n , R o , R p , R q , R r , R s are independently hydrogen, deuterium or C1 to C5 alkyl, and R 16 and R 17 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, carbazolyl substituted with phenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted triphenylene.

6. The composition according to claim 1, wherein The first compound for an organic photoelectric device is represented by Chemical Formula 1-3, and the second compound for an organic photoelectric device is represented by Chemical Formula 2-1 or Chemical Formula 2-2: [Chemical formula 1-3] Wherein, in chemical formula 1-3, X 1 is O or S, L 1 is a single bond or unsubstituted phenylene, L 2 and L 3 is a single key, R 1 To R 5 are independently hydrogen or deuterium, and Ar 1 and Ar 2 are independently substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, or substituted or unsubstituted C6 to C12 arylamine; In Chemical Formula 2-1 and Chemical Formula 2-2, Z 1 To Z 3 It is N, X 3 It's O. L 4 To L 6 are independently a single bond, or a substituted or unsubstituted phenylene group, R 16 and R 17 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, carbazolyl substituted with phenyl, or substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, R g , R h , R i and R j One of them is phenyl, and the other three are R k , R l , R m are independently hydrogen, deuterium or C1 to C5 alkyl.

7. The composition according to claim 1, wherein The first compound for an organic photoelectric device is represented by Chemical Formula 1a or Chemical Formula 1d, and The second compound for an organic photoelectric device is represented by Chemical Formula 2-1 or Chemical Formula 2-2: Wherein, in Chemical Formula 1a and Chemical Formula 1d, X 1 is O or S, L 1 is a single bond or unsubstituted phenylene, L 2 is an unsubstituted phenylene group, L 3 is a single key, R 1 To R 7 are independently hydrogen or deuterium, and Ar 2 is a substituted or unsubstituted biphenyl group, Ar 4 and Ar 5 are independently substituted or unsubstituted phenyl; In Chemical Formula 2-1 and Chemical Formula 2-2, Z 1 To Z 3 It is N, X 3 It's O. L 4 To L 6 is independently a single bond, or a substituted or unsubstituted phenylene group, R 16 and R 17 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, carbazolyl substituted with phenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, R g , R h , R i and R j One of them is phenyl, and the other three are R k , R l , R m are independently hydrogen, deuterium or C1 to C5 alkyl.

8. The composition of claim 1, further comprising a dopant.

9. An organic optoelectronic device, comprising The anode and cathode face each other, at least one organic layer between the anode and the cathode, in, The organic layer comprises the composition for an organic optoelectronic device according to any one of claims 1 to 8.

10. The organic optoelectronic device according to claim 9, wherein: The organic layer includes a light-emitting layer, and The light-emitting layer includes the composition for an organic photoelectric device.

11. The organic optoelectronic device according to claim 10, wherein: The first compound for an organic photoelectric device and the second compound for an organic photoelectric device are included as respective phosphorescent hosts of the light emitting layer.

12. The organic optoelectronic device according to claim 10, wherein: The composition for an organic optoelectronic device is a red light-emitting composition. 13 . A display device comprising the organic optoelectronic device according to claim 9 .

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