Composition for organic optoelectronic device, organic optoelectronic device, and display device

Abstract

Disclosed are a composition for an organic optoelectronic device, and an organic optoelectronic device and a display device comprising the same, the composition for an organic optoelectronic device comprising a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2. Details of the chemical formula 1 and the chemical formula 2 are described in the specification.

Description

Technical Field

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

[0002] An organic optoelectronic device (organic optoelectronic diode) is a device capable of converting electrical energy and light energy into each other.

[0003] According to the operating principle, organic optoelectronic devices can be roughly classified into two types. One is a photoelectric device that generates electrical energy by separating excitons formed using light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively, and the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to an electrode.

[0004] Examples of organic optoelectronic devices include organic optoelectronic elements, organic light-emitting diodes, organic solar cells, and organic photo-conductor drums.

[0005] Among these examples, due to the increasing demand for flat panel displays, organic light-emitting diodes (OLEDs) have been attracting much attention in recent years. An organic light-emitting diode is a device that converts electrical energy into light, and the performance of an organic light-emitting diode is greatly affected by the organic material between the electrodes. Summary of the Invention

[0006] [Technical Problem]

[0007] One embodiment provides a composition for an organic optoelectronic device, which can achieve an organic optoelectronic device having high efficiency and long life.

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

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

[0010] [Technical Solution]

[0011] According to an embodiment, a composition for an organic optoelectronic device includes a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2.

[0012] [Chemical Formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] Z 1 to Z 3 are each independently N or C-R a ,

[0016] Z 1 to Z 3 at least two of which are N,

[0017] L 1 is a single bond or a substituted or unsubstituted C6-C20 arylene group,

[0018] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6-C30 aryl group, and

[0019] R a and R 1 to R 8 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof;

[0020] [Chemical Formula 2]

[0021]

[0022] wherein, in Chemical Formula 2,

[0023] X 1 is O or S,

[0024] Ar 3 is a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof,

[0025] R 9 to R 12 are each independently hydrogen, deuterium, cyano, halogen, a substituted or unsubstituted amino group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C2-C30 heterocyclic group,

[0026] R 13 to R 15 are each independently hydrogen, deuterium, or a substituted or unsubstituted phenyl group,

[0027] m2, m3, m5, and m6 are each independently one of the integers from 1 to 3, and

[0028] m1, m4, and m7 are each independently one of the integers from 1 to 4.

[0029] According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other and at least one organic layer located between the anode and the cathode, wherein the organic layer contains the composition for the organic optoelectronic device.

[0030] [Advantages of the Invention]

[0031] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0032] An organic optoelectronic device with high efficiency, long lifespan, and low drive can be implemented. Description of the Drawings

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

[0034] [Reference Signs]

[0035] 100: Organic light-emitting diode

[0036] 105: Organic layer

[0037] 110: Cathode

[0038] 120: Anode

[0039] 130: Light-emitting layer

[0040] 140: Hole transport region

[0041] 150: Electron transport region Detailed Description of the Embodiments

[0042] 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 the present invention is defined by the scope of the claims.

[0043] In this specification, when no other definition is provided, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, a halogen, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C30 amino group, a nitro group, a substituted or unsubstituted C1-C40 silyl group, a C1-C30 alkyl group, a C1-C10 alkylsilyl group, a C6-C30 arylsilyl group, a C3-C30 cycloalkyl group, a C3-C30 heterocycloalkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C1-C20 alkoxy group, a C1-C10 trifluoroalkyl group, a cyano group, or a combination thereof.

[0044] In one example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, cyano, C1-C30 alkyl, C1-C10 alkylsilyl, C6-C30 arylamine, C6-C30 arylsilyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl or C2-C30 heteroaryl. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, cyano, C1-C20 alkyl, C6-C30 arylamine, C6-C3 aryl or C2-C30 heteroaryl. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, cyano, C1-C5 alkyl, C6-C20 arylamine, C6-C18 aryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl or pyridyl. In a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, C6-C20 arylamine, phenyl, biphenyl, terphenyl, naphthyl, triphenyl, fluorene, dibenzofuranyl, dibenzothiophenyl, carbazolyl or pyridyl.

[0045] In this specification, "unsubstituted" means that a hydrogen atom is not replaced by another substituent and the hydrogen atom is retained.

[0046] In this specification, "deuterium substitution (-D)" may include "tritium substitution (-T)".

[0047] In this specification, when no other definition is provided, "hetero" means including one to three heteroatoms selected from N, O, S, P and Si in a functional group and the rest being carbon.

[0048] In this specification, "aryl" means a group including at least one hydrocarbon aromatic moiety, and may include a group in which all elements of the hydrocarbon aromatic moiety have p-orbitals forming conjugation (such as phenyl, naphthyl and similar groups), a group in which two or more hydrocarbon aromatic moieties may be linked by a σ bond (such as biphenyl, terphenyl, quaterphenyl and similar groups), and a group in which two or more hydrocarbon aromatic moieties are directly or indirectly fused to provide a non-aromatic fused ring (such as fluorene and similar groups).

[0049] Aryl may include monocyclic, polycyclic or fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0050] 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 to replace carbon (C) in a cyclic compound, such as aryl, cycloalkyl, its fused ring or its combination. When the heterocyclic group is a fused ring, the whole ring or each ring of the heterocyclic group may include one or more heteroatoms.

[0051] For example, "heteroaryl" may refer to an aryl group including at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are directly linked by a σ bond, or when a heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.

[0052] More specifically, the substituted or unsubstituted C6-C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fused tetraphenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted group, a substituted or unsubstituted benzotriphenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but not limited thereto.

[0053] More specifically, the substituted or unsubstituted C2-C30 heterocyclic group may be a substituted or unsubstituted furyl group, 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 benzofuryl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl 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 dibenzofuryl group, or a substituted or unsubstituted dibenzothienyl group, or a combination thereof, but not limited thereto.

[0054] In this specification, the hole property refers to the following ability: when an electric field is applied, it donates an electron to form a hole, and due to the conductive property according to the highest occupied molecular orbital (HOMO) energy level, the hole formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0055] In addition, the electron property refers to the following ability: when an electric field is applied, it accepts an electron, and due to the conductive property according to the lowest unoccupied molecular orbital (LUMO) energy level, the electron formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0056] Hereinafter, a composition for an organic optoelectronic device according to an embodiment will be described.

[0057] The composition for an organic optoelectronic device according to an embodiment includes a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2.

[0058] The first compound can be represented by Chemical Formula 1.

[0059] [Chemical Formula 1]

[0060]

[0061] In Chemical Formula 1,

[0062] Z 1 to Z 3 are each independently N or C-R a ,

[0063] Z 1 to Z 3 at least two of them are N,

[0064] L 1 is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0065] Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 aryl group, and

[0066] R a and R 1 to R 8 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

[0067] The first compound represented by Chemical Formula 1 has a structure in which carbazole is the basic skeleton and at least one nitrogen-containing ring (a 6-membered nitrogen-containing ring) is substituted at the 9th position of carbazole.

[0068] The compound contains at least one nitrogen-containing ring, and thus, when an electric field is applied to the compound, the compound may have a structure that easily accepts electrons, and thus the driving voltage of an organic optoelectronic device manufactured using the compound is reduced.

[0069] In addition, the first compound can form a bipolar structure by including carbazole that easily accepts holes to appropriately balance the flow of holes and electrons, thereby improving the efficiency of an organic optoelectronic device including the compound.

[0070] In particular, by linking to a 6-membered nitrogen-containing ring in the 9th direction (N direction) of carbazole, π-bond cleavage achieved by a C-N bond, and the electron cloud between HOMO and LUMO is clearly confined to the hole transport part and the electron transport part, this widens the HOMO-LUMO band gap, and thus the efficiency of an organic light-emitting diode using it can be further improved.

[0071] As an example, Ar in Chemical Formula 1 1 and Ar 2 can each 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 terrylene group, or a substituted or unsubstituted fluorenyl group.

[0072] As a specific example, Ar in Chemical Formula 1 1 and Ar 2 can each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terrylene group.

[0073] As an example, R in Chemical Formula 1 1 to R 8 can each independently be hydrogen, deuterium, a cyano group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C2-C20 heterocyclic group.

[0074] As a specific example, R in Chemical Formula 1 1 to R 8Each may independently be hydrogen, deuterium, cyano, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0075] As an example, L in Chemical Formula 1 1 may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted triphenylenylene group.

[0076] For example, L in Chemical Formula 1 1 may be a substituted or unsubstituted phenylene group.

[0077] The first compound may be, for example, one selected from the compounds listed in Group 1.

[0078] [Group 1]

[0079]

[0080]

[0081]

[0082] The second compound may be represented by Chemical Formula 2.

[0083] [Chemical Formula 2]

[0084]

[0085] In Chemical Formula 2,

[0086] X 1 is O or S,

[0087] Ar 3 is a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C2 - C30 heterocyclic group, or a combination thereof,

[0088] R 9 to R 12 each independently is hydrogen, deuterium, cyano, halogen, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 - C30 alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6 - C30 aryl group, or a substituted or unsubstituted C2 - C30 heterocyclic group,

[0089] R 13 to R 15 each independently is hydrogen, deuterium, or a substituted or unsubstituted phenyl group,

[0090] m2, m3, m5, and m6 are each independently one of the integers from 1 to 3, and

[0091] m1, m4, and m7 are each independently one of the integers from 1 to 4.

[0092] The second compound has hole characteristics, and at least one N-direction substituent of the bi-carbazole is dibenzofuran (or dibenzothiophene), and dibenzofuran (or dibenzothiophene) has a phenyl-substituted structure at the 9th position.

[0093] The bi-carbazole having dibenzofuran (or dibenzothiophene) phenyl-substituted at the 9th position has the property of shortening the distance between the molecules of the hole characteristic compound and the molecules of the electron characteristic compound. In particular, the LUMO of the hole characteristic compound and the LUMO of the electron characteristic compound are closely arranged such that the LUMO of the electron characteristic compound extends to the LUMO of the hole characteristic compound, and are deposited in an arrangement favorable for electron transfer. Due to the above structural arrangement, high efficiency characteristics of the organic light emitting diode using the above structural arrangement can be achieved.

[0094] In particular, when used together with the above first compound, charge balance is appropriately maintained and exciton generation is favorable, thereby enabling high efficiency device characteristics to be implemented.

[0095] In Chemical Formula 2, when m1 is 2 or greater than 2, each R 9 may be the same as or different from each other.

[0096] In Chemical Formula 2, when m2 is 2 or greater than 2, each R 10 may be the same as or different from each other.

[0097] In Chemical Formula 2, when m3 is 2 or greater than 2, each R 11 may be the same as or different from each other.

[0098] In Chemical Formula 2, when m4 is greater than or equal to 2, each R 12 may be the same as or different from each other.

[0099] In Chemical Formula 2, when m5 is greater than or equal to 2, each R 13 may be the same as or different from each other.

[0100] In Chemical Formula 2, when m6 is greater than or equal to 2, each R 14 may be the same as or different from each other.

[0101] In Chemical Formula 2, when m7 is greater than or equal to 2, each R 15 may be the same as or different from each other.

[0102] For example, the second compound can be represented by any one of Chemical Formulas 2-1 to 2-4.

[0103] [Chemical Formula 2-1][Chemical Formula 2-2]

[0104]

[0105] [Chemical Formula 2-3][Chemical Formula 2-4]

[0106]

[0107] In Chemical Formulas 2-1 to 2-4, X 1 , Ar 3 , R 9 to R 15 and m1 to m7 are the same as those described above. As a specific example, Chemical Formula 2-1 can be represented by any one of Chemical Formulas 2-1-1 to 2-1-16. [Chemical Formula 2-1-1][Chemical Formula 2-1-2][Chemical Formula 2-1-3]

[0108]

[0109] [Chemical Formula 2-1-4][Chemical Formula 2-1-5][Chemical Formula 2-1-6]

[0110]

[0111] [Chemical Formula 2-1-7][Chemical Formula 2-1-8][Chemical Formula 2-1-9]

[0112]

[0113] [Chemical Formula 2-1-10][Chemical Formula 2-1-11][Chemical Formula 2-1-12]

[0114]

[0115] [Chemical Formula 2-1-13][Chemical Formula 2-1-14][Chemical Formula 2-1-15]

[0116]

[0117] [Chemical Formula 2-1-16]

[0118]

[0119] In Chemical Formulas 2-1-1 to 2-1-16, X 1 , Ar 3 , R 9 to R 15, m1 to m7 are the same as those above. As a specific example, Chemical Formula 2-2 can be represented by any one of Chemical Formulas 2-2-1 to 2-2-16.

[0120] [Chemical Formula 2-2-1][Chemical Formula 2-2-2][Chemical Formula 2-2-3]

[0121]

[0122] [Chemical Formula 2-2-4][Chemical Formula 2-2-5][Chemical Formula 2-2-6]

[0123]

[0124] [Chemical Formula 2-2-7][Chemical Formula 2-2-8][Chemical Formula 2-2-9]

[0125]

[0126] [Chemical Formula 2-2-10][Chemical Formula 2-2-11][Chemical Formula 2-2-12]

[0127]

[0128] [Chemical Formula 2-2-13][Chemical Formula 2-2-14][Chemical Formula 2-2-15]

[0129]

[0130] [Chemical Formula 2-2-16]

[0131]

[0132] In Chemical Formulas 2-2-1 to 2-2-16, X 1 、Ar 3 、R 9 to R 15 and m1 to m7 are the same as those above. As a specific example, Chemical Formula 2-3 can be represented by any one of Chemical Formulas 2-3-1 to 2-3-16.

[0133] [Chemical Formula 2-3-1][Chemical Formula 2-3-2][Chemical Formula 2-3-3]

[0134]

[0135] [Chemical Formula 2-3-4][Chemical Formula 2-3-5][Chemical Formula 2-3-6]

[0136]

[0137] [Chemical formula 2-3-7][Chemical formula 2-3-8][Chemical formula 2-3-9]

[0138]

[0139] [Chemical formula 2-3-10][Chemical formula 2-3-11][Chemical formula 2-3-12]

[0140]

[0141] [Chemical formula 2-3-13][Chemical formula 2-3-14][Chemical formula 2-3-15]

[0142]

[0143] [Chemical formula 2-3-16]

[0144]

[0145] In Chemical formulas 2-3-1 to 2-3-16, X 1 , Ar 3 , R 9 to R 15 and m1 to m7 are the same as those above. As a specific example, Chemical formula 2-4 can be represented by any one of Chemical formulas 2-4-1 to 2-4-10.

[0146] [Chemical formula 2-4-1][Chemical formula 2-4-2][Chemical formula 2-4-3]

[0147]

[0148] [Chemical formula 2-4-4][Chemical formula 2-4-5][Chemical formula 2-4-6]

[0149]

[0150] [Chemical formula 2-4-7][Chemical formula 2-4-8][Chemical formula 2-4-9]

[0151]

[0152] [Chemical formula 2-4-10][Chemical formula 2-4-11][Chemical formula 2-4-12]

[0153]

[0154] [Chemical formula 2-4-13][Chemical formula 2-4-14][Chemical formula 2-4-15]

[0155]

[0156] [Chemical formula 2-4-16]

[0157]

[0158] In Chemical formulas 2-4-1 to 2-4-16, X 1 , Ar 3 , R 9 to R 15 and m1 to m7 are the same as those described above.

[0159] For example, the second compound can be represented by any one of Chemical formulas 2-1-11, 2-2-11, 2-3-11, and 2-4-11.

[0160] For example, in Chemical formula 2, Ar 3 can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted terrylene group, or a substituted or unsubstituted fluorenyl group.

[0161] As a specific example, in Chemical formula 2, Ar 3 can be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

[0162] For example, in Chemical formula 2, R 9 to R 12 can each independently be hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C2-C20 heterocyclic group.

[0163] As a specific example, in Chemical formula 2, R 9 to R 12 can each independently be hydrogen, deuterium, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0164] As a more specific example, in Chemical formula 2, R 9 to R 12 can each independently be hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0165] For example, R in Chemical formula 2 9to R 12 may each independently be hydrogen or deuterium.

[0166] For example, the second compound may be one selected from the compounds listed in Group 2, but is not limited thereto.

[0167] [Group 2]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] The first compound and the second compound may be included in a weight ratio of, for example, 1:99 to 99:1. Within this range, the desired weight ratio can be adjusted using the electron transport ability of the first compound and the hole transport ability of the second compound to achieve bipolar characteristics and thus improve efficiency and lifespan. Within this range, the first compound and the second compound may be included in a weight ratio of, for example, 10:90 to 90:10, 20:80 to 80:20 (for example, 20:80 to 70:30, 20:80 to 60:40, or 30:70 to 60:40). As a specific example, the first compound and the second compound may be included in a weight ratio of 40:60, 50:50, or 60:40.

[0176] In addition to the above first compound and second compound, one or more compounds may also be included.

[0177] For example, the composition for the aforementioned organic optoelectronic device may also include a dopant.

[0178] 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.

[0179] The dopant is a material that is mixed in a small amount with the composition for the organic optoelectronic device to cause luminescence, and may generally be a material that emits light through multiple excitations to a triplet state or a higher state, such as a metal complex. The dopant may be, for example, an inorganic compound, an organic compound, or an organic-inorganic compound, and may include one or two or more types.

[0180] Examples of the dopant may be phosphorescent dopants, and examples of the phosphorescent dopants may include organometallic compounds, the 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 Chemical Formula Z, but is not limited thereto.

[0181] [Chemical Formula Z]

[0182] L 2 MX 2

[0183] In Chemical Formula Z, M is a metal, and L 2 and X 2 are the same or different and are ligands that form a complex compound with M.

[0184] M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof, and L and X 2 may be, for example, bidentate ligands.

[0185] Examples of the ligands represented by L 2 and X 2 may be selected from the chemical formulas of Group A, but are not limited thereto.

[0186] [Group A]

[0187]

[0188]

[0189] In Group A,

[0190] R 300 to R 302 are each independently hydrogen, deuterium, a C1 to C30 alkyl group that is halogen-substituted or unsubstituted, a C6 to C30 aryl group that is substituted or unsubstituted with a C1 to C30 alkyl group, or a halogen, and

[0191] R 303 to R 324Each independently is hydrogen, deuterium, a halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C30 heteroaryl group, a substituted or unsubstituted C1-C30 amino group, a substituted or unsubstituted C6-C30 arylamino group, SF5, a trialkylsilyl group having a substituted or unsubstituted C1-C30 alkyl group, a dialkylarylsilyl group having a substituted or unsubstituted C1-C30 alkyl group and a C6-C30 aryl group, or a triarylsilyl group having a substituted or unsubstituted C6-C30 aryl group.

[0192] For example, a dopant represented by Chemical Formula IV may be included.

[0193] [Chemical Formula IV]

[0194]

[0195] In Chemical Formula IV,

[0196] R 101 to R 116 Each independently is hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or -SiR 132 R 133 R 134 ,

[0197] R 132 to R 134 Each independently is a C1-C6 alkyl group,

[0198] R 101 to R 116 At least one of them is a functional group represented by Chemical Formula IV-1,

[0199] L 100 is a bidentate ligand of a monovalent anion and is a ligand that coordinates with iridium through a lone pair of carbon or a heteroatom, and

[0200] n1 and n2 each independently is any one of integers from 0 to 3, and n1 + n2 is any one of integers from 1 to 3,

[0201] [Chemical Formula IV-1]

[0202]

[0203] Among them, in Chemical Formula IV-1,

[0204] R 135To R 139 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,and

[0205] * means the moiety attached to the carbon atom.

[0206] For example, a dopant represented by Chemical Formula Z-1 may be included.

[0207] [Chemical formula Z-1]

[0208]

[0209] In the chemical formula Z-1, rings A, B, C and D may each independently be a 5-membered or 6-membered carbocyclic ring or heterocyclic ring;

[0210] R A , R B , R C and R D may be each independently mono-substituted, di-substituted, tri-substituted or tetra-substituted, or unsubstituted;

[0211] L B , L C and L D Each of them can be independently a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof. When nA is 1, L E It can be a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' or a combination thereof; and when nA is 0, L E does not exist;

[0212] R A , R B , R C , R D R, R and R' can each independently be hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amine, silane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphine or a combination thereof; any adjacent R A , R B , R C , R D , R and R' are optionally linked to each other to provide a ring; X B , X C , X D and XE each independently selected from carbon and nitrogen; and Q 1 、Q 2 、Q 3 and Q 4 each represents oxygen or a direct bond.

[0213] The dopant according to the embodiment may be a platinum complex and may be represented by Chemical Formula V.

[0214] [Chemical Formula V]

[0215]

[0216] In Chemical Formula V,

[0217] X 100 may be O, S or NR 131 ,

[0218] R 117 to R 131 may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or -SiR 132 R 133 R 134 ,

[0219] R 132 to R 134 may each independently be a C1 to C6 alkyl group, and

[0220] R 117 to R 131 at least one of which may be -SiR 132 R 133 R 134 or tert-butyl.

[0221] Hereinafter, an organic optoelectronic device including the aforementioned composition for an organic optoelectronic device is described.

[0222] The organic optoelectronic device may be a suitable device for converting electrical energy into light energy, such as an organic optoelectronic device, an organic light-emitting diode, an organic solar cell, or an organic photoreceptor drum, and vice versa.

[0223] Herein, an organic light-emitting diode as an example of an organic optoelectronic device is described with reference to the accompanying drawings.

[0224] Figure 1 is a cross-sectional view showing an organic light-emitting diode according to an embodiment.

[0225] Referring to Figure 1, the organic light-emitting diode 100 according to an embodiment may include an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110.

[0226] The anode 120 may be made of a conductor having a large work function to facilitate hole injection, and may be a metal, a metal oxide, or a conductive polymer. The anode 120 may be: a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, and similar metals or alloys thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and similar metal oxides; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, or polyaniline.

[0227] The cathode 110 may be made of a conductor having a small work function to facilitate electron injection, and may be a metal, a metal oxide, or a conductive polymer. The cathode 110 may be: a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, and similar metals or alloys thereof; or a multi-layer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, or BaF2 / Ca.

[0228] The organic layer 105 may contain the aforementioned composition for an organic optoelectronic device.

[0229] The organic layer 105 may include a light-emitting layer 130, and the light-emitting layer 130 may contain the aforementioned composition for an organic optoelectronic device.

[0230] The composition for an organic optoelectronic device further containing a dopant may be a green light-emitting composition.

[0231] The light-emitting layer 130 may contain the aforementioned composition for an organic optoelectronic device as a phosphorescent host.

[0232] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0233] The charge transport region may be a hole transport region 140.

[0234] The hole transport region 140 may help to further improve the hole injection and / or hole mobility between the anode 120 and the light-emitting layer 130, and may block electrons.

[0235] In an embodiment, the hole transport region 140 may include a hole transport layer located between the anode 120 and the light-emitting layer 130 and a hole transport auxiliary layer located between the light-emitting layer 130 and the hole transport layer, and at least one of the hole transport layer and the hole transport auxiliary layer may contain at least one of the compounds of Group B.

[0236] [Group B]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243] (Dn refers to the number of deuterium substitutions and represents a structure having one or more deuterium substitutions)

[0244] In the hole transport region, in addition to the above compounds, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds having similar structures can also be used.

[0245] In addition, the charge transport region may be, for example, the electron transport region 150.

[0246] The electron transport region 150 can further improve electron injection and / or electron mobility and can block holes between the cathode 110 and the light-emitting layer 130.

[0247] Specifically, the electron transport region 150 may include an electron transport layer located between the cathode 110 and the light-emitting layer 130 and an electron transport auxiliary layer located between the light-emitting layer 130 and the electron transport layer, and at least one of the electron transport layer and the electron transport auxiliary layer may contain at least one of the compounds of Group C.

[0248] [Group C]

[0249]

[0250]

[0251]

[0252] Embodiments of the present invention may provide an organic light emitting diode including a light emitting layer as an organic layer.

[0253] Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region and a light emitting layer as organic layers.

[0254] Another embodiment of the present invention may provide an organic light emitting diode including an electron transport region and a light emitting layer as organic layers.

[0255] As Figure 1 shown, embodiments of the present invention may provide an organic light emitting diode that also includes a hole transport region 140 and an electron transport region 150 as organic layers 105 in addition to the light emitting layer 130.

[0256] In another embodiment of the present invention, the organic light emitting diode may include, in addition to the light emitting layer, an electron injection layer (not shown), a hole injection layer (not shown), etc. as organic layers.

[0257] The organic light emitting diode 100 may be manufactured by forming an anode or a cathode on a substrate and then forming the organic layers by dry film methods such as evaporation, sputtering, plasma plating, and ion plating, and forming a cathode or an anode on the organic layers.

[0258] The organic light emitting diode may be applied to an organic light emitting display device.

[0259] [Mode of the Invention]

[0260] Hereinafter, embodiments will be described in more detail with reference to examples. However, these examples are merely exemplary, and the scope of the claims is not limited thereto.

[0261] (Synthesis of the First Compound)

[0262] Synthesis Example 1: Synthesis of Compound A-1

[0263] [Reaction Scheme 1]

[0264]

[0265] Step 1: Synthesis of Intermediate int-19

[0266] 3-Phenyl-9H-carbazole (30 g, 123.3 mmol), 1-bromo-4-chlorobenzene (23.6 g, 123.3 mmol), sodium tert-butoxide (23.7 g, 246.6 mmol), tri-tert-butylphosphine (2.5 g, 12.3 mmol), and Pd2(dba)3 (5.6 g, 6.2 mmol) were placed in a round-bottom flask and dissolved in xylene (600 mL), and then refluxed with stirring at 150 °C for 8 h. When the reaction was complete, after removing the salts by filtration, the filtrate obtained therefrom was adsorbed. 28.4 g (65%) of intermediate int-19 was obtained by column chromatography (hexane:dichloromethane (DCM) (25%)).

[0267] Step 2: Synthesis of intermediate int-20

[0268] Intermediate int-19 (28 g, 79.1 mmol), bis(pinacolato)diboron (24.1 g, 94.9 mmol), tricyclohexylphosphine (3.8 g, 15.8 mmol), potassium acetate (15.5 g, 158.3 mmol), and Pd(dppf)Cl2 (1.9 g, 2.4 mmol) were placed in a round-bottom flask and dissolved in 250 mL of xylene. The mixture was refluxed with stirring at 120 °C for 8 h. When the reaction was complete, the resulting product was cooled to room temperature, filtered to remove the salts, and extracted by adding an excess of DCM and distilled water. 20.4 g (82%) of intermediate int-20 was obtained by column chromatography (hexane:DCM (30%)).

[0269] Step 3: Synthesis of compound A-1

[0270] Intermediate int-20 (20.1 g, 45.1 mmol), 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine (14.1 g, 41.0 mmol), K2CO3 (11.3 g, 82.0 mmol), and Pd(PPh3)4 (2.4 g, 2.1 mmol) were placed in a round-bottom flask and dissolved in tetrahydrofuran (THF) (200 mL) and distilled water (40 mL), and then refluxed with stirring at 70 °C for 12 h. When the reaction was complete, the solid was separated therefrom by filtration and recrystallized from monochlorobenzene to obtain 18.5 g (72%) of compound A-1.

[0271] Synthesis Example 2: Synthesis of compound A-27

[0272] [Reaction Scheme 2]

[0273]

[0274] Step 1: Synthesis of Intermediate int-21

[0275] 2,4-Bis([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (40 g, 95.3 mmol), 4-chloro-2-fluorophenylboronic acid (15.8 g, 90.5 mmol), K2CO3 (26.3 g, 190.5 mmol) and Pd(PPh3)4 (5.5 g, 4.8 mmol) were placed in a round-bottom flask and dissolved in THF (320 mL) and distilled water (100 mL), and then refluxed with stirring at 70 °C for 12 hours. When the reaction was completed, the solid precipitated therefrom was filtered, and it was subjected to silica hot filtration using monochlorobenzene. The filtrate obtained therefrom was distilled under reduced pressure and recrystallized using monochlorobenzene to obtain 38.6 g (83%) of Intermediate int-21.

[0276] Step 2: Synthesis of Intermediate int-22

[0277] Intermediate int-21 (21.7 g, 42.2 mmol), phenylboronic acid (15.4 g, 126.7 mmol), Cs2CO3 (27.5 g, 84.4 mmol), tri-tert-butylphosphine (1.7 g, 8.4 mmol) and Pd2(dba)3 (1.9 g, 2.1 mmol) were placed in a round-bottom flask and dissolved in 1,4-dioxane (200 mL), and then refluxed with stirring at 120 °C for 8 hours. When the reaction was completed, an excess of distilled water was added to the resulting product and then stirred for 30 minutes, and the solid precipitated therein was filtered. After silica hot filtration using monochlorobenzene, the filtrate obtained therefrom was distilled under reduced pressure and recrystallized using monochlorobenzene to obtain 22.1 g (94%) of Intermediate int-22.

[0278] Step 3: Synthesis of Compound A-27

[0279] The intermediate int-22 (22.1 g, 39.8 mmol), 9H-carbazole (8.0 g, 47.7 mmol), and K3PO4 (16.9 g, 79.6 mmol) were placed in a round-bottom flask and dissolved in dimethyl formamide (DMF) (120 mL), and then refluxed and stirred at 150 °C for 4 hours. When the reaction was completed, the resulting product was slowly added dropwise to an excess of water to precipitate the solid, and the solid was filtered out therefrom. 24.6 g (88%) of compound A-27 was obtained using column chromatography (hexane:DCM (30%)).

[0280] (Synthesis of the second compound)

[0281] Synthesis Example 3: Synthesis of Compound B-1

[0282] [Reaction Scheme 3]

[0283]

[0284] Step 1: Synthesis of intermediate int-01

[0285] 1-Bromo-2,6-difluorobenzene (100 g, 518.2 mmol), 2,6-dimethoxyphenylboronic acid (99.0 g, 544.1 mmol), K2CO3 (179 g, 1295.4 mmol), and Pd(PPh3)4 (29.9 g, 25.9 mmol) were placed in a round-bottom flask and dissolved in THF (1000 mL) and distilled water (500 mL), and then refluxed and stirred at 70 °C for 12 hours. When the reaction was completed, after removing the aqueous layer, 78 g (60%) of intermediate int-01 was obtained by column chromatography (hexane:DCM (20%)).

[0286] Step 2: Synthesis of intermediate int-02

[0287] The intermediate int-01 (72 g, 287.7 mmol) and pyridine hydrochloride (166.3 g, 1438.6 mmol) were placed in a round-bottom flask, and then refluxed and stirred at 200 °C for 24 hours. When the reaction was completed, the resulting product was cooled to room temperature and slowly poured into distilled water, and then stirred for 1 hour. The solid obtained therefrom was filtered to obtain 60 g (94%) of intermediate int-02.

[0288] Step 3: Synthesis of intermediate int-03

[0289] The intermediate int-02 (64 g, 287.7 mmol) and K2CO3 (47.7 g, 345.3 mmol) were placed in a round-bottomed flask and dissolved in methylpyrrolidone (NMP) (200 mL), and then refluxed and stirred at 180 °C for 12 hours. When the reaction was completed, the mixture was poured into excess distilled water. The solid obtained therefrom was filtered, dissolved in ethyl acetate, dried over MgSO4, and the organic layer was removed therefrom under reduced pressure. 51 g (88%) of the intermediate int-03 was obtained using column chromatography (hexane:ethyl acetate (30%)).

[0290] Step 4: Synthesis of intermediate int-04

[0291] The intermediate int-03 (14 g, 69.2 mmol) and pyridine (8.4 mL, 103.9 mmol) were placed in a round-bottomed flask and dissolved in DCM (150 mL). After cooling to 0 °C, trifluoromethanesulfonic anhydride (13.9 mL, 83.1 mmol) was slowly added dropwise thereto. After stirring for 6 hours, when the reaction was completed, excess distilled water was added thereto, and then stirred for 30 minutes and extracted with DCM. After removing the organic solvent, 22 g (95%) of the intermediate int-04 was obtained by drying under reduced pressure in vacuo.

[0292] Step 5: Synthesis of intermediate int-05

[0293] Except for using the intermediate int-04 (21 g, 62.8 mmol), phenylboronic acid (8.4 g, 69.1 mmol), K2CO3 (13 g, 94.2 mmol) and Pd(PPh3)4 (3.6 g, 3.1 mmol), 12.5 g (76%) of the intermediate int-05 was synthesized in the same manner as in Step 1 of Synthesis Example 3.

[0294] Step 6: Synthesis of compound B-1

[0295] The intermediate int-05 (12 g, 45.8 mmol), 9-phenyl-3,3'-bicarbazole (22.4 g, 54.9 mmol) and K3PO4 (19.4 g, 91.5 mmol) were placed in a round-bottomed flask and dissolved in DMF (130 mL). The solution was refluxed and stirred at 160 °C for 6 hours. When the reaction was completed, the resulting product was filtered, and after removing the salt by filtration, the filtrate obtained therefrom was adsorbed. 19.4 g (65%) of compound B-1 was obtained using column chromatography (hexane:DCM (35%)).

[0296] Synthesis Example 4: Synthesis of compound B-36

[0297] [Reaction Scheme 4]

[0298]

[0299] Step 1: Synthesis of Intermediate int-06

[0300] 1-Bromo-3-fluoro-2-iodobenzene (80 g, 265.9 mmol), 5-chloro-2-methoxyphenylboronic acid (54.5 g, 292.5 mmol), K2CO3 (73.5 g, 531.8 mmol) and Pd(PPh3)4 (15.4 g, 13.3 mmol) were placed in a round-bottom flask and dissolved in THF (550 mL) and distilled water (250 mL), and then refluxed and stirred at 70 °C for 12 hours. When the reaction was completed, after removing the aqueous layer, 71.3 g (85%) of intermediate int-06 was obtained by column chromatography (hexane:DCM (20%)).

[0301] Step 2: Synthesis of Intermediate int-07

[0302] Except for using intermediate int-06 (70 g, 287.7 mmol) and pyridine hydrochloride (128.2 g, 1109.1 mmol), 61.5 g (92%) of intermediate int-07 was synthesized in the same manner as in Step 2 of Synthesis Example 3.

[0303] Step 3: Synthesis of Intermediate int-08

[0304] Except for using intermediate int-07 (61 g, 202.3 mmol) and K2CO3 (41.9 g, 303.4 mmol), 48.4 g (85%) of intermediate int-08 was synthesized in the same manner as in Step 2 of Synthesis Example 3.

[0305] Step 4: Synthesis of Intermediate int-09

[0306] Intermediate int-08 (48 g, 170.5 mmol), phenylboronic acid (22.9 g, 187.6 mmol), K2CO3 (47.3 g, 341.0 mmol) and Pd(PPh3)4 (9.9 g, 8.5 mmol) were placed in a round-bottom flask and dissolved in THF (560 mL) and distilled water (170 mL), and then refluxed and stirred at 70 °C for 12 hours. When the reaction was completed, after removing the aqueous layer, 35.2 g (74%) of intermediate int-09 was obtained by column chromatography (hexane:DCM (20%)).

[0307] Step 5: Synthesis of Compound B-36

[0308] The intermediate int-09 (30 g, 107.6 mmol), 9-phenyl-3,3'-bicarbazole (44 g, 107.6 mmol), sodium tert-butoxide (20.7 g, 215.3 mmol), tri-tert-butylphosphine (2.2 g, 10.8 mmol), and Pd2(dba)3 (4.9 g, 5.4 mmol) were placed in a round-bottom flask, dissolved in 360 mL of xylene, and then refluxed and stirred at 150 °C for 6 hours. When the reaction was completed, after removing the salts by filtration, the filtrate obtained therefrom was adsorbed using silica gel. 39.9 g (57%) of compound B-36 was obtained by column chromatography (hexane:DCM (35%)).

[0309] Synthesis Example 5: Synthesis of Compound B-71

[0310] [Reaction Scheme 5]

[0311]

[0312] Step 1: Synthesis of Intermediate int-10

[0313] Intermediate int-10 was synthesized in the same manner as in Step 1 of Synthesis Example 4, except that 4-chloro-2-methoxyphenylboronic acid was used instead of 5-chloro-2-methoxyphenylboronic acid.

[0314] Step 2: Synthesis of Intermediate int-11

[0315] Intermediate int-11 was synthesized in the same manner as in Step 2 of Synthesis Example 4.

[0316] Step 3: Synthesis of Intermediate int-12

[0317] Intermediate int-12 was synthesized in the same manner as in Step 3 of Synthesis Example 4.

[0318] Step 4: Synthesis of Intermediate int-13

[0319] Intermediate int-13 was synthesized in the same manner as in Step 4 of Synthesis Example 4.

[0320] Step 5: Synthesis of Compound B-71

[0321] Compound B-71 was synthesized in the same manner as in Step 5 of Synthesis Example 4.

[0322] Synthesis Example 6: Synthesis of Compound B-106

[0323] [Reaction Scheme 6]

[0324]

[0325] Step 1: Synthesis of Intermediate int-14

[0326] Intermediate int-14 was synthesized in the same manner as in Step 1 of Synthesis Example 3, except that 1-bromo-2,3-difluorobenzene was used instead of 1-bromo-2,6-difluorobenzene.

[0327] Step 2: Synthesis of Intermediate int-15

[0328] Intermediate int-15 was synthesized in the same manner as in Step 2 of Synthesis Example 3.

[0329] Step 3: Synthesis of Intermediate int-16

[0330] Intermediate int-16 was synthesized in the same manner as in Step 3 of Synthesis Example 3.

[0331] Step 4: Synthesis of Intermediate int-17

[0332] Intermediate int-17 was synthesized in the same manner as in Step 4 of Synthesis Example 3.

[0333] Step 5: Synthesis of Intermediate int-18

[0334] Intermediate int-18 was synthesized in the same manner as in Step 5 of Synthesis Example 3.

[0335] Step 6: Synthesis of Compound B-106

[0336] Compound B-106 was synthesized in the same manner as in Step 6 of Synthesis Example 3.

[0337] Comparative Synthesis Example 1: Synthesis of Compound C-1

[0338]

[0339] Compound C-1 was synthesized with reference to the known synthesis method in the registered patent KR 1849747 B1.

[0340] Comparative Synthesis Example 2: Synthesis of Compound C-2

[0341] [Reaction Scheme 7]

[0342]

[0343] Step 1: Synthesis of Intermediate int-23

[0344] 1,3 - Dibromo - 5 - chlorobenzene (45 g, 166.5 mmol), phenylboronic acid (19.3 g, 158.1 mmol), K2CO3 (41.4 g, 299.6 mmol) and Pd(PPh3)4 (9.6 g, 8.3 mmol) were placed in a round - bottom flask and dissolved in THF (600 mL) and distilled water (150 mL), and then refluxed with stirring at 70 °C for 8 hours. When the reaction was completed, after removing the aqueous layer, 25 g (59%) of intermediate int - 23 was obtained by column chromatography (hexane:DCM (15%)).

[0345] Step 2: Synthesis of intermediate int - 24

[0346] Intermediate int - 23 (25 g, 93.4 mmol), 3 - dibenzofuranylboronic acid (21.8 g, 102.8 mmol), K2CO3 (25.8 g, 186.9 mmol) and Pd(PPh3)4 (5.4 g, 4.7 mmol) were placed in a round - bottom flask and dissolved in THF (400 mL) and distilled water (100 mL), and then refluxed with stirring at 70 °C for 8 hours. When the reaction was completed, after removing the aqueous layer, 24.4 g (67%) of intermediate int - 24 was obtained by column chromatography (hexane:DCM (30%)).

[0347] Step 3: Synthesis of intermediate int - 25

[0348] Intermediate int - 24 (24 g, 67.6 mmol), bis(pinacolato)diboron (20.6 g, 81.2 mmol), tricyclohexylphosphine (3.3 g, 13.5 mmol), potassium acetate (13.3 g, 135.3 mmol) and Pd(dppf)Cl2 (1.7 g, 2.0 mmol) were placed in a round - bottom flask and dissolved in xylene (250 mL). The mixture was refluxed with stirring at 150 °C for 8 hours. When the reaction was completed, after cooling to room temperature and removing the salts by filtration, excess DCM and distilled water were added for extraction. 23.6 g (78%) of intermediate int - 25 was obtained using column chromatography (hexane:DCM (40%)).

[0349] Step 4: Synthesis of intermediate int - 26

[0350] 2,4-Dichloro-6-phenyl-1,3,5-triazine (20 g, 88.5 mmol), 3-dibenzofuranylboronic acid (17.8 g, 84.1 mmol), K2CO3 (24.5 g, 176.9 mmol), and Pd(dppf)Cl2 (3.6 g, 4.4 mmol) were placed in a round-bottom flask and dissolved in toluene (250 mL) and distilled water (90 mL), and then stirred at 60 °C for 6 h. When the reaction was complete, the aqueous layer was separated using a separatory funnel, and the organic layer obtained therefrom was distilled under reduced pressure. The product obtained therefrom was heated and dissolved in monochlorobenzene, and then filtered through silica and recrystallized to obtain 14.4 g (48%) of intermediate int-26.

[0351] Step 5: Synthesis of Compound C-2

[0352] Intermediate int-26 (14.1 g, 39.4 mmol), intermediate int-25 (18.5 g, 14.4 mmol), K2CO3 (10.9 g, 78.8 mmol), and Pd(PPh3)4 (2.3 g, 2.0 mmol) were placed in a round-bottom flask and dissolved in THF (200 mL) and distilled water (40 mL), and then refluxed and stirred at 70 °C for 8 h. When the reaction was complete, after removing the aqueous layer, the solid precipitated therein was filtered. The product obtained therefrom was heated and dissolved in monochlorobenzene, and then filtered through silica and recrystallized to obtain 18.2 g (72%) of compound C-2.

[0353] Comparative Synthesis Example 3: Synthesis of Compound C-3

[0354] [Reaction Scheme 8]

[0355]

[0356] Step 1: Synthesis of Intermediate int-27

[0357] 2-Bromo-4-chlorodibenzofuran (30.3 g, 107.6 mmol), 9H-carbazole (18.0 g, 107.6 mmol), sodium tert-butoxide (20.7 g, 215.3 mmol), tri-tert-butylphosphine (2.2 g, 10.8 mmol), and Pd2(dba)3 (4.9 g, 5.4 mmol) were placed in a round-bottom flask and dissolved in xylene (550 mL), and then refluxed and stirred at 150 °C for 8 h. When the reaction was complete, after removing the salt by filtration, the filtrate obtained therefrom was adsorbed. 21.4 g (54%) of intermediate int-27 was obtained by column chromatography (hexane:DCM (40%)).

[0358] Step 2: Synthesis of Intermediate int-28

[0359] Intermediate int-27 (21.2 g, 57.6 mmol), bis(pinacolato)diboron (17.6 g, 69.2 mmol), tricyclohexylphosphine (2.8 g, 11.5 mmol), potassium acetate (11.3 g, 115.3 mmol) and Pd2(dba)3 (1.6 g, 1.7 mmol) were placed in a round-bottom flask and dissolved in xylene (200 mL). The mixture was refluxed and stirred at 160 °C for 8 hours. When the reaction was complete, after cooling to room temperature and removing the salts by filtration, the filtrate obtained therefrom was extracted by adding an excess of DCM and distilled water. 23.3 g (88%) of intermediate int-28 were obtained using column chromatography (hexane:DCM (40%)).

[0360] Step 3: Synthesis of Compound C-3

[0361] Intermediate int-28 (18.9 g, 41.2 mmol), 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine (13.5 g, 39.3 mmol), K2CO3 (10.9 g, 78.5 mmol) and Pd(PPh3)4 (2.3 g, 2.0 mmol) were placed in a round-bottom flask and dissolved in THF (150 mL) and distilled water (40 mL), and then refluxed and stirred at 70 °C for 12 hours. When the reaction was complete, after separating the salts by filtration, 18.1 g (72%) of compound C-3 were obtained by recrystallization using monochlorobenzene.

[0362] Comparative Synthesis Example 4: Synthesis of Compound C-4

[0363]

[0364] Compound C-4 was synthesized by referring to the synthesis method known in the published patent CN 114075204 A.

[0365] Comparative Synthesis Example 5: Synthesis of Compound C-5

[0366]

[0367] Compound C-5 was synthesized by referring to the synthesis method known in the registered patent KR 2322795 B1.

[0368] Comparative Synthesis Example 6: Synthesis of Compound C-6

[0369] [Reaction Scheme 9]

[0370]

[0371] Step 1: Synthesis of Intermediate int-29

[0372] The intermediate int-29 was synthesized by referring to the synthesis method known from the registered patent KR 1862881 B1.

[0373] Step 2: Synthesis of Compound C-6

[0374] Compound C-6 was synthesized in the same manner as in Step 5 of Synthesis Example 4.

[0375] Comparative Synthesis Example 7: Synthesis of Compound C-7

[0376] [Reaction Scheme 10]

[0377]

[0378] Step 1: Synthesis of Intermediate int-30

[0379] The intermediate int-30 was synthesized by referring to the synthesis method known from the published patent WO 2017-100967 A1.

[0380] Step 2: Synthesis of Compound C-7 Compound C-7 was synthesized in the same manner as in Step 5 of Synthesis Example 4.

[0381] Comparative Synthesis Example 8: Synthesis of Compound C-8

[0382]

[0383] Compound C-8 was synthesized by referring to the synthesis method known from the registered patent KR 2290362 B1.

[0384] Comparative Synthesis Example 9: Synthesis of Compound C-9

[0385]

[0386] Compound C-9 was synthesized by referring to the synthesis method known from the registered patent KR 2247294 B1.

[0387] Comparative Synthesis Example 10: Synthesis of Compound C-10

[0388]

[0389] Compound C-10 was synthesized by referring to the synthesis method known from the published patent KR 2021-0152819.

[0390] (Manufacture of Organic Light-Emitting Diodes)

[0391] Example 1

[0392] The glass substrate coated with indium tin oxide (ITO) was washed using 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, and similar solvents) and dried, and then the glass substrate was moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and the glass substrate was moved to a vacuum depositor. The obtained ITO transparent electrode was used as the anode, and Compound A doped with 3% 2-(7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyrene-2-ylidene)-malononitrile (2-(7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyrene-2-ylidene)-malononitrile, NDP-9) (obtainable from Novaled) was vacuum deposited on the ITO substrate to form a 100 Å thick hole injection layer, and Compound A was deposited on the hole injection layer to form a 1350 Å thick hole transport layer. On the hole transport layer, Compound B with a thickness of 350 Å was deposited to form a hole transport auxiliary layer. On the hole transport auxiliary layer, a 380 Å thick light-emitting layer was formed by simultaneously using Compound A-1 obtained in Synthesis Example 1 and Compound B-1 obtained in Synthesis Example 3 as the host at a weight ratio of 3:7 and doping 10 wt% of PhGD as the dopant by vacuum deposition. Subsequently, on the light-emitting layer, Compound C with a thickness of 50 Å was deposited to form an electron transport auxiliary layer, and Compound D and LiQ were simultaneously vacuum deposited at a weight ratio of 1:1 to form a 300 Å thick electron transport layer. On the electron transport layer, 15 Å thick LiQ and 1,200 Å thick Al were sequentially vacuum deposited to fabricate an organic light-emitting diode.

[0393] ITO / Compound A (3% NDP-9 doped, 100 Å) / Compound A (1350 Å) / Compound B (350 Å) / EML [93 wt% host (Compound A-1:Compound B-1 = 3:7 w / w):10 wt% PhGD] (380 Å) / Compound C (50 Å) / Compound D:LiQ (300 Å) / LiQ (15 Å) / Al (1200 Å)

[0394] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0395] Compound B: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluorene)-2-amine

[0396] Compound C: 2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine

[0397] Compound D: 2-(biphenyl-4-yl)-4-(9,9-diphenyl-9H-fluoren-4-yl)-6-phenyl-1,3,5-triazine

[0398] [PhGD]

[0399]

[0400] Examples 2 to 5 and Comparative Examples 1 to 10

[0401] Diodes of Examples 2 to 5 and Comparative Examples 1 to 10 were fabricated in the same manner as Example 1, except that the host was changed as shown in Table 1.

[0402] Evaluation

[0403] (1) Measurement of current density change depending on voltage change

[0404] While increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), the current value flowing in the unit device of the obtained organic light-emitting diode was measured, and the measured current value was divided by the area to provide the result.

[0405] (2) Measurement of luminance change depending on voltage change

[0406] 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).

[0407] (3) Measurement of luminous efficiency

[0408] The luminous efficiency (candela per area (cd / A)) at the same current density (10 milliamperes per square centimeter (mA / cm 2 )) was calculated using the luminance and current density measured in (1) and (2) above.

[0409] The luminous efficiency ratios of Examples 1 to 5 and Comparative Examples 1 to 10 were calculated as relative values based on Comparative Example 1 and listed in Table 1.

[0410] (4) Measurement of driving voltage

[0411] The results were obtained by measuring the driving voltage of each diode at 15 mA / cm2 using a current-voltage meter (Keithley 2400).

[0412] The driving voltages of Examples 1 to 5 and Comparative Examples 1 to 10 were calculated as relative values based on Comparative Example 1 and listed in Table 1.

[0413] (Table 1)

[0414]

[0415] Referring to Table 1, compared to the organic light-emitting diodes according to Comparative Examples 1 to 10, the organic light-emitting diodes according to Examples 1 to 5 have significantly improved driving voltages while maintaining equal or higher efficiency.

[0416] Although the present invention has been described in connection with exemplary embodiments that are presently considered to be practical, it should be understood that the present invention is not limited to the disclosed embodiments. On the contrary, the present invention 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 represented by Chemical Formula 1; and a second compound represented by Chemical Formula 2: [Chemical Formula 1] Among them, In Chemical Formula 1, Z 1 to Z 3 each independently is N or C-R a , Z 1 to Z 3 at least two of which are N, L 1 is a single bond or a substituted or unsubstituted C6-C20 arylene group, Ar 1 and Ar 2 each independently is a substituted or unsubstituted C6-C30 aryl group, and R a and R 1 to R 8 each independently is hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof; [Chemical Formula 2] wherein, in Chemical Formula 2, X 1 is O or S, Ar 3 is a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof, R 9 to R 12 each independently is hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-C30 heterocyclic group, R 13 to R 15 each independently is hydrogen, deuterium or a substituted or unsubstituted phenyl group, m2, m3, m5, and m6 are each independently an integer from 1 to 3, and m1, m4, and m7 are each independently an integer from 1 to 4.

2. The composition for an organic optoelectronic device according to claim 1, wherein Ar in Chemical Formula 1 1 and Ar 2 each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted benzo[c][1,2,5]thiadiazolyl group, or a substituted or unsubstituted fluorene group.

3. The composition for an organic optoelectronic device according to claim 1, wherein R in Chemical Formula 1 1 to R 8 each independently represents hydrogen, deuterium, cyano group, substituted or unsubstituted C6-C20 aryl group or substituted or unsubstituted C2-C20 heterocyclic group.

4. The composition for an organic optoelectronic device according to claim 1, wherein the second compound is represented by any one of Chemical Formulas 2-1 to 2-4: Among them, In Chemical Formulas 2-1 to 2-4, X 1 、Ar 3 、R 9 to R 15 and m1 to m7 are as defined in claim 1.

5. The composition for an organic optoelectronic device according to claim 4, wherein the second compound is represented by any one of Chemical Formulas 2-1-11, 2-2-11, 2-3-11, and 2-4-11: Among them, In Chemical Formula 2-1-11, Chemical Formula 2-2-11, Chemical Formula 2-3-11, and Chemical Formula 2-4-11, X 1 , Ar 3 , R 9 to R 15 , m1 to m7 are as defined in claim 1.

6. The composition for an organic optoelectronic device according to claim 1, wherein Ar in Chemical Formula 2 3 is 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 anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.

7. The composition for an organic optoelectronic device according to claim 1, wherein the first compound is one selected from the compounds listed in Group 1, and the second compound is one selected from the compounds listed in Group 2: [Group 1] [Group 2] 8. An organic optoelectronic device, comprising: an anode and a cathode facing each other; and at least one organic layer between the anode and the cathode, wherein the organic layer contains the composition for an organic optoelectronic device according to any one of claims 1 to 7.

9. The organic optoelectronic device according to claim 8, wherein the organic layer includes a light-emitting layer, and the light-emitting layer contains the composition for an organic optoelectronic device.

10. The organic optoelectronic device according to claim 9, wherein the composition for an organic optoelectronic device further contains a phosphorescent dopant.

11. The organic optoelectronic device according to claim 10, wherein the composition for an organic optoelectronic device is a green light-emitting composition.

12. A display device, comprising the organic optoelectronic device according to claim 9.

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