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

Abstract

The invention provides a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device. The composition for an organic optoelectronic device comprises the compound for an organic optoelectronic device. The compound for an organic optoelectronic device is represented by Chemical Formula 1, the content of Chemical Formula 1 being as defined in the specification. [Chemical Formula 1]

Description

[0001] Citations of relevant applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0058071, filed with the Korean Intellectual Property Office on April 30, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application discloses compounds for organic optoelectronic devices, compositions for organic optoelectronic devices, organic optoelectronic devices, and display devices. Background Technology

[0004] Organic optoelectronic devices (organic optoelectronic diodes) are devices that can convert electrical energy and light energy into each other.

[0005] Based on their operating principles, organic optoelectronic devices can be mainly divided into two types. One type is a photoelectric device, which generates electrical energy by separating excitons formed by light energy into electrons and holes, and transferring the electrons and holes to different electrodes. The other type is a light-emitting device, which generates light energy from electrical energy by supplying voltage or current to the electrodes.

[0006] Examples of organic optoelectronic devices include organic photoelectric devices, organic light-emitting diodes, organic solar cells, and organic photoconductor drums.

[0007] Organic light-emitting diodes (OLEDs) have garnered significant attention in recent years due to the increasing demand for flat panel display devices. OLEDs are devices that convert electrical energy into light, and their performance is greatly influenced by the organic materials used between the electrodes. Summary of the Invention

[0008] One embodiment provides a compound for organic optoelectronic devices that can reduce driving voltage and enable high-efficiency and long-life organic optoelectronic devices.

[0009] Another embodiment provides a composition for an organic optoelectronic device comprising a compound for an organic optoelectronic device.

[0010] Another embodiment provides an organic optoelectronic device comprising a compound for an organic optoelectronic device or a composition for an organic optoelectronic device.

[0011] Another implementation provides a display device that includes organic optoelectronic devices.

[0012] According to one embodiment, a compound represented by chemical formula 1 for use in organic optoelectronic devices is provided.

[0013] [Chemical Formula 1]

[0014]

[0015] In chemical formula 1,

[0016] X 1 Is it O or S?

[0017] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C30 aryl group.

[0018] R 1 To R 14 Each is independently either hydrogen or deuterium, and

[0019] m1 is an integer from 1 to 3.

[0020] According to another embodiment, the composition for an organic optoelectronic device comprises a first compound and a second compound.

[0021] The first compound can be the compound described above for use in organic optoelectronic devices, while the second compound can be represented by chemical formula 2A or chemical formula 2B.

[0022]

[0023] In chemical formulas 2A and 2B,

[0024] Z 1 To Z 3 Each is independently N or CL a -R a ,

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

[0026] X 2 Is it O, S, or NR? b ,

[0027] L a and L 3 To L 5 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.

[0028] R a R b and R 23 To R 35Each of these elements independently comprises hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amino, halogen, cyano, or combinations thereof.

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

[0030] m5 is an integer from 1 to 3.

[0031] According to another embodiment, the organic optoelectronic device includes an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, wherein the organic layer includes a light-emitting layer and the light-emitting layer includes a compound for the organic optoelectronic device or a composition for the organic optoelectronic device.

[0032] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0033] It is possible to achieve high efficiency and long lifespan organic optoelectronic devices while reducing operating voltage. Attached Figure Description

[0034] Figure 1 This is a cross-sectional view of an organic light-emitting diode according to one embodiment. Detailed Implementation

[0035] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto; rather, the invention is defined by the scope of the claims.

[0036] In this specification, unless otherwise defined, “substituted” means that at least one hydrogen atom of a substituent or compound is replaced by one of the following: deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amino, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or combinations thereof.

[0037] In one embodiment of the invention, "substituted" means that at least one hydrogen atom of the substituent or compound is replaced by one of the following: deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, or cyano. In a specific embodiment of the invention, "substituted" means that at least one hydrogen atom of the substituent or compound is replaced by one of the following: deuterium, C1 to C20 alkyl, C1 to C5 alkylsilyl, C6 to C20 aryl, C2 to C20 heteroaryl, or cyano. In a specific embodiment of the invention, "substituted" means that at least one hydrogen atom of the substituent or compound is replaced by one of the following: deuterium, C1 to C5 alkyl, C1 to C5 alkylsilyl, C6 to C18 aryl, C2 to C18 heteroaryl, or cyano. In specific embodiments of the present invention, "substituted" means that at least one hydrogen atom of the substituent or compound is replaced by one of the following: deuterium, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trimethylsilyl, phenyl, biphenyl, terphenyl or naphthyl.

[0038] In this specification, "unsubstituted" means that the hydrogen atom is not replaced by another substituent and the hydrogen atom is retained.

[0039] In this specification, "hydrogen substitution (-H)" may include "deuterium substitution (-D)" or "tritium substitution (-T)".

[0040] In this specification, unless otherwise defined, “heterogeneous” means a functional group comprising one to three heteroatoms selected from N, O, S, P and Si, and the remaining carbon.

[0041] In this specification, "aryl" means a group comprising at least one aromatic hydrocarbon moiety, wherein all elements of the aromatic hydrocarbon moiety have conjugated p orbitals, such as phenyl, naphthyl, etc., and two or more aromatic hydrocarbon moiety may be linked by σ bonds and may be, for example, biphenyl, terphenyl, tetraphenyl, etc., and two or more aromatic hydrocarbon moiety may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorene.

[0042] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings that share adjacent carbon atom pairs) functional groups.

[0043] In this specification, "heterocyclic group" is a superordinate concept of a heteroaryl group and may include at least one heteroatom selected from N, O, S, P, and Si replacing a carbon (C) in a cyclic compound (such as an aryl, cycloalkyl, their fused rings, or combinations thereof). When the heterocyclic group is fused, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms.

[0044] For example, "heteroaryl" can refer to an aryl group comprising at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are directly connected by σ bonds, or when a heteroaryl group comprises two or more rings, the two or more rings can be fused. When a heteroaryl group is a fused ring, each ring can comprise 1 to 3 heteroatoms.

[0045] More specifically, the substituted or unsubstituted C6 to C30 aryl group can be a substituted or unsubstituted C6 to C30 aryl group, and can be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraquinone, a substituted or unsubstituted phenanthyl, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted pyrene, a substituted or unsubstituted biphenyl, a substituted or unsubstituted p-terphenyl, a substituted or unsubstituted meta-terphenyl, a substituted or unsubstituted o-terphenyl, or a substituted or unsubstituted terphenyl. The radical, substituted or unsubstituted benzo[a]phenanthrene, substituted or unsubstituted triphenyl, substituted or unsubstituted peryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted indene, or combinations thereof, but not limited thereto.

[0046] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group can be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted pyrrole 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 thiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indoleyl group, or a substituted or unsubstituted... The following are substituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridineyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted carbazoyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthophenyl, substituted or unsubstituted benzofuranfluorenyl, substituted or unsubstituted benzothiophenfluorenyl or combinations thereof, but not limited thereto.

[0047] In this specification, hole characteristics refer to the ability of contributing electrons to form holes when an electric field is applied, and due to the conductivity characteristics based on the highest occupied molecular orbital (HOMO) energy level, holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0048] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into and transported in the light-emitting layer.

[0049] The following describes a compound for an organic optoelectronic device according to one embodiment.

[0050] According to one embodiment, a compound for an organic optoelectronic device is represented by chemical formula 1.

[0051] [Chemical Formula 1]

[0052]

[0053] In chemical formula 1,

[0054] X 1 Is it O or S?

[0055] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C30 aryl group.

[0056] R 1 To R 14 Each is independently either hydrogen or deuterium, and

[0057] m1 is an integer from 1 to 3.

[0058] The compound represented by chemical formula 1 has the following structure: wherein the indolocarbazole core is fused at the 3rd and 4th positions of the carbazole core, and the dibenzofuran (or dibenzothiophene) is substituted in the N-direction of the core.

[0059] In particular, by including an additional substituent at the 8th position, dibenzofuran (or dibenzothiophene) has a low-region LUMO energy level, and thus can achieve the advantage of high efficiency in organic light-emitting diodes applied thereon.

[0060] When m1 is 2 or greater, each R 14 They can be the same or different.

[0061] For example, depending on the connection point of the dibenzofuran (or dibenzothiophene) substituted with indolocarbazole, Formula 1 can be represented by any one of Formulas 1-1 to 1-4.

[0062] [Chemical Formula 1-1]

[0063]

[0064] [Chemical Formula 1-2]

[0065]

[0066] [Chemical Formulas 1-3]

[0067]

[0068] [Chemical Formulas 1-4]

[0069]

[0070] In chemical formulas 1-1 to 1-4

[0071] X 1 Ar 1 and Ar 2 R 1 To R 14 The same applies to m1 as above.

[0072] In one embodiment, chemical formula 1 may be represented as any one of chemical formulas 1-1 to 1-3.

[0073] For example, Ar 1 It can be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, or a substituted or unsubstituted triphenylene.

[0074] For example, Ar 1 It can be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, or a substituted or unsubstituted triphenylene.

[0075] For example, Ar 2 It can be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, or a substituted or unsubstituted triphenylene.

[0076] For example, Ar 2 It can be a substituted or unsubstituted C6 to C30 unfused aryl group.

[0077] In one implementation scheme, Ar 2 It can be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted terphenyl.

[0078] In one specific embodiment, the compound for an organic optoelectronic device represented by Formula 1 may be selected from, but is not limited to, one of the compounds listed in Group 1.

[0079] [Group 1]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] In group 1, Dn refers to the number of deuterium substitutions.

[0087] According to another embodiment, the composition for an organic optoelectronic device comprises a first compound and a second compound, wherein the first compound is the aforementioned compound for an organic optoelectronic device, and the second compound may be represented by chemical formula 2A or chemical formula 2B.

[0088]

[0089] In chemical formulas 2A and 2B,

[0090] Z 1 To Z 3 Each is independently N or CL a -R a ,

[0091] Z 1 To Z 3 At least two of them are N.

[0092] X 2 Is it O, S, or NR? b ,

[0093] L a and L 3 To L 5 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.

[0094] R a R b and R 23 To R 35 Each of these elements independently comprises hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amino, halogen, cyano, or combinations thereof.

[0095] Ar 3 and Ar4 Each is independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, and

[0096] m5 is an integer from 1 to 3.

[0097] By including a nitrogen-containing hexagonal ring moiety, the second compound effectively extends the LUMO band and can therefore be included together with the first compound to increase the balance of holes and electrons, thereby significantly improving the lifetime characteristics of devices using it.

[0098] For example, Z 1 and Z 2 It can be nitrogen and Z 3 It can be N or CL a -R a .

[0099] For example, Z 1 and Z 3 It can be nitrogen and Z 2 It can be N or CL a -R a .

[0100] For example, Z 1 To Z 3 Each of them can be nitrogen (N).

[0101] In chemical formula 2B, when m5 is 2 or higher, each R 31 They can be the same or different.

[0102] As a specific embodiment, chemical formula 2A can be represented by any one of chemical formulas 2A-I to 2A-III, and chemical formula 2B can be represented by any one of chemical formulas 2B-I to 2B-IV.

[0103]

[0104]

[0105] In chemical formulas 2A-I to 2A-III and 2B-I to 2B-IV, L 3 To L 5 Ar 3 and Ar 4 R 23 To R 35 m5 is the same as above.

[0106] R 53 To R 60Each is independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl or substituted or unsubstituted C6 to C12 aryl.

[0107] For example, L 3 To L 5 Each can be a single bond or a substituted or unsubstituted C6 to C12 aryl group.

[0108] For example, R 53 To R 60 Each of them can be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl or substituted or unsubstituted C6 to C12 aryl.

[0109] For example, Ar 3 and Ar 4 Each of these can be independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, or substituted or unsubstituted carbazoyl.

[0110] For example, R 23 To R 35 Each of them can be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl or substituted or unsubstituted C6 to C12 aryl.

[0111] For example, L 3 To L 5 Each can be independently a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted dibenzofuranylene, or a substituted or unsubstituted dibenzothiopheneylene.

[0112] For example, Ar 3 and Ar 4 Each of these can be independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.

[0113] For example, R 23 To R 35 and R 53 To R 60Each of them can be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl, substituted or unsubstituted phenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.

[0114] In one specific embodiment, the second compound may be represented by the above-described chemical formula 2A-I or chemical formula 2B-II.

[0115] For example, in chemical formula 2A-I, L 3 and L 4 Each can be a single bond or a substituted or unsubstituted C6 to C12 aryl group, L 5 It can be a substituted or unsubstituted C6 to C12 aryl group, Ar 3 and Ar 4 Each can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted terphenyl, and R 23 To R 30 Each of them can be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl or substituted or unsubstituted C6 to C12 aryl.

[0116] For example, in chemical formula 2B-II, L 3 and L 4 Each can be a single bond or a substituted or unsubstituted C6 to C12 aryl group, L 5 It can be a substituted or unsubstituted C6 to C12 aryl group, Ar 3 and Ar 4 Each of these can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothiopheneyl, and R 31 To R 35 Each of them can be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl or substituted or unsubstituted C6 to C12 aryl.

[0117] The second compound may be, for example, selected from one of the compounds listed in Group 2, but is not limited thereto.

[0118] [Group 2]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] The first and second compounds can be contained in a weight ratio of, for example, 1:99 to 99:1. By including them within the above range, efficiency and lifetime can be improved by adjusting the appropriate weight ratio using the hole transport capability of the first compound and the electron transport capability of the second compound to achieve bipolar characteristics. Within the above range, they can be contained in weight ratios of, for example, about 10:90 to 90:10, about 20:80 to 80:20, for example, about 20:80 to about 70:30, about 20:80 to about 60:40, and about 30:70 to about 60:40. As a specific embodiment, they can be contained in a weight ratio of 40:60, 50:50, or 60:40.

[0132] In the following text, an organic optoelectronic device comprising the above-described compound for an organic optoelectronic device or a composition for an organic optoelectronic device will be described.

[0133] Organic optoelectronic devices can be suitable devices that convert electrical energy into light energy and vice versa, such as organic photoelectric devices, organic light-emitting diodes, organic solar cells, or organic photoconductor drums.

[0134] In this document, an organic light-emitting diode (OLED) is described as one embodiment of an organic optoelectronic device with reference to the accompanying drawings.

[0135] Figure 1 This is a cross-sectional view of an organic light-emitting diode according to some exemplary embodiments.

[0136] refer to Figure 1 An organic light-emitting diode 100 according to some exemplary embodiments 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.

[0137] The anode 120 may be made of a conductor with a high work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or alloys thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; a combination of metals and oxides such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0138] The cathode 110 may be made of a conductor with a low work function to aid electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof; a multilayer material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0139] The organic layer 105 may contain the compounds or compositions described above for organic optoelectronic devices.

[0140] The organic layer 105 may include a light-emitting layer 130, which may include a host and a dopant. The host may include the compounds or compositions described above for organic optoelectronic devices, and the dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, for example, a red or green phosphorescent dopant.

[0141] A dopant is a material that is mixed in small amounts with a compound or composition used in organic optoelectronic devices to induce luminescence, and is typically a material that emits light by being excited multiple times to a triplet or more states, such as a metal complex. Dopants can be, for example, inorganic, organic, or organic-inorganic compounds, and one or more of these types can be used.

[0142] Examples of dopants can be phosphorescent dopants, and examples of phosphorescent dopants can be organometallic compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof. Phosphorescent dopants can be, for example, compounds represented by the chemical formula Z, but are not limited thereto.

[0143] [Chemical Formula Z]

[0144] L 7 MX 4

[0145] In the chemical formula Z, M is a metal, and L 7 and X 4 The same or different, and is a ligand that forms a complex with M.

[0146] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof, and L 7 and X 4 It could be, for example, a dipterine ligand.

[0147] By L 7 and X 4 Examples of ligands represented may be selected from, but are not limited to, the chemical formulas listed in group A.

[0148] [Group A]

[0149]

[0150] In group A,

[0151] R 300 To R 302 Each is independently hydrogen, deuterium, a C1 to C30 alkyl group substituted or unsubstituted with a halogen, a C6 to C30 aryl group substituted or unsubstituted with a C1 to C30 alkyl group, or a halogen.

[0152] R 303 To R 324 Each of the following is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroaryl, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C6 to C30 arylamino, SF5, trialkylsilyl having substituted or unsubstituted C1 to C30 alkyl, dialkylarylsilyl having substituted or unsubstituted C1 to C30 alkyl and C6 to C30 aryl, or triarylsilyl having substituted or unsubstituted C6 to C30 aryl, and

[0153] n1 is an integer from 0 to 5, n2 is an integer from 0 to 4, n3 is an integer from 0 to 3, n4 is an integer from 0 to 2, and n5 is an integer from 0 to 6.

[0154] The dopant according to some exemplary embodiments may be an iridium complex and may include, for example, a dopant represented by chemical formula 4-1 or chemical formula 4-2.

[0155] [Chemical Formula 4-1]

[0156]

[0157] In chemical formula 4-1,

[0158] R 101 To R 116 Each of these elements is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR. 132 R 133 R 134 ,

[0159] R 132 To R 134 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0160] R 101 To R 116 At least one of them is a functional group represented by the chemical formula V-1.

[0161] L 100 It is a bidentate ligand for monovalent anions, and a ligand coordinated to iridium via a lone pair of carbon or heteroatom.

[0162] m21 and m22 are each independent integers from 0 to 3, and m21+m22 is any integer from 1 to 3.

[0163] [Chemical Formula V-1]

[0164]

[0165] In chemical formula V-1,

[0166] R 135 To R 139 Each of these elements is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR. 132 R 133 R 134 ,

[0167] R 132 To R 134 Each is independently a substituted or unsubstituted C1 to C6 alkyl group, and

[0168] * refers to the part that is attached to a carbon atom.

[0169] [Chemical Formula 4-2]

[0170]

[0171] In chemical formula 4-2,

[0172] R 101 To R 117 Each of these elements is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR. 133 R 134 R 135 ,

[0173] R 133 To R 135 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0174] L 100 It is a bidentate ligand for monovalent anions, and a ligand coordinated to iridium via a lone pair of carbon or heteroatom.

[0175] n1 and n2 are each independent integers from 0 to 3, and n1+n2 is an integer from 1 to 3.

[0176] The dopant according to some exemplary embodiments may be a platinum complex and may be represented by, for example, the chemical formula Z-1.

[0177] [Chemical Formula Z-1]

[0178]

[0179] In chemical formula Z-1, rings A, B, C, and D are each independently a 5- or 6-membered carbon ring or a heterocycle;

[0180] R A R B R C and R D Each can be independently mono-, di-, tri-, or tetra-substituted or unsubstituted;

[0181] L B L C and L D Each of these can be independently a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', or a combination thereof.

[0182] 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 It does not exist;

[0183] R A R B R C RD R and R' are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiosulfinyl, sulfinyl, phosphinyl, or combinations thereof; any adjacent R A R B R C R D R and R' are optionally connected to each other to provide a loop; X B X C X D and X E Each is independently selected from carbon and nitrogen; and Q 1 Q 2 Q 3 and Q 4 Each represents oxygen or a direct bond.

[0184] Platinum complexes can be represented, for example, by chemical formula 5-1 or chemical formula 5-2.

[0185] [Chemical Formula 5-1]

[0186]

[0187] [Chemical Formula 5-2]

[0188]

[0189] In chemical formulas 5-1 and 5-2,

[0190] X 100 Selected from O, S and NR 132 ,

[0191] R 118 To R 132 Each of these elements is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR. 133 R 134 R 135 ,

[0192] R 133 To R 135 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0193] R 118 To R 132 At least one of them is -SiR 133 R 134 R 135 Or tert-butyl, and

[0194] R 133 To R 135 Each is independently a substituted or unsubstituted C1 to C6 alkyl group.

[0195] In addition to the light-emitting layer, the organic layer may also include charge transport regions.

[0196] The charge transport region can be, for example, the hole transport region 140.

[0197] The hole transport region 140 can further increase hole injection and / or hole mobility between the anode 120 and the light-emitting layer 130, and block electrons.

[0198] Specifically, the hole transport region 140 may include a hole transport layer between the anode 120 and the light-emitting layer 130 and a hole transport auxiliary layer between the light-emitting layer 130 and the hole transport layer, and at least one of the hole transport layer and the hole transport auxiliary layer may contain at least one of the compounds listed in Group B.

[0199] [Group B]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] (Dn refers to the number of deuterium substitutions and represents the structure substituted by one or more deuteriums)

[0207] In the hole transport region, in addition to the compounds mentioned above, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A and compounds with similar structures may also be used.

[0208] Furthermore, the charge transport region can be, for example, the electron transport region 150.

[0209] The electron transport region 150 can further increase electron injection and / or electron mobility and block holes between the cathode 110 and the light-emitting layer 130.

[0210] Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light-emitting layer 130, and an electron transport auxiliary layer between the light-emitting layer 130 and the electron transport layer, and at least one of the electron transport layer and the electron transport auxiliary layer may include at least one of the group C compounds.

[0211] [Group C]

[0212]

[0213]

[0214]

[0215] One implementation can provide an organic light-emitting diode that includes a light-emitting layer as an organic layer.

[0216] Another implementation can provide an organic light-emitting diode that includes an emitting layer and a hole transport region as an organic layer.

[0217] Another implementation can provide an organic light-emitting diode that includes an emitting layer and an electron transport region as organic layers.

[0218] like Figure 1 As shown, in addition to the light-emitting layer 130, the organic light-emitting diode according to the embodiment of the present invention also includes a hole transport region 140 and an electron transport region 150 as an organic layer 105.

[0219] On the other hand, in addition to the light-emitting layer, an organic light-emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), etc., as organic layers.

[0220] Organic light-emitting diode 100 can be manufactured by the following steps: forming an anode or cathode on a substrate, then forming an organic layer by a dry film method (such as vacuum deposition, sputtering, plasma electroplating and ion electroplating), and forming a cathode or anode thereon.

[0221] The aforementioned organic light-emitting diodes can be applied to organic light-emitting display devices.

[0222] The embodiments are described in more detail below with reference to examples. However, these embodiments are exemplary and the scope of this application is not limited thereto.

[0223] Unless otherwise specified, the starting materials and reactants used in the examples and synthesis examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo Chemical Industry, or P&H Tech, or synthesized by known methods.

[0224] (Synthesis of compounds for organic optoelectronic devices)

[0225] Synthesis Example 1: Synthesis of Compound 1-1

[0226] [Reaction Formula 1]

[0227]

[0228] Step 1: Synthesis of intermediate Int-1

[0229] 20 g (71 mmol) of 2-bromo-9-chlorodibenzo[b,d]furan, 9.5 g (78 mmol) of phenylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended under reflux in 236 mL of THF and 106 mL of distilled water for 12 hours. When the reaction was complete, 18 g (91%) of intermediate Int-1 was obtained by extraction with toluene and recrystallization of the product.

[0230] Step 2: Synthesis of Compound 1-1

[0231] 15 g (54 mmol) of intermediate Int-1, 17 g (51 mmol) of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 26 g (84%) of compound 1-1.

[0232] LC-mass spectrometry (theoretical value: 574.20 g / mol, measured value: M+ = 574.68 g / mol)

[0233] Synthesis Example 2: Synthesis of Compounds 1-19

[0234] [Reaction 2]

[0235]

[0236] Step 1: Synthesis of intermediate Int-2

[0237] 20 g (71 mmol) of 2-bromo-9-chlorodibenzo[b,d]furan, 15.5 g (78 mmol) of 3-biphenylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended in 236 mL of THF and 106 mL of distilled water under a nitrogen atmosphere and stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 21 g (83%) of intermediate Int-2.

[0238] Step 2: Synthesis of compounds 1-19

[0239] 15 g (42 mmol) of intermediate Int-2, 16.4 g (40 mmol) of 5-[1,1'-biphenyl]-3-yl-5,8-dihydroindolo[2,3-c]carbazole, 1.9 g (2 mmol) of Pd2(dba)3, 7.1 g (13 mmol) of tricyclohexylphosphine, and 6.1 g (63 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 70 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 27.8 g (91%) of compounds 1-19.

[0240] LC-mass spectrometry (theoretical value: 726.27 g / mol, measured value: M+ = 726.88 g / mol)

[0241] Synthesis Example 3: Synthesis of Compounds 1-30

[0242] [Reaction 3]

[0243]

[0244] Step 1: Synthesis of intermediate Int-3

[0245] Under a nitrogen stream, 20 g (71 mmol) of 2-bromo-9-chlorodibenzo[b,d]furan, 21.3 g (78 mmol) of triphenyl-2-ylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended in 236 mL of THF and 106 mL of distilled water and stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 25 g (82%) of intermediate Int-3.

[0246] Step 2: Synthesis of compounds 1-30

[0247] 20 g (47 mmol) of intermediate Int-3, 14.7 g (44 mmol) of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, 2.1 g (2 mmol) of Pd2(dba)3, 7.9 g (14 mmol) of tricyclohexylphosphine, and 6.7 g (70 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 78 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 26.3 g (78%) of compound 1-30.

[0248] LC-mass spectrometry (theoretical value: 724.25 g / mol, measured value: M+ = 724.86 g / mol)

[0249] Synthesis Example 4: Synthesis of Compounds 1-37

[0250] [Reaction 4]

[0251]

[0252] Step 1: Synthesis of intermediate Int-4

[0253] 20 g (71 mmol) of 2-bromo-8-chlorodibenzo[b,d]furan, 9.5 g (78 mmol) of phenylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended in 236 mL of THF and 106 mL of distilled water under a nitrogen atmosphere and stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 16.5 g (83%) of intermediate Int-4.

[0254] Step 2: Synthesis of compounds 1-37

[0255] 15 g (54 mmol) of intermediate Int-4, 17 g (51 mmol) of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and then dissolved in DCM. After removing the water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 28 g (91%) of compound 1-37.

[0256] LC-mass spectrometry (theoretical value: 574.20 g / mol, measured value: M+ = 574.68 g / mol)

[0257] Synthesis Example 5: Synthesis of Compounds 1-49

[0258] [Reaction 5]

[0259]

[0260] 15 g (54 mmol) of intermediate Int-4, 20.9 g (51 mmol) of 5-[1,1'-biphenyl]-4-yl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 31 g (89%) of compound 1-49.

[0261] LC-mass spectrometry (theoretical value: 650.24 g / mol, measured value: M+ = 650.78 g / mol)

[0262] Synthesis Example 6: Synthesis of Compounds 1-68

[0263] [Reaction Formula 6]

[0264]

[0265] 15 g (54 mmol) of intermediate Int-4, 24.7 g (51 mmol) of 5-(bitriphenyl-2-yl)-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (3 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 34 g (87%) of compound 1-68.

[0266] LC-mass spectrometry (theoretical value: 724.25 g / mol, measured value: M+ = 724.86 g / mol)

[0267] Synthesis Example 7: Synthesis of Compounds 1-73

[0268] [Reaction Formula 7]

[0269]

[0270] Step 1: Synthesis of intermediate Int-5

[0271] 20 g (71 mmol) of 2-bromo-7-chlorodibenzo[b,d]furan, 9.5 g (78 mmol) of phenylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended in 236 mL of THF and 106 mL of distilled water under a nitrogen atmosphere and stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 17.8 g (83%) of intermediate Int-5.

[0272] Step 2: Synthesis of compounds 1-73

[0273] 15 g (54 mmol) of intermediate Int-5, 17 g (51 mmol) of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 26.5 g (86%) of compound 1-73.

[0274] LC-mass spectrometry (theoretical value: 574.20 g / mol, measured value: M+ = 574.68 g / mol)

[0275] Synthesis Example 8: Synthesis of Compounds 1-105

[0276] [Reaction Equation 8]

[0277]

[0278] Step 1: Synthesis of intermediate Int-6

[0279] 20 g (65 mmol) of 1-bromo-3,5-diphenylbenzene, 15.8 g (61 mmol) of 5,8-dihydroindolo[2,-c]carbazole, 3 g (3 mmol) of Pd2(dba)3, 10.9 g (19 mmol) of tricyclohexylphosphine, and 9.3 g (97 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 108 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing the water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to obtain 23 g (73%) of intermediate Int-6.

[0280] Step 2: Synthesis of Compound 1-105

[0281] 10 g (36 mmol) of intermediate Int-5, 16.5 g (34 mmol) of intermediate Int-6, 1.6 g (2 mmol) of Pd2(dba)3, 6 g (11 mmol) of tricyclohexylphosphine, and 5.2 g (54 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 60 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 24 g (92%) of compound 1-105.

[0282] LC-mass spectrometry (theoretical value: 726.27 g / mol, measured value: M+ = 726.88 g / mol)

[0283] Synthesis Example 9: Synthesis of Compounds 1-109

[0284] [Reaction Formula 9]

[0285]

[0286] Step 1: Synthesis of intermediate Int-7

[0287] 20 g (71 mmol) of 2-bromo-6-chlorodibenzo[b,d]furan, 9.5 g (78 mmol) of phenylboronic acid, 29.5 g (213 mmol) of K₂CO₃, and 4.9 g (4 mmol) of Pd(PPh₃)₄ were suspended in 236 mL of THF and 106 mL of distilled water under a nitrogen atmosphere and stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 16.8 g (85%) of intermediate Int-7.

[0288] Step 2: Synthesis of Compounds 1-109

[0289] 15 g (54 mmol) of intermediate Int-7, 17 g (51 mmol) of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 27.8 g (90%) of compound 1-109.

[0290] LC-mass spectrometry (theoretical value: 574.20 g / mol, measured value: M+ = 574.68 g / mol)

[0291] Synthesis Example 10: Synthesis of Compounds 1-129

[0292] [Reaction Formula 10]

[0293]

[0294] 15 g (54 mmol) of intermediate Int-7, 21 g (51 mmol) of 5-[1,1'-biphenyl]-2-yl-5,8-dihydroindolo[2,3-c]carbazole, 2.5 g (3 mmol) of Pd2(dba)3, 9.1 g (16 mmol) of tricyclohexylphosphine, and 7.8 g (81 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 90 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 30.5 g (87%) of compound 1-129.

[0295] LC-mass spectrometry (theoretical value: 650.24 g / mol, measured value: M+ = 650.78 g / mol)

[0296] Comparative Synthesis Example 1: Synthesis of Compound Body-1

[0297] [Reaction Formula 11]

[0298]

[0299] Step 1: Synthesis of compound bulk 1

[0300] 20 g (65 mmol) of 1-bromo-3,5-diphenylbenzene, 25 g (61 mmol) of 5-[1,1'-biphenyl]-2-yl-5,8-dihydroindolo[2,3-c]carbazole, 3 g (3 mmol) of Pd2(dba)3, 11 g (19 mmol) of tricyclohexylphosphine, and 9.3 g (97 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 108 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 h. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 h. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to obtain 38 g (92%) of the compound body. LC-mass spectrometry (theoretical value: 636.26 g / mol, measured value: M+ = 636.80 g / mol)

[0301] Comparative Synthesis Example 2: Synthesis of Compound Body-2

[0302] [Reaction 12]

[0303]

[0304] 20 g (76 mmol) of 3-chloro-1,1':2',1”-terphenyl, 29.3 g (72 mmol) of 5-[1,1'-biphenyl]-3-yl-5,8-dihydroindolo[2,3-c]carbazole, 3.5 g (4 mmol) of Pd2(dba)3, 12.7 g (23 mmol) of tricyclohexylphosphine, and 11 g (113 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 126 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing the water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to obtain 41 g (85%) of compound body-2.

[0305] LC-mass spectrometry (theoretical value: 636.26 g / mol, measured value: M+ = 636.80 g / mol)

[0306] Synthesis Example 11: Synthesis of Compound A-29

[0307] [Reaction Formula 13]

[0308]

[0309] 10 g (41 mmol) of 3-phenyl-9H-carbazole, 20 g (43 mmol) of 2-(3-bromophenyl)-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine, 2 g (2 mmol) of Pd2(dba)3, 7.3 g (13 mmol) of tricyclohexylphosphine, and 6.2 g (65 mmol) of sodium tert-butoxide were added to a round-bottom flask and dissolved in 72 mL of xylene. The mixture was stirred under reflux at 160 °C for 10 hours. When the reaction was complete, the mixture was poured into excess distilled water and stirred for 1 hour. The solid was filtered off and dissolved in DCM. After removing water with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid was recrystallized from ethyl acetate and hexane to give 25 g (93%) of compound A-29.

[0310] LC-mass spectrometry (theoretical value: 626.25 g / mol, measured value: M+ = 626.76 g / mol)

[0311] Synthesis Example 12: Synthesis of Compound A-39

[0312] [Reaction Formula 14]

[0313]

[0314] Under a nitrogen stream, 20 g (58 mmol) of 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine, 24 g (64 mmol) of 9-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl]-9H-carbazole, 24.1 g (175 mmol) of K₂CO₃, and 4 g (3 mmol) of Pd(PPh₃)₄ were suspended in 194 mL of THF and 87 mL of distilled water, and then stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 30.2 g (94%) of compound A-39.

[0315] LC-mass spectrometry (theoretical value: 550.22 g / mol, measured value: M+ = 550.67 g / mol)

[0316] Synthesis Example 13: Synthesis of Compound B-182

[0317] [Reaction Formula 15]

[0318]

[0319] 20 g (45 mmol) of 2-[1,1'-biphenyl]-4-yl-4-chloro-6-(3-dibenzofuranyl)-1,3,5-triazine, 16.7 g (45 mmol) of 4,4,5,5-tetramethyl-2-(9-phenyldibenzo[b,d]furan-3-yl)-1,3,2-dioxane, 18.7 g (135 mmol) of K₂CO₃, and 3.1 g (3 mmol) of Pd(PPh₃)₄ were suspended in 150 mL of THF and 67 mL of distilled water under a nitrogen atmosphere, and then stirred under reflux for 12 hours. When the reaction was complete, the product was extracted with toluene and recrystallized to obtain 24 g (83%) of compound B-182.

[0320] LC-mass spectrometry (theoretical value: 641.21 g / mol, measured value: M+ = 641.73 g / mol)

[0321] Comparative Synthesis Example 3: Synthesis of Compound Body-3

[0322]

[0323] The compound host-3 was synthesized using the synthetic method described in publication number KR 10-2022-0095942A.

[0324] Example 1: Manufacturing a green organic light-emitting diode (single host)

[0325] The glass substrate coated with an ITO (indium tin oxide) film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with solvents such as isopropanol, acetone, and methanol, and then dried. It was then transferred to a plasma cleaner and cleaned with oxygen plasma for 10 minutes before being transferred to a vacuum depositor. The prepared ITO transparent electrode was used as the anode, and compound A (Novaled GmbH) doped with 3% NDP-9 was vacuum deposited onto the ITO substrate to form... A thick hole injection layer, and compound A is deposited on the hole injection layer until... The thickness is increased to form a hole transport layer. Compound B is deposited on the hole transport layer to... The thickness is adjusted to form a hole transport auxiliary layer. On the hole transport auxiliary layer, compound 1-1 synthesized in Synthesis Example 1 is used as the host and doped with 10 wt% PhGD as a dopant to form the layer by vacuum deposition. A thick luminescent layer. Subsequently, compound C is deposited on the luminescent layer to form... A thick electron transport auxiliary layer was formed, and compounds D and Liq were simultaneously vacuum-deposited at a 1:1 weight ratio to form A thick electron transport layer. On the electron transport layer, sequential vacuum deposition... LiQ and Al forms the cathode, thereby manufacturing an organic light-emitting diode.

[0326] Organic light-emitting diodes are fabricated with ITO / compound A (3% NDP-9 doping). Compound A / Compound B / EML[Body (Compound 1-1): PhGD = 90wt% : 10wt%] / Compound C / Compound D:LiQ / LiQ / Al The structure.

[0327] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine

[0328] Compound B: N-[4-(4-dibenzofuranyl)phenyl]-N-[4-(9-phenyl-9H-fluorene-9-yl)phenyl][1,1'-biphenyl]-4-amine

[0329] Compound C: 2,4-Diphenyl-6-(4',5',6'-triphenyl[1,1':2',1”:3”,1”':3”,1””-pentaphenyl]-3””-yl)-1,3,5-triazine

[0330] Compound D: 2-(1,1'-biphenyl-4-yl)-4-(9,9-diphenylfluorene-4-yl)-6-phenyl-1,3,5-triazine

[0331] [PhGD]

[0332]

[0333] Examples 2 to 10 and Comparative Examples 1 to 2

[0334] Organic light-emitting diodes were manufactured in the same manner as in Example 1, except that the compositions were changed to those shown in Table 1.

[0335] Example 11: Fabrication of a Green Organic Light Emitting Diode (Hybrid Body)

[0336] The glass substrate coated with an ITO (indium tin oxide) film was ultrasonically cleaned with distilled water. After washing with distilled water, the glass substrate was ultrasonically cleaned with solvents such as isopropanol, acetone, and methanol, and then dried. It was then transferred to a plasma cleaner and cleaned with oxygen plasma for 10 minutes before being transferred to a vacuum depositor. The prepared ITO transparent electrode was used as the anode, and compound A (Novaled GmbH) doped with 3% NDP-9 was vacuum deposited onto the ITO substrate to form... A thick hole injection layer, and compound A is deposited on the hole injection layer until... The thickness is increased to form a hole transport layer. Compound E is deposited on the hole transport layer to... The thickness was increased to form a hole transport auxiliary layer. On the hole transport auxiliary layer, compounds 1-30 synthesized in Synthesis Example 3 and compound A-29 synthesized in Synthesis Example 11 were used simultaneously in a 7:3 weight ratio as the host, and PtGD was doped with 15 wt% as a dopant by vacuum deposition to form... A thick luminescent layer. Subsequently, compound F is deposited on the luminescent layer to... The thickness is adjusted to form an electron transport auxiliary layer, and simultaneously, compounds G and Liq are vacuum deposited in a 1:1 weight ratio to form a layer with... An electron transport layer of a certain thickness. On the electron transport layer, sequential vacuum deposition... LiQ and Al forms the cathode, thereby manufacturing an organic light-emitting diode.

[0337] Organic light-emitting diodes are fabricated with ITO / compound A (3% NDP-9 doping). Compound A-29 / Compound E / EML[Body (Compounds 1-30: Compound B-8 = 7: 3wt% / wt%): PtGD = 85wt%: 15wt%] / compound F / Compound G:LiQ / LiQ / Al The structure.

[0338] Compound E: N,N-bis(9,9-dimethyl-9H-fluorene-4-yl)-9,9-spirodi(fluorene)-2-amine

[0339] Compound F: 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine

[0340] Compound G: 2-[4-[4-(4'-cyano-1,1'-biphenyl-4-yl)-1-naphthyl]phenyl]-4,6-diphenyl-1,3,5-triazine

[0341] [PtGD]

[0342]

[0343] Examples 12 to 18 and Comparative Examples 3 to 7

[0344] Each organic light-emitting diode was manufactured in the same manner as in Example 11, except that the composition was changed to those shown in Table 2.

[0345] evaluate

[0346] The driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting diodes according to Examples 1 to 18 and Comparative Examples 1 to 7 were evaluated.

[0347] The specific measurement methods are as follows, and the results are shown in Tables 1 and 2.

[0348] (1) Measure the change in current density based on voltage change.

[0349] The voltage was increased from 0V to 10V using a current-voltmeter (Keithley 2400), and the current flowing through the organic light-emitting diode in the unit device was measured. The measured current value was then divided by the area to provide the result.

[0350] (2) Measure the brightness change based on voltage changes

[0351] The brightness was measured using a luminance meter (Minolta Cs-1000A) when the voltage of the organic light-emitting diode was increased from 0V to 10V.

[0352] (3) Measure luminous efficiency

[0353] The brightness and current density, as well as the voltage, from (1) and (2) above were used to calculate the voltage at the same current density (10 mA / cm²). 2 Luminous efficiency (cd / A) at ).

[0354] Based on Comparative Example 1, the luminous efficiency values ​​of Examples 1 to 10 and Comparative Examples 1 to 2 were calculated as relative values ​​and are shown in Table 1.

[0355] Based on Comparative Example 3, the luminous efficiency values ​​of Examples 11 to 18 and Comparative Examples 3 to 7 were calculated as relative values ​​and are shown in Table 2.

[0356] (4) Measurement of lifespan

[0357] By using brightness (cd / m 2 Maintain at 24000 cd / m 2 The results were obtained by measuring the time it took for the current efficiency (cd / A) to drop to 97%.

[0358] Based on Comparative Example 1, lifetime measurements of Examples 1 to 10 and Comparative Examples 1 to 2 were calculated as relative values ​​and are shown in Table 1.

[0359] Based on Comparative Example 3, lifetime measurements of Examples 11 to 18 and Comparative Examples 3 to 7 were calculated as relative values ​​and are shown in Table 2.

[0360] (5) Measure the driving voltage

[0361] Using a current-voltmeter (Keithley 2400) at 15mA / cm 2 The results are obtained by measuring the drive voltage of each diode.

[0362] Based on Comparative Example 1, the driving voltages of Examples 1 to 10 and Comparative Examples 1 to 2 were calculated as relative values ​​and are shown in Table 1.

[0363] Based on Comparative Example 3, the driving voltages of Examples 11 to 18 and Comparative Examples 3 to 7 were calculated as relative values ​​and are shown in Table 2.

[0364] (Table 1)

[0365] serial number compound Drive voltage (%) Luminous efficiency (%) life(%) Example 1 1-1 95 105 105 Example 2 1-19 94 106 106 Example 3 1-30 94 105 107 Example 4 1-37 95 107 110 Example 5 1-49 93 108 108 Example 6 1-68 97 104 105 Example 7 1-73 95 105 105 Example 8 1-105 95 105 107 Example 9 1-109 96 105 103 Example 10 1-129 97 104 100 Comparative Example 1 Main body-1 100 100 100 Comparative Example 2 Main body-2 97 101 86

[0366] (Table 2)

[0367]

[0368]

[0369] Referring to Tables 1 and 2, compared with the organic light-emitting devices according to Comparative Examples 1 to 7, the organic light-emitting diodes according to Examples 1 to 18 have significantly improved driving voltage, luminous efficiency and lifetime characteristics.

[0370] Although the invention has been described in conjunction with embodiments now regarded as practical exemplary embodiments, it should be understood that the invention is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0371] Explanation of reference numerals in the attached figures:

[0372] 100: Organic Light Emitting Diode

[0373] 105: Organic layer

[0374] 110: Cathode

[0375] 120: Anode

[0376] 130: Emissive layer

[0377] 140: Hole transport region

[0378] 150: Electronic transmission area.

Claims

1. A compound for use in organic optoelectronic devices, said compound being represented by chemical formula 1: [Chemical Formula 1] In chemical formula 1, X 1 Is it O or S? Ar 1 and Ar 2 Each is independently a substituted or unsubstituted C6 to C30 aryl group. R 1 To R 14 Each is independently either hydrogen or deuterium, and m1 is an integer from 1 to 3.

2. The compound for organic optoelectronic devices according to claim 1, wherein, Chemical formula 1 can be represented by any one of chemical formulas 1-1 to 1-4: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formulas 1-3] [Chemical Formulas 1-4] In chemical formulas 1-1 to 1-4, X 1 Ar 1 and Ar 2 R 1 To R 14 And m1 is the same as defined in claim 1.

3. The compound for organic optoelectronic devices according to claim 2, wherein... Chemical formula 1 is represented by any one of chemical formulas 1-1 to 1-3.

4. The compound for organic optoelectronic devices according to claim 1, wherein, Ar 1 It is a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, or a substituted or unsubstituted triphenylene.

5. The compound for organic optoelectronic devices according to claim 1, wherein, Ar 2 It is a substituted or unsubstituted C6 to C30 unfused aryl group.

6. The compound for organic optoelectronic devices according to claim 1, wherein, Ar 2 It is a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted terphenyl.

7. The compound for organic optoelectronic devices according to claim 1, wherein, The compound is selected from one of the compounds listed in Group 1: [Group 1] In group 1, Dn refers to the number of deuterium substitutions.

8. A composition for use in an organic optoelectronic device, comprising: First compound and second compound, in, The first compound is the compound for organic optoelectronic devices according to any one of claims 1 to 7, and The second compound is represented by chemical formula 2A or chemical formula 2B: [Chemical Formula 2A][Chemical Formula 2B] In chemical formulas 2A and 2B, Z 1 To Z 3 Each is independently N or CL a -R a , Z 1 To Z 3 At least two of them are N. X 2 Is it O, S, or NR? b , L a and L 3 To L 5 Each is independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof. R a R b and R 23 To R 35 Each of these elements independently comprises hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amino, halogen, cyano, or combinations thereof. Ar 3 and Ar 4 Each is independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, and m5 is an integer from 1 to 3.

9. The composition for an organic optoelectronic device according to claim 8, wherein, Chemical formula 2A can be represented by any one of chemical formulas 2A-I to 2A-III, and Chemical formula 2B can be represented by any one of chemical formulas 2B-I to 2B-IV: [Chemical formula 2A-I] [Chemical formula 2A-II] [Chemical Formula 2A-III] [Chemical Formula 2B-I][Chemical Formula 2B-II] [Chemical Formula 2B-III][Chemical Formula 2B-IV] In chemical formulas 2A-I to 2A-III and 2B-I to 2B-IV L 3 To L 5 Each is independently a single bond or a substituted or unsubstituted C6 to C12 aryl group, Ar 3 and Ar 4 Each of these can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted triphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted triphenylene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiopheneyl, or a substituted or unsubstituted carbazoleyl. R 23 To R 35 and R 53 To R 60 Each is independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkylsilyl, or substituted or unsubstituted C6 to C12 aryl, and m5 is an integer from 1 to 3.

10. An organic optoelectronic device, comprising: The anode and cathode facing each other, and At least one organic layer between the anode and the cathode, The organic layer includes: The compound for an organic optoelectronic device according to any one of claims 1 to 7; or The composition for an organic optoelectronic device as described in claim 8 or claim 9.

11. The organic optoelectronic device according to claim 10, wherein... The organic layer includes a light-emitting layer, and The light-emitting layer comprises the compound for organic optoelectronic devices or the composition for organic optoelectronic devices.

12. A display device comprising the organic optoelectronic device of claim 10.

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