Organic compounds and organic light-emitting diodes containing them

Abstract

The organic compound represented by chemical formula A of the present invention can excellently achieve hole transport characteristics. Furthermore, the hole transport layer or hole transport auxiliary layer of the organic light-emitting diode of the present invention contains the organic compound represented by chemical formula A of the present invention, thereby improving the driving voltage, efficiency, and lifetime characteristics of the organic light-emitting diode.

Description

Technical Field

[0001] This invention relates to an organic compound and an organic light-emitting diode comprising the same. Background Technology

[0002] Compared with other flat panel display diodes such as liquid crystal displays (LCDs), plasma display panels (PDPs), and field emission displays (FEDs), organic light-emitting diodes (OLEDs) have many advantages in terms of simple structure and manufacturing process. They also have high brightness and excellent viewing angle characteristics, as well as fast response speed and low driving voltage. Therefore, they are being actively developed and commercialized as light sources for flat panel displays such as wall-mounted TVs (TVs) or for backlighting, illumination, and advertising boards.

[0003] An organic light-emitting diode (OLED) consists of an organic layer between two electrodes. It works by injecting electrons and holes into the light-emitting layer from the two electrodes. When electrons and holes combine, they generate excitons. When these excitons transition from an excited state to a ground state, they emit light.

[0004] Organic light-emitting diodes (OLEDs) may include at least one light-emitting layer. Typically, OLEDs with multiple light-emitting layers include light-emitting layers that emit light with different peak wavelengths, and a specific color is achieved by combining light with different peak wavelengths.

[0005] Such organic light-emitting diodes (OLEDs) can be divided into front-emitting diodes (LEDs) and back-emitting diodes (NEDs). Front-emitting diodes use a reflective second electrode (cathode) to emit light emitted from the light-emitting layer towards the semi-transparent or transparent first electrode (anode). Conversely, back-emitting diodes use a reflective first electrode to emit light emitted from the light-emitting layer and reflected from the first electrode towards the transparent second electrode, which is the direction in which the thin-film transistor is driven.

[0006] Existing technical documents

[0007] Patent documents

[0008] Existing patent document 1: KR 2020-0122116 A

[0009] Existing patent document 2: WO 2021 / 070964 A1

[0010] Existing patent document 3: US 2018-0219157 A1 Summary of the Invention

[0011] Technical issues

[0012] The purpose of this invention is to provide a novel organic compound and an organic light-emitting diode comprising the same.

[0013] Apart from the technical issues mentioned above, technical issues not specifically mentioned will be explained through embodiments of the present invention.

[0014] The objectives of this invention are not limited to those mentioned above. Other objectives and advantages of the invention not mentioned can be understood through the following description, and will become more apparent through embodiments of the invention. Furthermore, it will be understood that the objectives and advantages of the invention can be achieved through the means and combinations thereof shown in the claims.

[0015] Technical solution

[0016] According to one embodiment of the present invention, an organic compound represented by the following chemical formula A can be provided. The definition of chemical formula A is the same as that described in this specification and the claims.

[0017] Chemical formula A:

[0018]

[0019] In the chemical formula A,

[0020] Ar is selected from one of the structures M2, M3, M4, M11, M12, M13, M14, M15, M16, M17, M18, M19, M20, M21, M22, M23, M24, M25, M26, M27, M28, M29, M30, and M31.

[0021] R1 to R 17 They may be the same as or different from each other, and each independently consists of one selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups of 1 to 30, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups of 3 to 60 carbon atoms.

[0022] n1 and n2 may be the same or different from each other, and each is an independent integer from 0 to 5.

[0023] n3 is an integer from 0 to 3.

[0024] n4 is an integer from 0 to 4.

[0025] In Ar and R1 to R 17When substituted, the substituents may be the same or different from each other, and can be selected from deuterium, cyano, trifluoromethyl, nitro, halogen group, hydroxyl, trimethylsilyl (TMS), alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, cycloalkenyl with 3 to 20 carbon atoms, alkynyl with 2 to 30 carbon atoms, cycloalkynyl with 3 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms, heteroaryl with 3 to 60 carbon atoms, heteroaryl with 4 to 60 carbon atoms, amine The substituents are one or more of the group consisting of alkylamino, alkylamino with 1 to 30 carbon atoms, arylalkylamino with 7 to 30 carbon atoms, arylamino with 6 to 30 carbon atoms, heteroarylamino with 3 to 60 carbon atoms, silyl, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, aryloxy with 6 to 30 carbon atoms, alkylthio with 1 to 30 carbon atoms, and arylthio with 6 to 30 carbon atoms, wherein when there are multiple substituents, the substituents may be the same or different from each other.

[0026] The effects of the invention

[0027] The organic compound represented by chemical formula A of the present invention can achieve excellent hole transport characteristics.

[0028] Furthermore, one or more of the hole transport layer and hole transport auxiliary layer of the organic light-emitting diode of the present invention contain the organic compound represented by chemical formula A of the present invention, thereby improving the driving voltage, external quantum efficiency and lifetime characteristics of the organic light-emitting diode.

[0029] Furthermore, when the organic compound represented by chemical formula A of the present invention is used as the hole transport auxiliary layer material, it can have an appropriate energy level as a hole transport auxiliary layer, which plays the role of transporting holes from the hole transport layer to the light-emitting layer and blocking electrons from the light-emitting layer.

[0030] Furthermore, the organic light-emitting diode of the present invention includes a hole transport layer and / or a hole transport auxiliary layer comprising an organic compound represented by chemical formula A of the present invention, which can excellently achieve the color coordinates targeted by the light-emitting layer even when combined with a light-emitting layer of any color.

[0031] The effects of this invention are not limited to those described above. Those skilled in the art will clearly understand other effects not mentioned through the full description in this specification. The above and other effects will be described in detail below. Detailed Implementation

[0032] The foregoing objectives, features, and advantages will be described in detail below, and those skilled in the art to which this invention pertains can easily implement the technical ideas of this invention.

[0033] In describing this specification, detailed descriptions of well-known technologies related to this invention will be omitted when it is determined that such descriptions may unnecessarily obscure the essence of the invention.

[0034] In this specification, when structural elements such as "including," "having," "forming," "setting," and "possessing" are mentioned, other parts may be added unless limited by "only." Unless otherwise expressly stated, the use of the singular to express structural elements includes the plural case.

[0035] In this specification, when interpreting structural elements, even if not explicitly stated, it is interpreted as including the range of error.

[0036] In this specification, when referring to the “upper (or lower) part” of a structural element or the “upper (or lower) part” of a structural element having any structure, it not only indicates that the arbitrary structure is arranged in contact with the upper (or lower) part of the structural element, but also indicates that there are other structures intervening between the structural element and the arbitrary structure arranged on the upper (or lower) part of the structural element.

[0037] The term "halogen group" as used in this specification includes fluorine, chlorine, bromine, and iodine.

[0038] As used in this specification, the term "alkyl" refers to both straight-chain alkyl radicals and branched-chain alkyl radicals. Unless otherwise specified, an alkyl group contains 1 to 30 carbon atoms and may include, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, etc. Furthermore, alkyl groups may be substituted in any way.

[0039] As used in this specification, the term "cycloalkyl" refers to a cyclic alkyl radical. Unless otherwise specified, a cycloalkyl group contains 3 to 20 carbon atoms and may include, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. Furthermore, the cycloalkyl group may be substituted in any way.

[0040] As used in this specification, the term "alkenyl" refers to a straight-chain alkenyl radical and a branched alkenyl radical having one or more carbon-carbon double bonds. Unless otherwise specified, an alkenyl group contains 2 to 30 carbon atoms and may include, but is not limited to, vinyl, allyl, isopropenyl, 2-butenyl, etc. Furthermore, the alkenyl group can be arbitrarily substituted.

[0041] As used in this specification, the term "cycloalkenyl" refers to a cyclic alkenyl radical. Unless otherwise specified, a cycloalkenyl radical contains 3 to 20 carbon atoms, and furthermore, the cycloalkenyl radical can be arbitrarily substituted.

[0042] As used in this specification, the term "alkynyl" refers to a straight-chain alkynyl radical and a branched alkynyl radical having one or more carbon-carbon triple bonds. Unless otherwise specified, an alkynyl radical contains 2 to 30 carbon atoms. It may include, but is not limited to, ethynyl and 2-propynyl. Furthermore, the alkynyl group may be arbitrarily substituted.

[0043] As used in this specification, the term "cycloynyl" refers to a cyclic ynyl radical. Unless otherwise specified, a cycloynyl radical contains 3 to 20 carbon atoms, and furthermore, the cycloynyl radical can be arbitrarily substituted.

[0044] The terms “aralkyl” or “arylalkyl” used in this specification may be used interchangeably and refer to an alkyl group having an aromatic group as a substituent. Furthermore, aralkyl (arylalkyl) may be substituted in any way.

[0045] The terms "aryl" or "aromatic group" used in this specification have the same meaning, and aryl includes monocyclic and polycyclic groups. Polycyclic groups can include "fused rings" consisting of two or more rings shared by two adjacent rings, with two carbon atoms. Furthermore, they can also include forms where two or more rings are simply linked or fused together. Unless otherwise specified, aryl groups contain 6 to 30 carbon atoms and can include, but are not limited to, phenyl, naphthyl, phenanthryl, anthraceneyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, etc. Furthermore, aryl groups can be substituted in any way.

[0046] The terms "heteroaryl" or "heteroaromatic group" used in this specification have the same meaning, and heteroaryl includes monocyclic and polycyclic groups. Polycyclic groups can include "fused rings" of two or more rings shared by two adjacent rings as two carbon atoms or heteroatoms. Furthermore, they can also include forms in which two or more rings are simply connected or fused together. Unless otherwise specified, the heteroaryl group contains 3 to 60 carbon atoms. In this case, one or more carbon atoms in the ring are replaced by heteroatoms such as oxygen (O), nitrogen (N), sulfur (S), or selenium (Se). It can include 6-membered monocyclic rings, such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings, such as phenoxthiayl, indoleazinyl, indoleyl, purine, quinolinyl, isoquinolinyl, benzoxazolyl, benzothiazolyl, dibenzoxazolyl, dibenzothiazolyl, benzimidazolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, phenylcarbazolyl, and 9-phenylcarbazolyl; and 2-furanyl, N-imidazolyl, 2-isooxazolyl, 2-pyridinyl, and 2-pyrimidinyl, but is not limited thereto. Furthermore, the heteroaryl group can be arbitrarily substituted.

[0047] As used in this specification, the term "heterocyclic group" refers to a group in which one or more carbon atoms constituting aryl, cycloalkyl, cycloalkenyl, cycloalkynyl, aralkyl, arylamino, etc., are replaced by heteroatoms such as oxygen (O), nitrogen (N), and sulfur (S). Referring to the above definition, it includes heteroaryl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, heteroaromaticyl, heteroaromaticamino, etc. Furthermore, heterocyclic groups can be arbitrarily substituted.

[0048] Unless otherwise specified, the term "carbon ring" as used in this specification may be used as a term that simultaneously includes "cycloalkyl", "cycloalkenyl", "cycloynyl" as alicyclic cyclic groups and "aryl (aromatic group)" as an aromatic cyclic group.

[0049] The terms “heteroalkyl,” “heteroalkenyl,” “heteroynyl,” and “heteroaryl” used in this specification refer to a form in which one or more carbon atoms constituting the carbon atom are replaced by heteroatoms such as oxygen (O), nitrogen (N), and sulfur (S). Furthermore, heteroalkyl, heteroalkenyl, heteroynyl, and heteroaryl can be arbitrarily substituted.

[0050] As used in this specification, the terms "alkylamino", "arylalkylamino", "arylamino", and "heteroarylamino" refer to amino groups (or amino groups) that are substituted by the alkyl, arylalkyl, aryl, or heteroaryl groups, and simultaneously include primary, secondary, or tertiary amino groups (or amino groups). Furthermore, alkylamino, arylalkylamino, arylamino, and heteroarylamino groups can be substituted in any way.

[0051] The terms “alkylsilyl”, “arylsilyl”, “alkoxy”, “aryloxy”, “alkathio”, and “arylthio” used in this specification refer to the substitution of silyl, oxy, and thio groups by the alkyl and aryl groups, respectively. Furthermore, alkylsilyl, arylsilyl, alkoxy, aryloxy, alkathio, and arylthio can be substituted in any way.

[0052] As used in this specification, the terms "arylene," "arylalkylene," "heteroarylene," and "heteroarylalkylene" refer to the aryl, aralkyl, heteroaryl, and heteroaryl groups each comprising one or more divalent substituents. Furthermore, the arylene, arylalkylene, heteroarylene, and heteroarylalkylene groups may be substituted in any way.

[0053] As used in this specification, the term "substitution" means replacing hydrogen (H) atoms bonded to carbon atoms, nitrogen atoms, etc., of the compounds of the present invention with substituents other than hydrogen. In the case of multiple substituents, the substituents may be the same as or different from each other.

[0054] The substituents may be independently selected from deuterium, cyano, trifluoromethyl, nitro, halogen group, hydroxyl, trimethylsilyl (TMS), alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, cycloalkenyl with 3 to 20 carbon atoms, alkynyl with 2 to 30 carbon atoms, cycloalkynyl with 3 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms, heteroaryl with 3 to 60 carbon atoms, and carbon atom. Among the following groups: heteroaryl, amino, alkylamino, arylalkylamino, arylalkylamino, arylamino, heteroarylamino, silyl, alkylsilyl, arylsilyl, alkoxy, aryloxy, alkathio, alkylthio, and arylthio.

[0055] In this specification, unless otherwise specified, the position of substitution is not limited, as long as it is the position where a hydrogen atom is substituted, that is, the position where the substituent can be substituted. When there are two or more substituents, the substituents can be the same or different from each other.

[0056] Unless otherwise specified, the objects and substituents defined in this specification may be the same or different.

[0057] Unless otherwise specified, all units in this specification are in weight (wt). For example, if stated as "%", it means weight percentage (wt%).

[0058] The organic compounds of the present invention and organic light-emitting diodes comprising the thereof will be described in detail below.

[0059] The organic compounds of the present invention can be represented by the following chemical formula A.

[0060] Chemical formula A:

[0061]

[0062] In the chemical formula A,

[0063] Ar is an aryl group with 6 to 30 carbon atoms, either substituted or unsubstituted.

[0064] R1 to R 17 They may be the same as or different from each other, and each independently consists of one selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups of 1 to 30, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups of 3 to 60 carbon atoms.

[0065] n1 and n2 may be the same or different from each other, and each is an independent integer from 0 to 5.

[0066] n3 is an integer from 0 to 3.

[0067] n4 is an integer from 0 to 4.

[0068] In Ar and R1 to R 17 When substituted, the substituents may be the same or different from each other, and can be selected from deuterium, cyano, trifluoromethyl, nitro, halogen group, hydroxyl, trimethylsilyl (TMS), alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, cycloalkenyl with 3 to 20 carbon atoms, alkynyl with 2 to 30 carbon atoms, cycloalkynyl with 3 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms, heteroaryl with 3 to 60 carbon atoms, heteroaryl with 4 to 60 carbon atoms, amine The substituents are one or more of the group consisting of alkylamino, alkylamino with 1 to 30 carbon atoms, arylalkylamino with 7 to 30 carbon atoms, arylamino with 6 to 30 carbon atoms, heteroarylamino with 3 to 60 carbon atoms, silyl, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, aryloxy with 6 to 30 carbon atoms, alkylthio with 1 to 30 carbon atoms, and arylthio with 6 to 30 carbon atoms, wherein when there are multiple substituents, the substituents may be the same or different from each other.

[0069] According to one embodiment of the present invention, the Ar can be an aryl group with 6 to 25, 6 to 15, 6 to 12 or 6 to 10 carbon atoms, either substituted or unsubstituted.

[0070] According to one embodiment of the present invention, Ar may be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraceneyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted dimethylfluorenyl, a substituted or unsubstituted diphenylfluorenyl, a substituted or unsubstituted spirodifluorenyl, a substituted or unsubstituted naphthyl-phenyl, a substituted or unsubstituted dimethylfluorenyl-phenyl, or a substituted or unsubstituted phenanthrene-phenyl.

[0071] According to one embodiment of the present invention, Ar may be a deuterated or unsubstituted phenyl, a deuterated or unsubstituted biphenyl, a deuterated or unsubstituted naphthyl, a deuterated or unsubstituted dimethylfluorenyl, a deuterated or unsubstituted naphthyl-phenyl, a deuterated or unsubstituted dimethylfluorenyl-phenyl, or a deuterated or unsubstituted phenanthrene-phenyl.

[0072] According to one embodiment of the present invention, Ar can be a structure in which a phenylene (linking group) is substituted by a monocyclic or fused ring. For example, the monocyclic ring can be phenyl, and the fused ring can be dimethylfluorenyl, naphthyl, or phenanthrene.

[0073] According to one embodiment of the present invention, Ar can be one of the substituents represented by M1 to M31 below. In M1 to M31 below, * indicates a bonding site. For example, Ar can be one of the substituent structures represented by M2, M3, M4, M11, M12, M13, M14, M15, M16, M17, M18, M19, M20, M21, M22, M23, M24, M25, M26, M27, M28, M29, M30 and M31 below.

[0074] According to one embodiment of the present invention, in M1 to M31 below, Dn refers to the number of deuteriums replaced in the structure, where n, representing the number of deuteriums, is an integer greater than or equal to 0.

[0075] According to an embodiment of the present invention, in formula M1, n is an integer selected from 0 to 5; in formulas M2 to M4, n is an integer selected from 0 to 9; in formulas M5 and M6, n is an integer selected from 0 to 7; in formulas M7 to M10, n is an integer selected from 0 to 13; in formulas M11 to M16, n is an integer selected from 0 to 11; in formulas M17 to M28, n is an integer selected from 0 to 17; and in formulas M29 to M31, n is an integer selected from 0 to 13.

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] According to an embodiment of the present invention, R1 to R 17 They can be the same or different from each other, and can be hydrogen or deuterium independently.

[0085] According to one embodiment of the present invention, the compound represented by chemical formula A may be selected from the group consisting of the following compounds, but is not limited thereto.

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] An organic light-emitting diode according to an embodiment of the present invention includes: a first electrode (anode); a second electrode (cathode) disposed opposite to the first electrode; and one or more organic layers located inside the first electrode and the second electrode, wherein at least one of the more than one organic layers is a hole transport layer or a hole transport auxiliary layer containing the organic compound represented by the chemical formula A.

[0100] The organic layer may include one or more of the following: Hole Injection Layer (HIL), Hole Transport Layer (HTL), Hole Transport Auxiliary Layer, Emitting Layer (EML), Electron Transport Auxiliary Layer, Electron Transport Layer (ETL), and Electron Injection Layer (EIL).

[0101] For example, an organic light-emitting diode can have a structure in which a first electrode, a hole injection layer (HIL), a hole transport layer (HTL), a hole transport auxiliary layer, an emissive layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), and a second electrode are stacked sequentially.

[0102] The organic layer containing the organic compound represented by chemical formula A in an embodiment of the present invention can be a hole transport layer (HTL) or a hole transport auxiliary layer.

[0103] The organic layer or more may further include one or more selected from the group consisting of a hole injection layer, a light-emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.

[0104] The first electrode can be an anode, and the first electrode can contain transparent and highly conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), and zinc oxide (ZnO).

[0105] The second electrode can be a cathode, and it can contain materials such as lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). Furthermore, in the case of a back-emitting organic light-emitting diode, indium tin oxide (ITO) or indium zinc oxide (IZO) can be used to form a transparent second electrode that allows light to pass through.

[0106] The surface of the second electrode can be covered with a capping layer (CPL) by a composition for forming the capping layer.

[0107] Furthermore, a protective layer (encapsulation layer or protecting layer) can be provided on the cover layer to protect the organic light-emitting diode from the effects of moisture and oxygen. This protective layer can be made of a curable adhesive composition containing an inorganic hygroscopic agent.

[0108] An organic light-emitting diode according to an embodiment of the present invention includes a first electrode (anode); a second electrode (cathode) disposed opposite to the first electrode; and one or more organic layers located inside the first electrode and the second electrode, wherein at least one of the organic layers is a hole transport auxiliary layer containing the organic compound represented by the chemical formula A.

[0109] Wherein, when the organic layer containing the organic compound represented by chemical formula A in an embodiment of the present invention is a hole transport auxiliary layer, the hole injection layer, light emission layer, electron transport auxiliary layer, electron transport layer and electron injection layer constituting the organic layer or more can be defined as the following compounds, but are not limited thereto.

[0110] The hole injection layer or hole transport layer compound is not particularly limited, and any compound commonly used as a hole injection layer or hole transport layer compound can be used. Non-limiting examples of hole injection layer or hole transport layer compounds may include phthalocyanine derivatives, porphyrin derivatives, triarylamine derivatives, indole-carbazole derivatives, etc. For example, it may include 1,4,5,8,9,11-hexaazabenzophenanthrene-hexacarboxynitrile (HAT-CN), copper phthalocyanine (CuPc), 4,4',4”-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4”-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB), 4,4',4”-tris(N-carbazolyl)triphenylamine (TCTA), 4,4',4”-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine (2-TNATA), N4,N4,N4',N4'-tetra([1,1' [1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (N4,N4,N4',N4'-Tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine), bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-bis(naphthyl-1-yl)-N,N'-biphenyl-benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), etc.

[0111] The compounds contained in the luminescent layer are not particularly limited, and any compound commonly used as a luminescent layer compound can be used. A single luminescent compound or a host luminescent compound can be used.

[0112] According to one embodiment of the present invention, the light-emitting layer can be a blue or green light-emitting layer. When used as a blue light-emitting layer, excellent diode performance can be achieved.

[0113] According to one embodiment of the present invention, when used as a blue emitting layer, the CIEx and CIEy color coordinate systems are not particularly limited, as long as they correspond to the blue emitting layer. For example, CIEx can be 0.10 to 0.15, and CIEy can be 0.03 to 0.10.

[0114] The luminescent compound serving as the luminescent layer may include, but is not limited to, compounds capable of emitting phosphorescence, fluorescence, thermal ignition delayed fluorescence (TADF, or also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes to achieve luminescence. Depending on the desired luminescence color, the luminescent compound can be selected from a variety of materials. Non-limiting examples of luminescent compounds may include phenanthrene, anthracene, pyrene, tetraphenylene, pentaphenylene, perylene, naphthopyrene, dibenzopyrene, fluorene and β-cyclohexane derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bis(styrene) derivatives, bis(styrene)-arylene derivatives, diazaindenene derivatives, furan derivatives, benzofuran derivatives, isobenzofuran derivatives, dibenzofuran derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, and polymethimide derivatives. Anthocyanin derivatives, oxabenzanthracene derivatives, xanthones derivatives, rhodamine derivatives, fluorescein derivatives, pyranonium derivatives, quinolone derivatives, acridine derivatives, oxazine derivatives, benzodioxin derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furanopyridine derivatives, 1,2,5-thiadiazolpyrene derivatives, promethazine derivatives, violacetone derivatives, pyrrolopyrrole derivatives, squaric acid cyanide derivatives, violacetone derivatives, phenazine derivatives, acridineone derivatives, desoxyflavin derivatives, fluorene derivatives, benzo[a]fluorene derivatives, aromatic boron derivatives, aromatic nitrogen-boron derivatives, and metal complexes (complexes formed by metals such as Ir, Pt, Au, Eu, Ru, Re, Ag, and Cu with heterocyclic ligands, etc.).For example, including N1,N1,N6,N6-tetrakis(4-(1-methylyl)phenyl)pyrene-1,6-diamine, 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-7-(3,5-di-tert-butylphenyl)-5,9-dihydro-5,9-diaza-13b-boronanaphene[3,2,1-de]anthracene (t-DABNA-dtB), platinum octaethylporphyrin (PtOEP), Ir(ppy)3, Ir(ppy)2(acac), Ir(mppy)3, Ir(PPy)2(m-bppy), BtpIr(acac), Ir(btp)2(acac), Ir(2-phq)3, Hex-Ir(phq)3, Ir(fbi)2(acac), fac- Tris(2-(3-p-xylyl)phenyl)pyridineiridium(III), Eu(dbm)3(Phen), Ir(piq)3, Ir(piq)2(acac), Ir(Fliq)2(acac), Ir(Flq)2(acac), Ru(dtb-bpy)3·2(PF6), Ir(BT)2(aca c), Ir(DMP)3, Ir(Mphq)3IR(phq)2tpy, fac-Ir(ppy)2Pc, Ir(dp)PQ2, Ir(Dpm)(Piq)2, H ex-Ir(piq)2(acac), Hex-Ir(piq)3, Ir(dmpq)3, Ir(dmpq)2(acac), FPQIrpic, FIrpic, etc.

[0115] The host compound for the luminescent layer can be a luminescent host, a hole-transporting host, an electron-transporting host, or a combination thereof. Non-limiting examples of the luminescent host compound include fused-ring derivatives such as anthracene or pyrene, bis(5-phenylene)-anthracene derivatives or stilbene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzo[a]fluorene derivatives, n-phenylcarbazole (9-phenylcarbazole) derivatives, carbazole nitrile derivatives, etc. Non-limiting examples of the hole-transporting host substance include carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, triarylamine derivatives, indole[a]carbazole derivatives, and benzo[a]oxazine[a]phenoxazine derivatives, etc. Non-limiting examples of the electron-transporting host substance include pyridine derivatives, triazine derivatives, phosphine oxide derivatives, benzo[a]furan[a]pyridine derivatives, and dibenzo[a]oxasiloline derivatives, etc. Examples include 9,10-bis(2-naphthyl)anthracene (ADN), tris(8-hydroxyquinoline)aluminum (Alq3), BAlq (8-hydroxyquinoline beryllium salt), DPVBi (4,4'-bis(2,2-bistyryl)-1,1'-biphenyl) series, spiro-DPVBi (spiro-4,4'-bis(2,2-bistyryl)-1,1'-biphenyl), LiPBO (2-(2-benzoxazolyl)phenol lithium salt), bis(bistyryl)benzene, aluminum-quinoline metal complexes, imidazole, thiazole and oxazole metal complexes, etc.

[0116] The electron injection layer or electron transport layer compound is not particularly limited, and any compound commonly used as an electron injection layer or electron transport layer compound may be used. Non-limiting examples of electron injection layer or electron transport layer compounds may include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, violet ketone derivatives, coumarin derivatives, naphthylimide derivatives, anthraquinone derivatives, dibenzoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, metal complexes of oxime derivatives, quinoline metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzo[a]azole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, and triazine derivatives. Pyrazine derivatives, benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives, naphthidine derivatives, aldehyde azide derivatives, carbazole derivatives, indole derivatives, phosphine oxide derivatives, bis(5-phenylene oxide) metal complexes, quinoline alcohol metal complexes, hydroxyazole metal complexes, azomethyl alkaloid metal complexes, tyrosine metal complexes, flavonol metal complexes, benzoquinoline metal complexes, metal salts, etc. These materials can be used alone or in combination with other materials. For example, they may include 2-(4-(9,10-bis(naphthyl-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, tris(8-hydroxyquinoline)aluminum (Alq3), LiF, Liq, Li2O, BaO, NaCl, CsF, etc.

[0117] The electron transport auxiliary layer compound located between the electron transport layer and the luminescent layer is not particularly limited, and any compound commonly used as an electron transport auxiliary layer compound can be used. For example, the electron transport auxiliary layer can contain pyrimidine derivatives, etc.

[0118] The organic light-emitting diode of one embodiment of the present invention can be either rear-emitting or front-emitting.

[0119] An organic light-emitting diode according to an embodiment of the present invention can be used in a display device.

[0120] The organic light-emitting diode of one embodiment of the present invention can be applied to transparent display devices, mobile display devices, flexible display devices, etc., but is not limited thereto.

[0121] An embodiment of the present invention may include an organic light-emitting diode (OLED) comprising a series structure, which includes multiple light-emitting stacks between an anode and a cathode.

[0122] The following examples illustrate the method for synthesizing the compounds. However, the method for synthesizing the compounds of the present invention is not limited to the methods described in the examples below, and the implementation of the present invention is not limited to the following embodiments and experimental examples.

[0123] Synthesis example

[0124] Representatively, examples of the synthesis of compound 4 are described. Compounds 5 to 12, 21, 23, 27, 28, 30, 32, 34, 38, 41, 44, 47 and compounds of chemical formula A of the present invention can be synthesized in a similar manner to the reaction of compound 4.

[0125] The solvents, catalysts, protecting groups, leaving groups, reaction temperatures, and reaction times in the following reaction formulas are representative examples, and equivalent solvents, catalysts, protecting groups, leaving groups, reaction temperatures, reaction times, and reactant stoichiometry can also be used.

[0126] 1. Synthesize compound 4

[0127] Reaction 1

[0128]

[0129] Under a nitrogen atmosphere, reactant 1 (22 mmol), reactant 2 (20 mmol), Pd2(dba)3 (0.8 mmol), Sphos (1.6 mmol), t-BuONa (50 mmol), and toluene (representing compound 4) were added to a reaction flask and stirred under reflux. The organic layer was extracted with toluene and water. The extracted solution was treated with MgSO4 to remove residual water, concentrated under reduced pressure, purified by column chromatography, and recrystallized to obtain the product of compound 4, represented by chemical formula A, as described in this invention.

[0130] The products synthesized according to the representative example of reaction formula 1, reactants 1 and 2 used to synthesize them are shown in Table 1 below. The compounds corresponding to the chemical formula A and similar compounds can be synthesized by the synthesis example of reaction formula 1.

[0131] Table 1

[0132]

[0133]

[0134]

[0135]

[0136] Experiment Example 1: Performance Evaluation of Organic Light Emitting Diodes (Blue Diode)

[0137] For the organic light-emitting diodes of Examples 1 to 20 and Comparative Examples 1 to 6 prepared as follows, a CS-2000 from Konica Minolta was used to apply an application of 10 mA / cm². 2 The driving voltage (V), efficiency (Cd / A), and Y color coordinate (CIE 1931 standard, CIEy) were measured using the current. The Blue Index (BI = Cd / A(B) / CIEy(B)) was calculated and recorded using the efficiency and color coordinate values. Furthermore, the driving voltage (V), efficiency (Cd / A), and Y color coordinate (CIEy) were measured using a McScience M6000 at 10 mA / cm². 2 The constant current drive was used to confirm the method of measuring the time it takes for the brightness to decrease from the initial brightness level to 95% to determine the lifetime (LT95). The measurement results are shown in Table 2 below.

[0138] Example 1: Fabrication of an organic light-emitting diode (blue light-emitting layer)

[0139] The substrate with ITO (100nm) layered on top of the first electrode (anode) of the organic light-emitting diode is divided into a second electrode (cathode) region, a first electrode (anode) region and an insulating layer by photolithography and patterned. Then, in order to improve the work function of the first electrode (ITO) and to clean it, the surface is treated by ultraviolet (UV)-ozone treatment and O2:N2 plasma.

[0140] Then, a 10 nm thick hole injection layer (HIL) was formed by depositing a mixture of NDP-9 (2-(7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyrene-2-ylidene)-malononitrile and N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine) in a 3:97 ratio on the anode. Next, a hole transport layer with a thickness of 100 nm is formed by vacuum deposition of N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (N4,N4,N4',N4'-Tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine) on the hole injection layer. Compound 4 with a thickness of 15 nm is formed on the hole transport layer (HTL) as a hole transport auxiliary layer.

[0141] Using 9,10-bis(2-naphthyl)anthracene (ADN) as the main component and 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-7-(3,5-di-tert-butylphenyl)-5,9-dihydro-5,9-diaza-13b-borona[3,2,1-de]anthracene (2,12-Di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-7-(3,5-di-tert-butylphenyl)-5,9-dihydro5,9-diaza-13b- A 25 nm thick blue emitting layer is deposited on top of the hole transport assist layer using boranaphtho[3,2,1-de]anthracene, t-DABNA-dtB) as a dopant, wherein the host-to-dopant mixing ratio (by weight) is 97:3. A 25 nm thick mixture of 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (2-(4-(9,10-Di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole) and Liq in a 1:1 weight ratio is deposited on top of the blue emitting layer as an electron transport layer (ETL). A 1 nm thick electron injection layer (Liq) is deposited on top of the electron transport layer (ETL), and a 16 nm thick mixture of magnesium and silver in a 1:4 weight ratio is deposited as a cathode. A 60 nm thick layer of N4,N4'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) is deposited on the cathode as a capping layer. An encapsulation layer or protecting layer is formed by bonding a seal cap containing a desiccant to the capping layer using a UV-curable adhesive. This protects the organic light-emitting diode (OLED) from atmospheric oxygen or moisture, thereby fabricating the OLED.

[0142] Examples 2 to 20

[0143] Except for replacing compound 4, which was used as the hole transport auxiliary layer material in Example 1, with the compounds shown in Table 2 below, organic light-emitting diodes of Examples 2 to 20 were prepared using the same method as in Example 1.

[0144] Comparative Examples 1 to 6

[0145] Organic light-emitting diodes of Comparative Examples 1 to 6 were prepared using the same method as in Example 1, except that compound 4, which was used as the hole transport auxiliary layer material in Example 1, was replaced with comparative compounds 1 to 6 as shown in Table 2 below.

[0146] Table 2

[0147]

[0148]

[0149]

[0150]

[0151]

[0152] Referring to Table 2, it was confirmed that when using comparative compounds 1 to 6, compared with the case of using the compound represented by chemical formula A of the present invention, the driving voltage was increased, the efficiency and lifetime were reduced, and the BI value was also reduced in the diode evaluation results.

[0153] Based on the chemical formula A of this invention, the structural difference between Comparative Compound 1 and Chemical Formula A is that Ar is a heteroaryl group instead of an aryl group. The structural difference between Comparative Compound 2 and Chemical Formula A is that its bonding relationship differs from the terphenyl structure in Chemical Formula A, where three phenyl groups are bonded in the para position. Furthermore, based on Chemical Formula A, the Ar structures of Comparative Compounds 2, 3, and 6 are structures directly connected to the aryl group without a linking group, while the Ar structures of Comparative Compounds 4 to 5 correspond to structures with excessively long linking groups connecting the aryl group. That is, it can be confirmed that the embodiment compounds with the Ar structure described in claim 1 of this invention have superior diode performance and improved BI values ​​compared to Comparative Compounds 1 to 6, which do not have this structure.

[0154] Experimental Example 2: Measurement of HOMO and LUMO - Simulation Results of Hole Transport Auxiliary Layer

[0155] The hole transport auxiliary layer serves to reduce hole accumulation at the emissive layer interface due to the HOMO energy level difference between the hole transport layer and the emissive layer. Therefore, it is preferable that the HOMO energy level difference with the emissive layer is smaller than the HOMO energy level difference with the hole transport layer. Furthermore, it should have an energy level higher than the LUMO energy level of the emissive layer to minimize electron leakage from the emissive layer to the hole transport layer.

[0156] To confirm whether the compound represented by chemical formula A of the present invention is suitable as a hole transport auxiliary layer material, the HOMO level (eV) and LUMO level (eV) of the compounds in Table 3 below were calculated using Gaussian software (B3LYP DFT 6-31G* by Gaussian 16) and are shown in Table 3 below. It was confirmed that the compound represented by chemical formula A of the present invention meets the HOMO range of -4.80 eV to -5.00 eV, and is therefore suitable as a hole transport auxiliary layer material. Comparative compounds 2 and 3 do not meet the HOMO range and are therefore unsuitable as hole transport auxiliary layer materials.

[0157] Table 3

[0158]

[0159]

[0160]

[0161]

[0162] Experiment Example 3: Triplet Energy (T1) Calculation - Quantum Computing

[0163] For the compounds listed in Table 4 below, which are compounds represented by chemical formula A as described in this invention, and comparative compounds 1 to 6, the triplet energy (T1, absolute value) was calculated by quantum computing experiments using Gaussian software (B3LYP DFT 6-31G* by Gaussian 16), and the results are shown in Table 4 below.

[0164] Table 4

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] Referring to Table 4, the organic compound represented by chemical formula A of the present invention, as a hole transport layer or hole transport auxiliary layer, has a triplet energy level (T1) in an appropriate range of 2.60~2.80 eV, thereby effectively suppressing the outward diffusion of triplet excitons generated from the light-emitting layer and improving luminous efficiency and diode lifetime characteristics.

[0171] On the other hand, when the triplet energy level is too high, it may lead to the deepening of the HOMO energy level, which may result in a decrease in hole transport characteristics or an increase in the driving voltage of the diode.

[0172] Conversely, when the triplet energy level is too low, it may be impossible to prevent the diffusion of triplet excitons generated from the light-emitting layer, leading to a decrease in diode efficiency.

[0173] Therefore, the organic compound represented by chemical formula A of the present invention can have triplet energy levels within a range that ensures a balance between the binding effect of triplet excitons and charge transport properties.

[0174] Experimental Example 4: Determination of Deposition Temperature (Te)

[0175] The deposition temperatures (Te) of the compounds represented by chemical formula A of the present invention and comparative compounds 1 to 6 were determined and are shown in Table 5 below. In this case, the deposition temperature refers to the temperature (°C) at which the compound sublimates under a pressure of 10 Pa and its weight decreases by 10%, and is determined using thermogravimetric analysis (TGA).

[0176] Table 5

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] Since the organic compounds used in organic light-emitting diodes are typically deposited to form layers, a suitable deposition temperature is required to be approximately 290–370°C. If the deposition temperature exceeds 370°C, the purity of the formed layer may decrease and it may become unstable.

[0183] Referring to Table 5, it can be confirmed that the organic compound represented by chemical formula A of the present invention has a suitable deposition temperature. However, based on chemical formula A, in comparative compound 4 and comparative compound 5, the molecular weight increases as the linking group connected to nitrogen in Ar becomes longer, and the deposition temperature is too high.

[0184] Although the embodiments of this specification have been described in more detail above, this specification is not necessarily limited to these embodiments. Various modifications and implementations can be made without departing from the technical concept of this specification.

[0185] Therefore, the embodiments disclosed in this specification are not intended to limit the technical ideas of this specification, but rather to illustrate them, and these embodiments do not limit the scope of the technical ideas of this specification. Thus, the above embodiments should be understood as illustrative in all respects, and not restrictive.

Claims

1. An organic compound represented by the following chemical formula A, characterized in that, Chemical formula A: ， In the chemical formula A, Ar is selected from one of the following structures: M2, M3, M4, M11, M12, M13, M14, M15, M16, M17, M18, M19, M20, M21, M22, M23, M24, M25, M26, M27, M28, M29, M30, and M31. Dn is the number of deuterium atoms replaced, where n, representing the number of deuterium atoms, is an integer greater than or equal to 0. R1 to R 17 They may be the same as or different from each other, and each independently consists of one selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl groups of 1 to 30, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups of 3 to 60 carbon atoms. n1 and n2 may be the same or different from each other, and each is an independent integer from 0 to 5. n3 is an integer from 0 to 3. n4 is an integer from 0 to 4. From R1 to R 17 When substituted, the substituents may be the same as or different from each other, and may be selected from deuterium, cyano, trifluoromethyl, nitro, halogen group, hydroxyl, trimethylsilyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, cycloalkenyl with 3 to 20 carbon atoms, alkynyl with 2 to 30 carbon atoms, cycloalkynyl with 3 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms, heteroaryl with 3 to 60 carbon atoms, heteroaryl with 4 to 60 carbon atoms, amino, etc. The substituents are one or more of the group consisting of alkylamino with 1 to 30 carbon atoms, arylalkylamino with 7 to 30 carbon atoms, aromaticamino with 6 to 30 carbon atoms, heteroaromaticamino with 3 to 60 carbon atoms, silyl, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, aryloxy with 6 to 30 carbon atoms, alkylthio with 1 to 30 carbon atoms, and arylthio with 6 to 30 carbon atoms, wherein if there are multiple substituents, the substituents may be the same or different from each other.

2. The organic compound according to claim 1, characterized in that, The R1 to R 17 They may be the same or different from each other, and each can be hydrogen or deuterium independently.

3. The organic compound according to claim 1, characterized in that, The compound represented by the chemical formula A is selected from the group consisting of the following compounds. 。 4. An organic light-emitting diode, characterized in that, include: First electrode; The second electrode is disposed opposite to the first electrode; and One or more organic layers are located between the first electrode and the second electrode. At least one of the organic layers contains an organic compound represented by chemical formula A according to claim 1.

5. The organic light-emitting diode according to claim 4, characterized in that, The organic layer containing the organic compound represented by the chemical formula A is a hole transport layer or a hole transport auxiliary layer.

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