Organic light emitting device

Abstract

The present invention provides an organic light emitting device comprising: an anode; a cathode; and an emissive layer disposed between the anode and the cathode, wherein the emissive layer comprises a plurality of host compounds.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0097618, filed with the Korean Intellectual Property Office on August 4, 2020, and Korean Patent Application No. 10-2021-0102171, filed with the Korean Intellectual Property Office on August 3, 2021, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This disclosure relates to organic light-emitting devices. Background Technology

[0004] Organic light emission generally refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit characteristics such as wide viewing angle, excellent contrast ratio, fast response time, and superior brightness, driving voltage, and response speed, and have therefore been the subject of much research.

[0005] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode, a cathode, and an organic material layer between the anode and cathode. The organic material layer often has a multilayer structure containing different materials to improve the efficiency and stability of the OLED. For example, the organic material layer can be formed from a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of an OLED, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic material layer, and electrons are injected from the cathode into the organic material layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons return to the ground state.

[0006] There is a continued need to develop new organic materials for use in organic light-emitting devices as described above.

[0007] [Existing Technical Documents]

[0008] [Patent Literature]

[0009] (Patent Document 1) Korean Unexamined Patent Publication No. 10-2000-0051826 Summary of the Invention

[0010] Technical issues

[0011] This disclosure relates to organic light-emitting devices with improved drive voltage, efficiency, and lifetime.

[0012] Technical solution

[0013] To achieve the above objectives, this disclosure provides the following organic light-emitting devices:

[0014] Organic light-emitting devices, including:

[0015] Anode, cathode, and the light-emitting layer between the anode and cathode,

[0016] The light-emitting layer comprises a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, and a compound represented by the following chemical formula 3.

[0017] [Chemical Formula 1]

[0018]

[0019] In chemical formula 1,

[0020] A is a benzene ring fused with two adjacent pentagonal rings.

[0021] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics,

[0022] R1 is hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl; and

[0023] a is an integer from 0 to 10.

[0024] [Chemical Formula 2]

[0025]

[0026] In chemical formula 2,

[0027] Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics,

[0028] R2 and R3 are each independently hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl, and

[0029] b and c are each an independent integer from 0 to 7.

[0030] [Chemical Formula 3]

[0031]

[0032] In chemical formula 3,

[0033] B represents C, which is either substituted or unsubstituted and fused with the adjacent pentagonal ring. 6-60 Aromatic rings; or substituted or unsubstituted C-rings containing any or more of N, O, and S fused with adjacent pentagonal rings. 2-60 Mixed Fragrances Ring

[0034] X1 to X3 are each independently N or CH, provided that at least one of X1 to X3 is N.

[0035] Ar5 and Ar6 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics,

[0036] Ar7 is C with or without substitution. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics,

[0037] L1 is a single bond; C may be substituted or unsubstituted. 6-60 Aromatic; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl;

[0038] R4 and R5 are each independently hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics,

[0039] d is an integer from 0 to 10, and

[0040] e is an integer from 0 to 3.

[0041] Beneficial effects

[0042] The aforementioned organic light-emitting devices exhibit excellent driving voltage, efficiency, and lifetime. Attached Figure Description

[0043] Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0044] Figure 2An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4.

[0045] Figure 3 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light-emitting layer 3, a hole blocking layer 10, an electron transport layer 7, an electron injection layer 8, and a cathode 4. Detailed Implementation

[0046] The embodiments of this disclosure will be described in more detail below to aid in understanding the invention.

[0047] As used in this article, symbols and This refers to a bond that is connected to another substituent.

[0048] As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from: deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; aryl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkylamino group; aralkylamino group; heteroarylamino group; arylamino group; arylphosphyl group; or heteroaryl group containing at least one of N, O, and S atoms, or unsubstituted or substituted with two or more substituents linked together from the substituents exemplified above. For example, "substituents linked together with two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can also be interpreted as a substituent linked together with two phenyl groups.

[0049] In this disclosure, the number of carbon atoms in the carbonyl group is not particularly limited, but is preferably from 1 to 40. Specifically, the carbonyl group can be a substituent having the following structural formula, but is not limited thereto.

[0050]

[0051] In this disclosure, the ester group may have a structure in which the oxygen atom of the ester group is substituted by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or by an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent having the following structural formulas, but is not limited thereto.

[0052]

[0053] In this disclosure, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25.

[0054] Specifically, the imide group can be a substituent having the following structural formula, but is not limited thereto.

[0055]

[0056] In this disclosure, silane specifically includes, but is not limited to, trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc.

[0057] In this disclosure, boron group specifically includes, but is not limited to, trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, and phenylboronyl.

[0058] Examples of halogen groups in this disclosure include fluorine, chlorine, bromine, or iodine.

[0059] In this disclosure, the alkyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably from 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbons. According to another embodiment, the alkyl group has 1 to 10 carbons. According to yet another embodiment, the alkyl group has 1 to 6 carbons. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc.

[0060] In this disclosure, the alkenyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbons. According to another embodiment, the alkenyl group has 2 to 10 carbons. According to yet another embodiment, the alkenyl group has 2 to 6 carbons. Specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc.

[0061] In this disclosure, the cycloalkyl group is not particularly limited, but it is preferably composed of 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc.

[0062] In this disclosure, the aryl group is not particularly limited, but it is preferably composed of 6 to 60 carbon atoms, and can be either a monocyclic aryl or a polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. As a monocyclic aryl group, the aryl group can be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. Polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes, but is not limited to, methyl, fluorene, etc.

[0063] In this disclosure, the fluorene group can be substituted, and two substituents can be linked together to form a spirostructure. When the fluorene group is substituted, a spirostructure can be formed. However, the structure is not limited to this.

[0064] In this disclosure, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heteroatoms, and its carbon number is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazolyl, thiazolyl, and others. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthrolinel, iso Azolyl, thiadiazolyl, phenthiazinyl, dibenzofuranyl, etc., but not limited to these.

[0065] In this disclosure, the aryl group in aralkyl, arylenyl, alkylaryl, and arylamine is the same as the aforementioned examples of aryl. In this disclosure, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the aforementioned examples of alkyl. In this disclosure, the heteroaryl group in heteroarylamine can be described using the aforementioned description of heterocyclic groups. In this disclosure, the alkenyl group in arylenyl is the same as the aforementioned examples of alkenyl. In this disclosure, the aforementioned description of aryl can be applied, except that the arylene group is a divalent group. In this disclosure, the aforementioned description of heteroaryl can be applied, except that the heteroarylene group is a divalent group. In this disclosure, the aforementioned description of aryl or cycloalkyl can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In this disclosure, the aforementioned description of heterocyclic groups can be applied, except that the heterocycle is not a monovalent group but is formed by combining two substituents.

[0066] The contents of this disclosure will be described in detail below for each configuration.

[0067] Anode and cathode

[0068] As used in this disclosure, anode and cathode refer to electrodes used in organic light-emitting devices.

[0069] As an anode material, materials with a large work function are generally preferred, allowing holes to be smoothly injected into the organic material layer. Specific examples of anode materials include metals, such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline; and so on, but are not limited thereto.

[0070] As cathode materials, materials with a small work function are generally preferred, allowing electrons to be easily injected into the organic material layer. Specific examples of cathode materials include: metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials, such as LiF / Al or LiO2 / Al; and so on, but are not limited to these.

[0071] Emissive layer

[0072] As used in this disclosure, a light-emitting layer refers to a layer that emits light in the visible light region by combining holes and electrons transported from the anode and cathode. Typically, a light-emitting layer comprises a host material and a dopant material. In this disclosure, compounds represented by the following chemical formula 1, compounds represented by the following chemical formula 2, and compounds represented by the following chemical formula 3 are used as the host material.

[0073] The indolocarbazole-based compound represented by Formula 1 and the biscarbazole-based compound represented by Formula 2 each have excellent hole transport capabilities and are therefore used as P-type hosts; and the compound represented by Formula 3, in which carbazole and triazine are bonded at the ortho position, is used as an N-type host.

[0074] Typically, when a P-type host and an N-type host are mixed and used as the host of the light-emitting layer, an excitocomplex is formed. Thus, when all three types of compounds are mixed and used as the host, the characteristics of the device can be improved compared to the case where only one of the P-type host and N-type host is used.

[0075] Preferably, chemical formula 1 can be represented by any of the following chemical formulas 1-1 to 1-5:

[0076] [Chemical Formula 1-1]

[0077]

[0078] [Chemical Formula 1-2]

[0079]

[0080] [Chemical Formulas 1-3]

[0081]

[0082] [Chemical Formulas 1-4]

[0083]

[0084] [Chemical Formulas 1-5]

[0085]

[0086] In chemical formulas 1-1 to 1-5,

[0087] Ar1, Ar2, R1 and a are as defined in chemical formula 1.

[0088] Preferably, Ar1 and Ar2 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0089] More preferably, Ar1 and Ar2 can each independently be phenyl, biphenyl, phenyl-biphenyl, terphenyl, dimethylfluorenyl, dimethylfluorenylphenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dibenzofuranyl, dibenzothiophenyl, phenyl substituted with 5 deuterium, biphenyl substituted with 5 deuterium, or terphenyl substituted with 5 deuterium.

[0090] Most preferably, Ar1 and Ar2 can each be independently selected from any of the following:

[0091]

[0092] Preferably, at least one of Ar1 and Ar2 can be substituted or unsubstituted C. 6-20 Aryl, and more preferably, at least one of Ar1 and Ar2 can be phenyl, biphenyl, terphenyl, phenyl substituted with 5 deuterium, or biphenyl substituted with 5 deuterium.

[0093] Preferably, R1 can be hydrogen; deuterium; or substituted or unsubstituted C. 1-10 Alkyl; substituted or unsubstituted C 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Heteroaryl; and more preferably, R1 can be hydrogen or deuterium.

[0094] Preferably, a is an integer of 0, 1, or 8.

[0095] Representative examples of compounds represented by chemical formula 1 are as follows:

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] The compound represented by chemical formula 1 can be prepared, for example, by the preparation method shown in reaction scheme 1 below, and other remaining compounds can be prepared in a similar manner.

[0113] [Reaction Scheme 1]

[0114]

[0115] In reaction scheme 1, A, Ar1, Ar2, R1 and a are defined as in chemical formula 1, X'1 and X'2 are each independently halogens, and more preferably, X'1 and X'2 are each independently chlorine or bromine.

[0116] Steps 1 and 2 of reaction scheme 1 are preferably amine substitution reactions carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction can be modified as is known in the art. The above preparation method can be further presented in the preparation examples described below.

[0117] Preferably, chemical formula 2 can be represented by the following chemical formula 2-1.

[0118] [Chemical Formula 2-1]

[0119]

[0120] In chemical formula 2-1,

[0121] Ar3, Ar4, R2, R3, b, and c are as defined in chemical formula 2.

[0122] Preferably, Ar3 and Ar4 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0123] More preferably, Ar3 and Ar4 can each be independently phenyl, biphenyl, phenyl-biphenyl, terphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiopheneyl, phenyl with 5 deuterium substitutions, or biphenyl with 1 to 5 deuterium substitutions.

[0124] Preferably, R2 and R3 can each be independently hydrogen; deuterium; substituted or unsubstituted C. 1-10 Alkyl; substituted or unsubstituted C 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0125] More specifically, R2 and R3 can each be hydrogen, deuterium, or phenyl, independently.

[0126] Preferably, b and c can each be 0, 1 or 5 independently.

[0127] Representative examples of compounds represented by chemical formula 2 are as follows:

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] The compound represented by chemical formula 2 can be prepared, for example, by the preparation method shown in reaction scheme 2 below, and other remaining compounds can be prepared in a similar manner.

[0135] [Reaction Scheme 2]

[0136]

[0137] In reaction scheme 2, Ar3, Ar4, R2, R3, b and c are as defined in chemical formula 2, X'3 is a halogen, and more preferably, X'3 is chlorine or bromine.

[0138] Reaction scheme 2 is a preferred amine substitution reaction carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction can be modified as is known in the art. The above preparation methods can be further illustrated in the preparation examples described below.

[0139] Simultaneously, by using a compound represented by Formula 3 as the N-type host, and with carbazole (possessing hole transport properties) and triazine (possessing electron transport properties) adjacent to each other in the ortho position, internal charge transfer can be readily achieved. Subsequently, the molecule exhibits high stability, which is beneficial for both hole and electron transport. Furthermore, various nitrogen-containing heterocycles are additionally substituted in Ar5 and Ar6 of Formula 3, allowing for diverse control over electron transport properties, which is advantageous for matching charge balance based on changes in the common layer.

[0140] Preferably, B can be a benzene ring, a naphthalene ring, a phenanthrene ring, a triphenylene ring, a phenylcarbazole ring, a dimethylfluorene ring, a dibenzofuran ring, or a dibenzothiophene ring.

[0141] More preferably, chemical formula 3 can be represented by any of the following chemical formulas 3-1 to 3-10:

[0142]

[0143] In chemical formulas 3-1 to 3-10,

[0144] X1 to X3, Ar5, Ar6, Ar7, L1, R4, R5, d and e are as defined in chemical formula 3.

[0145] Preferably, at least two of X1 to X3 can be N.

[0146] Preferably, Ar5 and Ar6 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0147] More preferably, Ar5 and Ar6 can each independently be phenyl, a phenyl group substituted with 5 deuterium groups, naphthyl, phenanthryl, triphenylene, dimethylfluorenyl, carbazole, a carbazole group substituted with 8 deuterium groups, dibenzofuranyl, dibenzothiopheneyl, or

[0148] Preferably, Ar7 can be substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0149] More preferably, Ar7 can be dibenzothiophene group, or selected from any of the following:

[0150]

[0151] Among the above groups,

[0152] Y1 to Y3 are each independently either N or CH, provided that at least one of Y1 to Y3 is N.

[0153] Ar'1 and Ar'2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl, and

[0154] R'1 to R'7 are each independently hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatic compounds.

[0155] Preferably, Ar'1 and Ar'2 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0156] More preferably, Ar'1 and Ar'2 may each be independently phenyl, biphenyl, naphthyl, phenanthrene, triphenylene, phenyl substituted with 5 deuterium groups, phenyl substituted with one cyano group, phenyl substituted with one trifluoromethyl group, benzothiophene, dibenzofuranyl, or dibenzothiophene.

[0157] Preferably, R'1 to R'7 can each be independently hydrogen; deuterium; substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0158] More preferably, R'1 to R'7 can each be hydrogen, deuterium or phenyl independently.

[0159] Preferably, L1 can be a single bond; substituted or unsubstituted C 6-20 Aromatic; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Hybrid aryl.

[0160] More preferably, L1 can be a single bond, phenylene, naphthyl, dibenzofurandiyl, or dibenzothiophenediyl.

[0161] Preferably, R4 and R5 can each be hydrogen; deuterium; substituted or unsubstituted C. 1-10 Alkyl; substituted or unsubstituted C 6-20 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-20 Mixed aromatic compounds.

[0162] More preferably, R4 and R5 can each be independently hydrogen, deuterium, phenyl, naphthyl, carbazolyl, benzothiophene, dibenzofuranyl, dibenzothiophene, a phenyl substituted with 4 deuteriums, or a phenyl substituted with 5 deuteriums.

[0163] Representative examples of compounds represented by chemical formula 3 are as follows:

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] The compound represented by chemical formula 3 can be prepared, for example, by the preparation method shown in reaction scheme 3 below, and other remaining compounds can be prepared in a similar manner.

[0172] [Reaction Scheme 3]

[0173]

[0174] In reaction scheme 3, Ar5 to Ar7, L1, R4, R5, X1 to X3, d and e are as defined in chemical formula 3, X'4 is a halogen, and more preferably, X'4 is fluorine or chlorine.

[0175] Reaction scheme 3 is a preferred amine substitution reaction carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction can be modified as is known in the art. The above preparation methods can be further illustrated in the preparation examples described below.

[0176] In the luminescent layer, the weight ratio between the compound represented by chemical formula 1 and the compound represented by chemical formula 2 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10.

[0177] In the luminescent layer, the weight ratio between the compound represented by chemical formula 1 and the compound represented by chemical formula 3 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10.

[0178] There are no particular restrictions on the dopant materials, as long as they are materials used in organic light-emitting devices. Examples include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of aromatic amine derivatives include fused aromatic ring derivatives with aryl amino groups, whether substituted or unsubstituted. Examples of fused aromatic ring derivatives include pyrene, anthracene, etc., with aryl amino groups. And diindromepyrene, etc. Styrenicoamine compounds are compounds in which at least one aryl vinyl group is substituted in a substituted or unsubstituted aryl amine, wherein one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples of styrenicoamine compounds include, but are not limited to, styrenicoamine, styrenicodiamine, styrenicotriamine, styrenicotetraamine, etc. Furthermore, examples of metal complexes include, but are not limited to, iridium complexes, platinum complexes, etc.

[0179] Hole injection layer

[0180] If necessary, the organic light-emitting device according to this disclosure may also include a hole injection layer between the anode and the hole transport layer.

[0181] The hole injection layer is a layer in which holes from the electrode are injected, and the hole injection material is preferably a compound that has the ability to transport holes, has the effect of injecting holes into the anode, and has excellent hole injection effect on the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and has excellent thin film formation ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the work function of the anode material and the HOMO of the surrounding organic material layer.

[0182] Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, conductive polymers based on polyaniline and polythiophene, etc.

[0183] Hole transport layer

[0184] Organic light-emitting devices according to this disclosure may include a hole transport layer between a light-emitting layer or an electron-blocking layer and a hole injection layer, as described later.

[0185] The hole transport layer is the layer that receives holes from the hole injection layer and transports them to the light-emitting layer. Suitable hole transport materials are those with high hole mobility, capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer.

[0186] Specific examples of hole transport materials may include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers containing both conjugated and non-conjugated portions.

[0187] Electron blocking layer

[0188] Organic light-emitting devices according to this disclosure may include an electron blocking layer between a hole injection layer and a light-emitting layer.

[0189] An electron blocking layer is a layer disposed between the hole transport layer and the light-emitting layer to prevent electrons injected from the cathode from transferring to the hole transport layer and recombinating in the light-emitting layer. The electron blocking layer can also be called an electron suppression layer. Preferably, the electron blocking layer is made of a material with a lower electron affinity than the electron transport layer.

[0190] Cavity barrier

[0191] Organic light-emitting devices according to this disclosure may include a hole-blocking layer between the light-emitting layer and the electron transport layer, as described later.

[0192] A hole blocking layer is a layer placed between the electron transport layer and the light-emitting layer to prevent holes injected in the anode from transferring to the electron transport layer and recombinating in the light-emitting layer. The hole blocking layer can also be called a hole suppression layer. Preferably, the hole blocking layer is made of a material with high ionization energy.

[0193] Electron transport layer

[0194] Organic light-emitting devices according to this disclosure may include an electron transport layer between the light-emitting layer and the cathode.

[0195] An electron transport layer is a layer that receives electrons from the cathode and an electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, while suppressing the transfer of holes from the light-emitting layer. The electron transport material is appropriately a material that can well receive electrons from the cathode and transfer them to the light-emitting layer, and has a large electron mobility.

[0196] Specific examples of electron transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic radical compounds; hydroxyflavonoid-metal complexes, etc. The electron transport layer can be used with any desired cathode material, as employed according to conventional techniques. In particular, suitable examples of cathode materials are typically materials with low work functions followed by an aluminum or silver layer. Specific examples include cesium, barium, calcium, ytterbium, and samarium, each followed by an aluminum or silver layer.

[0197] Electron injection layer

[0198] If necessary, the organic light-emitting device according to this disclosure may also include an electron injection layer between the electron transport layer and the cathode.

[0199] An electron injection layer is a layer that injects electrons from an electrode, and preferably a compound that has the ability to transport electrons, has the effect of injecting electrons from a cathode, and has an excellent effect of injecting electrons into a light-emitting layer or light-emitting material, prevents excitons generated by the light-emitting layer from moving to the hole injection layer, and is also excellent in terms of the ability to form a thin film.

[0200] Specific examples of materials that can be used as electron injection layers include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives; metal complexes; nitrogen-containing 5-membered ring derivatives; and so on, but not limited to these.

[0201] Examples of metal complex compounds include, but are not limited to, lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)chlorogallium, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium.

[0202] Organic light-emitting devices

[0203] Figures 1 to 3 The structure of an organic light-emitting device according to this disclosure is shown in the figure. Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. Figure 2An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4. Figure 3 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light-emitting layer 3, a hole blocking layer 10, an electron transport layer 7, an electron injection layer 8, and a cathode 4.

[0204] The organic light-emitting device according to this disclosure can be manufactured by sequentially stacking the above-described structures. In this case, the organic light-emitting device can be manufactured by depositing a metal, a conductive metal oxide or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode, forming the aforementioned layers on the anode, and then depositing a material that can be used as a cathode on the aforementioned layers.

[0205] In addition to this method, organic light-emitting devices can also be fabricated by depositing materials sequentially from cathode to anode on a substrate in the reverse order of the above configuration (WO 2003 / 012890). Furthermore, the light-emitting layer can be formed by subjecting the host and dopant to vacuum deposition and solution coating methods. In this document, solution coating methods refer to, but are not limited to, spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, etc.

[0206] On the other hand, the organic light-emitting device according to this disclosure can be a bottom-emitting device, a top-emitting device, or a dual-sided emitting device, and in particular, it can be a bottom-emitting light-emitting device that requires relatively high luminous efficiency.

[0207] Preferred embodiments are presented below to aid in understanding this disclosure. However, these embodiments are provided merely for a better understanding of this disclosure and are not intended to limit its scope.

[0208] [Synthesis example]

[0209] Synthesis Example 1: Synthesis of Compound 1-1

[0210]

[0211] Step 1) Synthesis of compound 1-1-a

[0212] 11,12-dihydroindolo[2,3-a]carbazole (30 g, 117 mmol) and bromobenzene (18.4 g, 117 mmol) were added to 600 mL of toluene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (33.8 g, 351.1 mmol) was added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (1.8 g, 3.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts, followed by distillation. This was then added to 389 mL (10 times the volume) of chloroform and dissolved, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to prepare a yellow solid compound 1-1-a (30 g, yield: 77%, MS: [M+H)). + =333.4).

[0213] Step 2) Synthesis of Compound 1-1

[0214] Compound 1-1-a (30 g, 90.2 mmol) and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 (23.2 g, 90.2 mmol) were added to 600 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (26 g, 270.7 mmol) was then added, and the mixture was stirred thoroughly. Bis(tri-tert-butylphosphine)palladium (1.4 g, 2.7 mmol) was then added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was then added to 511 mL (10 times the volume) of chloroform and dissolved. The mixture was washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to prepare a white solid compound 1-1 (39.3 g, yield: 77%, MS: [M+H)). + =566.7).

[0215] Synthesis Example 2: Synthesis of Compounds 1-2

[0216]

[0217] Compound 1-2 (MS[M+H)) was prepared in the same manner as compound 1-1. +=642.8), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 1,3-dihydroindolo[2,3-b]carbazole, 4-chloro-1,1'-biphenyl-2’,3',4’,5’,6’-d5 and 3-chloro-1,1':4',1”-terphenyl, respectively.

[0218] Synthesis Example 3: Synthesis of Compounds 1-3

[0219]

[0220] Compounds 1-3 (MS[M+H)) were prepared in the same manner as those for compound 1-1. + =637.3), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 5,8-dihydroindolo[2,3-c]carbazole, 4-chloro-1,1'-biphenyl and 4-chloro-1,1':3',1”-terphenyl, respectively.

[0221] Synthesis Example 4: Synthesis of Compounds 1-4

[0222]

[0223] Compounds 1-4 (MS[M+H)) were prepared in the same manner as those for compound 1-1. + =561.2), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 5,8-dihydroindolo[2,3-c]carbazole, and bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 4-bromo-1,1'-biphenyl.

[0224] Synthesis Example 5: Synthesis of Compounds 1-5

[0225]

[0226] Compounds 1-5 (MS[M+H)) were prepared in the same manner as those for compound 1-1. +=580.2), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 5,8-dihydroindolo[2,3-c]carbazole, 3-bromodibenzo[b,d]furan and 4-chloro-1,1'-biphenyl-2',3',4',5',6'-d5, respectively.

[0227] Synthesis Example 6: Synthesis of Compounds 1-6

[0228]

[0229] Compounds 1-6 (MS[M+H)) were prepared in the same manner as those for compound 1-1. + =561.2), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 5,11-dihydroindolo[3,2-b]carbazole, and bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 3-bromo-1,1'-biphenyl.

[0230] Synthesis Example 7: Synthesis of Compounds 1-7

[0231]

[0232] Compounds 1-7 (MS[M+H)) were prepared in the same manner as those for compound 1-1. + =561.2), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 5,12-dihydroindolo[3,2-a]carbazole, and bromobenzene and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 were replaced with 4-bromo-1,1'-biphenyl, respectively.

[0233] Synthesis Example 8: Synthesis of Compounds 1-8

[0234]

[0235] Compounds 1-8 (MS[M+H)) were prepared in the same manner as those for compound 1-1. + =408.1), the difference being that in Synthesis Example 1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 1,3-dihydroindolo[2,3-b]carbazole, and 4-chloro-1,1':3',1”-terphenyl-2”,3”,4”,5”,6”-d5 was replaced with bromobenzene.

[0236] Synthesis Example 9: Synthesis of Compound 2-1

[0237]

[0238] Step 1) Synthesis of compound 2-1-a

[0239] 3-Chloro-9H-carbazole (30 g, 148.8 mmol) and 4-bromo-1,1'-biphenyl (34.7 g, 148.8 mmol) were added to 600 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (42.9 g, 446.3 mmol) was added, and the mixture was stirred thoroughly. Bis(tri-tert-butylphosphine)palladium (BTP, 0.8 g, 1.5 mmol) was then added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was then added to 526 mL (10 times the volume) of chloroform and dissolved. The mixture was washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to prepare a white solid compound 2-1-a (45.3 g, yield: 86%, MS: [M+H)). + =354.8).

[0240] Step 2) Synthesis of compound 2-1-b

[0241] Compound 2-1-a (20 g, 56.5 mmol) and (9H-carbazole-3-yl)boronic acid (11.9 g, 56.5 mmol) were added to 400 ml of 1,4-dioxane under a nitrogen atmosphere. The mixture was stirred and refluxed in alkane. Then, tripotassium phosphate (36 g, 169.6 mmol) dissolved in 36 mL of water was added to the mixture, and the mixture was stirred thoroughly. Then, palladium dibenzylacetone (1 g, 1.7 mmol) and tricyclohexylphosphine (1 g, 3.4 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the resulting solid was filtered. The solid was added to 822 mL (30 times the volume) of chloroform and dissolved. The mixture was washed twice with water to separate the organic layer. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound 2-1-b (20.8 g, 76%, MS: [M+H)). + =485.6).

[0242] Step 3) Synthesis of Compound 2-1

[0243] Compound 2-1-b (30 g, 61.9 mmol) and 4-bromobenzene (9.7 g, 61.9 mmol) were added to 600 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (17.9 g, 185.7 mmol) was then added, and the mixture was stirred thoroughly. Bis(tri-tert-butylphosphine)palladium (BTP, 0.3 g, 0.6 mmol) was then added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was then added to 347 mL (10 times the volume) of chloroform and dissolved. The mixture was washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to prepare compound 2-1 (20.5 g, yield: 59%, MS: [M+H)). + =561.2).

[0244] Synthesis Example 10: Synthesis of Compound 2-2

[0245]

[0246] Compound 2-2 (MS[M+H)) was prepared in the same manner as compound 2-1. + =637.3), the difference being that in Synthesis Example 9, bromobenzene was replaced with 2-bromo-1,1'-biphenyl.

[0247] Synthetic Example 11: Synthesis of Compounds 2-3

[0248]

[0249] Compound 2-3 (MS[M+H)) was prepared in the same manner as compound 2-1. + =652.4), the difference being that in Synthesis Example 9, 3-chloro-9H-carbazole, 4-bromo-1,1'-biphenyl, (9H-carbazole-3-yl)boronic acid and 4-bromobenzene are replaced with 3-chloro-9H-carbazole-1,4,5,6,8-d5, 3-bromo-1,1'-biphenyl-2,4',6-d3, (9H-carbazole-3-yl-1,4,5,6,8-d5)boronic acid and 3-bromo-1,1'-biphenyl-2,4'-d2.

[0250] Synthesis Example 12: Synthesis of Compounds 2-4

[0251]

[0252] Compound 2-4 (MS[M+H)) was prepared in the same manner as compound 2-1. +=573.3), the difference being that in Synthesis Example 9, 4-bromo-1,1'-biphenyl was replaced with 3-bromodibenzo[b,d]furan.

[0253] Synthesis Example 13: Synthesis of Compounds 2-5

[0254]

[0255] Compound 2-5 (MS[M+H)) was prepared in the same manner as compound 2-1. + =637.3), the difference being that in Synthesis Example 9, (9H-carbazole-3-yl)boronic acid was replaced with (6-phenyl-9H-carbazole-3-yl)boronic acid.

[0256] Synthesis Example 14: Synthesis of Compound 3-1

[0257]

[0258] Step 1) Synthesis of compound 3-1-a

[0259] (5-Chloro-2-fluorophenyl)boronic acid (50 g, 286.8 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (76.8 g, 286.8 mmol) were added to 1000 mL of tetrahydrofuran under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (118.9 g, 860.3 mmol) was then dissolved in 119 mL of water and added to the mixture, which was stirred thoroughly. Tetraphenylphosphine palladium (9.9 g, 8.6 mmol) was then added. After reacting for 1 hour, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was then added to 2075 mL (20 times the volume) of chloroform and dissolved, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized using chloroform and ethyl acetate to prepare a white solid compound 3-1-a (89.2 g, yield: 86%, MS: [M+H)). + =362.8).

[0260] Step 2) Synthesis of compound 3-1-b

[0261] Compound 3-1-a (30 g, 82.9 mmol) and bis(pinacol)diboron (21.1 g, 82.9 mmol) were added to 600 ml of 1,4-dioxane under a nitrogen atmosphere. The mixture was stirred and refluxed in alkane. Potassium acetate (52.8 g, 248.8 mmol) was then added, and the mixture was stirred thoroughly. Dibenzylacetone palladium (1.4 g, 2.5 mmol) and tricyclohexylphosphine (1.4 g, 5 mmol) were then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was then added to 376 mL (10 times the volume) of chloroform and dissolved. The mixture was washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare a white solid compound 3-1-b (29.7 g, yield: 79%, MS: [M+H)). + =454.3).

[0262] 3) Synthesis of compound 3-1-c

[0263] Compound 3-1-b (50 g, 110.3 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (29.5 g, 110.3 mmol) were added to 1000 mL of tetrahydrofuran under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (45.7 g, 330.9 mmol) was then dissolved in 46 mL of water and added to the mixture, which was stirred thoroughly. Tetraphenylphosphine palladium (3.8 g, 3.3 mmol) was then added. After reacting for 1 hour, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was then added to 1232 mL (20 times the volume) of chloroform and dissolved, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare a white solid compound 3-1-c (46.2 g, yield: 75%, MS: [M+H)). + =559.6).

[0264] Step 4) Synthesis of compound 3-1

[0265] Compound 3-1-c (20 g, 35.8 mmol) and 9H-carbazole-1,3,4,5,6,8-d6 (6.2 g, 35.8 mmol) were added to 400 mL of dimethylformamide under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, cesium carbonate (35 g, 107.4 mmol) was added, and the mixture was heated and stirred. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the resulting solid was filtered. The solid was added to 765 mL (30 times the volume) of chloroform and dissolved. The mixture was washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to prepare a yellow solid compound 3-1 (16.3 g, 64%, MS: [M+H)). + =712.9).

[0266] Synthetic Example 15: Synthesis of Compound 3-2

[0267]

[0268] Compound 3-2 (MS[M+H)) was prepared in the same manner as compound 3-1. + =787.4), the difference being that in synthetic example 14, 9H-carbazole-1,3,4,5,6,8-d6 was replaced with 3-(phenyl-d5)-9H-carbazole.

[0269] Synthesis Example 16: Synthesis of Compound 3-3

[0270]

[0271] Compound 3-3 (MS[M+H)) was prepared in the same manner as compound 3-1. + =803.4), the difference being that in synthetic example 14, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole-1,3,4,5,6,8-d6 were replaced with 9-(4-chloro-6-phenyl-1,3,5-triazine-2-yl)-9H-carbazole-1,2,3,4,5,6,7,8-d8 and 9H-carbazole.

[0272] Synthesis Example 17: Synthesis of Compounds 3-4

[0273]

[0274] Compound 3-4 (MS[M+H)) was prepared in the same manner as compound 3-1. +=878.4), the difference being that in synthetic example 14, 9H-carbazole-1,3,4,5,6,8-d6 was replaced with 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole-1,3,5,6,7,8,10-d7.

[0275] Synthesis Example 18: Synthesis of Compounds 3-5

[0276]

[0277] Compound 3-5 (MS[M+H)) was prepared in the same manner as compound 3-1. + =796.3), the difference being that in Synthesis Example 14, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole-1,3,4,5,6,8-d6 were replaced with 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole.

[0278] Synthesis Example 19: Synthesis of Compounds 3-6

[0279]

[0280] Compound 3-6 (MS[M+H)) was prepared in the same manner as compound 3-1. + =787.4), the difference being that in Synthesis Example 14, (5-chloro-2-fluorophenyl)boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole-1,3,4,5,6,8-d6 were replaced with (2-chloro-5-fluoro-[1,1'-biphenyl]-4-yl)boronic acid, 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine and 9H-carbazole.

[0281] Synthesis Example 20: Synthesis of Compounds 3-7

[0282]

[0283] Compound 3-7 (MS[M+H)) was prepared in the same manner as compound 3-1. + =663.4), the difference being that in Synthesis Example 14, 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 4-bromodibenzo[b,d]thiophene.

[0284] Synthesis Example 21: Synthesis of Compounds 3-8

[0285]

[0286] Compound 3-8 (MS[M+H)) was prepared in the same manner as compound 3-1.+ =787.4), the difference being that in Synthesis Example 14, the 2-chloro-4,6-diphenyl-1,3,5-triazine in step 1), the 2-chloro-4,6-diphenyl-1,3,5-triazine in step 3), and 9H-carbazole-1,3,4,5,6,8-d6 are replaced with 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine, 2-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, and 9H-carbazole.

[0287] [Example]

[0288] Example 1: Fabrication of Organic Light-Emitting Devices

[0289] It is coated with a thickness of The glass substrate of the ITO (indium tin oxide) thin film was immersed in distilled water containing a cleaning agent dissolved therein and ultrasonically washed. In this case, the cleaning agent used was a commercially available product from Fischer Co., and the distilled water was distilled water filtered twice using a commercially available filter from Millipore Co. The ITO was washed for 30 minutes, followed by two more ultrasonic washes of 10 minutes each using distilled water. After washing with distilled water, the substrate was ultrasonically washed with isopropanol, acetone, and methanol solvents, dried, and then transported to a plasma cleaner. The substrate was then cleaned with oxygen plasma for 5 minutes and transferred to a vacuum evaporator.

[0290] On the ITO transparent electrode prepared therefrom, 95 wt% of the following compound HT-A and 5 wt% of the following compound PD were thermally vacuum deposited onto the electrode. The thickness is increased to form a hole injection layer, and then only the following compound HT-A is deposited to... The thickness is increased to form a hole transport layer. The following compound, HT-B, is thermally vacuum deposited onto the hole transport layer. The thickness is such that an electron blocking layer is formed.

[0291] Then, 92 wt% of a matrix comprising a previously prepared compound 1-1 as the first matrix, a previously prepared compound 2-1 as the second matrix, and a previously prepared compound 3-1 as the third matrix, and 8 wt% of the following compounds GD were vacuum deposited onto an electron blocking layer. The thickness is increased to form a light-emitting layer.

[0292] Then, the following compound ET-A was vacuum deposited to... The thickness is increased to form a hole-blocking layer. Then, the following compounds, ET-B and Liq, are thermally vacuum deposited at a 1:1 ratio onto... The thickness is increased to form an electron transport layer, and Yb is vacuum deposited onto the substrate. The thickness is such that an electron injection layer is formed.

[0293] Magnesium and silver were deposited on the electron-injected layer at a weight ratio of 1:4. The thickness is increased to form the cathode, thereby completing the fabrication of the organic light-emitting device.

[0294]

[0295] In the above process, the vacuum deposition rate of organic materials is maintained at / seconds / second, maintaining the deposition rate of magnesium and silver at / second, and maintain the vacuum level during deposition at 2*10 -7 Up to 5*10 -6 This allows for the fabrication of organic light-emitting devices.

[0296] Examples 2 to 21 and Comparative Examples 1 to 13

[0297] Organic light-emitting devices of Examples 2 to 21 and Comparative Examples 1 to 13 were manufactured in the same manner as in Example 1, except that the host materials were changed as shown in Table 1 below. Here, the ratio refers to the weight ratio of the first host, the second host, and the third host. Furthermore, compounds C1, C2, and C3 are shown in Table 1 as follows.

[0298]

[0299] [Experimental Example: Evaluation of Device Characteristics]

[0300] The organic light-emitting devices manufactured in Examples 1 to 21 and Comparative Examples 1 to 13 were heat-treated in an oven at 120°C for 30 minutes, then removed, and the voltage, efficiency, and lifetime (T95) were measured by applying a current. The results are shown in Table 1 below. At this time, by applying 10 mA / cm... 2 The current density is measured at voltage and efficiency, and lifetime (T95) refers to 20 mA / cm². 2 The time (in hours) required for the brightness to decrease to 95% of the initial brightness at a given current density.

[0301] [Table 1]

[0302]

[0303]

[0304]

[0305] As shown in Table 1, it was determined that, compared with Comparative Examples 1 to 13, Examples 1 to 21 significantly reduced the drive voltage of the device and significantly improved efficiency and lifetime.

[0306] Compared to Comparative Examples 1 to 4 and 7, in which only one of the P-type and N-type substrates is used, Examples 1 to 21, in which the P-type and N-type substrates are mixed and used as the substrate for the light-emitting layer, show a significant reduction in the driving voltage of the device and a significant improvement in efficiency and lifetime.

[0307] Furthermore, when the two types of P-type substrates of Formula 1 and 2 and the N-type substrate of Formula 3 are mixed and used, the device characteristics can be improved compared to the case where only one type of P-type substrate of Formula 1 and 2 is mixed with the N-type substrate of Formula 3. The P-type substrate of Formula 1 has a structure containing indole-carbazole and therefore exhibits low voltage characteristics, while the P-type substrate of Formula 2 exhibits high efficiency and long lifetime characteristics due to its structure containing biscarbazole. Therefore, it is determined that using these as mixtures is beneficial for uniformly improving the voltage, efficiency, and lifetime characteristics of the device.

[0308] In fact, in Examples 1 to 21 in which two types of P-type substrates of Chemical Formula 1 and 2 are mixed with an N-type substrate of Chemical Formula 3, the voltage, efficiency and lifetime characteristics of the device are improved as a whole compared with Comparative Examples 5, 6, 8, 9, 10, 12 and 13 in which only one type of P-type substrate of Chemical Formula 1 and 2 is mixed with an N-type substrate.

[0309] It can be seen that in Examples 1 to 21 (particularly Examples 1 to 4) in which the two types of P-type substrates of Chemical Formula 1 and 2 are mixed with the N-type substrate of Chemical Formula 3, the overall improvement in the voltage, efficiency and lifetime characteristics of the device is caused by the effect of the N-type substrate of Chemical Formula 3, compared with Comparative Example 11 in which a compound having a structure completely different from the structure of Chemical Formula 3 is used instead of the N-type substrate.

[0310] [Figure Labels]

[0311] 1: Substrate 2: Anode

[0312] 3: Light-emitting layer 4: Cathode

[0313] 5: Hole injection layer; 6: Hole transport layer

[0314] 7: Electron transport layer; 8: Electron injection layer

[0315] 9: Electron blocking layer; 10: Hole blocking layer

Claims

1. An organic light-emitting device, comprising: Anode, cathode, and light-emitting layer between the anode and the cathode, The light-emitting layer comprises a compound represented by chemical formula 1, a compound represented by chemical formula 2, and a compound represented by chemical formula 3. [Chemical Formula 1] In chemical formula 1, A is a benzene ring fused with two adjacent pentagonal rings. Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics, R1 is hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl; and a is an integer from 0 to 10. [Chemical Formula 2] In chemical formula 2, Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics, R2 and R3 are each independently hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl, and b and c are each an independent integer from 0 to 7. [Chemical Formula 3] In chemical formula 3, B represents C, which is either substituted or unsubstituted and fused with the adjacent pentagonal ring. 6-60 Aromatic rings; or substituted or unsubstituted C-rings containing any or more of N, O, and S fused with adjacent pentagonal rings. 2-60 Mixed Fragrances Ring X1 to X3 are each independently N or CH, provided that at least one of X1 to X3 is N. Ar5 and Ar6 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics, L1 is a single bond; C may be substituted or unsubstituted. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl; R4 and R5 are each independently hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatics, d is an integer from 0 to 10, and e is an integer from 0 to 3. Ar7 is dibenzothiophene group, or selected from any of the following: Among the above groups, Y1 to Y3 are each independently either N or CH, provided that at least one of Y1 to Y3 is N. Ar'1 and Ar'2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 heteroaryl, and R'1 to R'7 are each independently hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing any or more of N, O, and S. 2-60 Mixed aromatic compounds.

2. The organic light-emitting device according to claim 1, wherein... Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-5: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formulas 1-3] [Chemical Formulas 1-4] [Chemical Formulas 1-5] In chemical formulas 1-1 to 1-5, Ar1, Ar2, R1 and a are as defined in claim 1.

3. The organic light-emitting device according to claim 1, wherein... Ar1 and Ar2 are each independently phenyl, biphenyl, phenyl-biphenyl, terphenyl, dimethylfluorenyl, dimethylfluorenylphenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dibenzofuranyl, dibenzothiophenyl, phenyl substituted with 5 deuterium, biphenyl substituted with 5 deuterium, or terphenyl substituted with 5 deuterium.

4. The organic light-emitting device according to claim 1, wherein... at least one of Ar1and Ar2is substituted or unsubstituted C 6-20 aryl.

5. The organic light-emitting device according to claim 1, wherein... The compound represented by chemical formula 1 is selected from any of the following compounds: 。 6. The organic light-emitting device according to claim 1, wherein... Chemical formula 2 is represented by the following chemical formula 2-1: [Chemical Formula 2-1] In chemical formula 2-1, Ar3, Ar4, R2, R3, b, and c are as defined in claim 1.

7. The organic light-emitting device according to claim 1, wherein... Ar3 and Ar4 are each independently phenyl, biphenyl, phenyl-biphenyl, terphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiopheneyl, phenyl with 5 deuterium substitutions, or biphenyl with 1 to 5 deuterium substitutions.

8. The organic light-emitting device according to claim 1, wherein... R2 and R3 can be hydrogen, deuterium, or phenyl, respectively.

9. The organic light-emitting device according to claim 1, wherein... b and c are each independently 0, 1, or 5.

10. The organic light-emitting device according to claim 1, wherein... The compound represented by chemical formula 2 is selected from any of the following compounds: 。 11. The organic light-emitting device according to claim 1, wherein... B can be a benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, phenylcarbazole ring, dimethylfluorene ring, dibenzofuran ring, or dibenzothiophene ring.

12. The organic light-emitting device according to claim 1, wherein... The chemical formula 3 is represented by any one of the following chemical formulas 3-1 to 3-10: In chemical formulas 3-1 to 3-10, X1 to X3, Ar5, Ar6, Ar7, L1, R4, R5, d and e are as defined in claim 1.

13. The organic light-emitting device according to claim 1, wherein... Ar5 and Ar6 are each independently phenyl, phenyl with 5 deuterium substitutions, naphthyl, phenanthryl, triphenylene, dimethylfluorenyl, carbazole, carbazole with 8 deuterium substitutions, dibenzofuranyl, dibenzothiopheneyl, or .

14. The organic light-emitting device according to claim 1, wherein... Ar'1 and Ar'2 are each independently phenyl, biphenyl, naphthyl, phenanthrene, triphenylene, phenyl substituted with 5 deuterium groups, phenyl substituted with one cyano group, phenyl substituted with one trifluoromethyl group, benzothiophene, dibenzofuranyl, or dibenzothiophene.

15. The organic light-emitting device according to claim 1, wherein... R'1 to R'7 are each independently hydrogen, deuterium, or phenyl.

16. The organic light-emitting device according to claim 1, wherein... L1 can be a single bond, phenylene, naphthyl, dibenzofurandiyl, or dibenzothiophenediyl.

17. The organic light-emitting device according to claim 1, wherein... R4 and R5 are each independently hydrogen, deuterium, phenyl, naphthyl, carbazolyl, benzothiophene, dibenzofuranyl, dibenzothiophene, phenyl substituted with 4 deuterium groups, or phenyl substituted with 5 deuterium groups.

18. The organic light-emitting device according to claim 1, wherein... The compound represented by chemical formula 3 is selected from any of the following: 。

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