Organic light-emitting devices

Abstract

The present invention provides an organic light emitting device having improved driving voltage and / or lifetime by including two types of host compounds in a light emitting layer.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims the priority based on Korean Patent Application No. 10-2019-0097650 filed on August 9, 2019 and Korean Patent Application No. 10-2020-0097980 filed on August 5, 2020, and incorporates all the contents disclosed in the documents of the Korean patent applications as a part of this specification.

[0003] The present invention relates to organic light emitting devices. Background Art

[0004] Generally speaking, the organic light-emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting devices using the organic light-emitting phenomenon have wide viewing angles, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, so a lot of research is being carried out.

[0005] An organic light-emitting device generally has a structure including an anode and a cathode and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is usually formed by a multilayer structure composed of different substances, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. For such an organic light-emitting device structure, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition back to the ground state, light is emitted.

[0006] As for organic substances used for organic light-emitting devices as described above, development of new materials continues to be required.

[0007] Prior art literature

[0008] Patent Document (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the invention

[0009] Technical issues

[0010] The present invention relates to organic light emitting devices.

[0011] Solution to the problem

[0012] The present invention provides the following organic light-emitting device, comprising:

[0013] anode;

[0014] a cathode disposed opposite to the anode; and

[0015] A light-emitting layer is provided between the anode and the cathode,

[0016] The light-emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:

[0017] [Chemical formula 1]

[0018]

[0019] In the above chemical formula 1,

[0020] X is O or S,

[0021] X1 to X3 are each independently N or CH, but at least one of X1 to X3 is N,

[0022] Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl,

[0023] R1 to R3 are each independently hydrogen; deuterium; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60 Alkyl; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl; substituted or unsubstituted C 6-60 Aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl,

[0024] a+b is an integer from 0 to 6,

[0025] c is an integer from 0 to 8,

[0026] [Chemical formula 2]

[0027]

[0028] In the above chemical formula 2,

[0029] A is a benzene ring fused to two adjacent five-membered rings,

[0030] Ar3 and Ar4 are each independently substituted or unsubstituted C 6-60 Aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl,

[0031] R4 is hydrogen; deuterium; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60Alkyl; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl; substituted or unsubstituted C 6-60 Aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl,

[0032] d is an integer from 0 to 10,

[0033] When a, b, c and d are each 2 or more, the substituents in the brackets may be the same as or different from each other.

[0034] Effects of the Invention

[0035] The organic light-emitting device comprises two host compounds in the light-emitting layer, so that the efficiency, driving voltage and / or lifespan characteristics can be improved in the organic light-emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 An example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown.

[0037] Figure 2 An example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport and injection layer 8, and a cathode 4 is shown. DETAILED DESCRIPTION

[0038] In the following, the present invention will be described in more detail to help understanding the present invention.

[0039] In this manual, or represents a bond to other substituents, D represents deuterium, and Ph represents phenyl.

[0040] In the present specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group ( alkyl thioxy); arylthio aryl thioxy); alkylsulfonyl ( alkyl sulfoxy); arylsulfonyl ( The present invention may be substituted or unsubstituted with one or more substituents in a heterocyclic group containing one or more N, O and S atoms, or may be substituted or unsubstituted with a substituent formed by connecting two or more substituents among the substituents exemplified above. For example, "a substituent formed by connecting two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may also be interpreted as a substituent formed by connecting two phenyl groups.

[0041] In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably the number of carbon atoms is 1 to 40. Specifically, the group may have the following structure, but is not limited thereto.

[0042]

[0043] In the present specification, in the ester group, the oxygen of the ester group may be substituted by a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the group may be a group of the following structural formula, but is not limited thereto.

[0044]

[0045] In the present specification, the number of carbon atoms in the imide group is not particularly limited, but the number of carbon atoms is preferably 1 to 25. Specifically, the group may have the following structure, but is not limited thereto.

[0046]

[0047] In the present specification, specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0048] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but are not limited thereto.

[0049] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0050] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 6. Specific examples of the alkyl group include 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, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl, but are not limited thereto.

[0051] In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. As specific examples, there are 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-(naphthalene-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc., but are not limited thereto.

[0052] In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 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 another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are 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., but are not limited thereto.

[0053] In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. Regarding the aryl group, as a monocyclic aryl group, it may be phenyl, biphenyl, triphenyl, etc., but it is not limited thereto. As the polycyclic aryl group, it may be naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, yl, fluorenyl, etc., but are not limited to these.

[0054] In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. etc. However, the present invention is not limited thereto.

[0055] In the present specification, the heteroaryl group is a heterocyclic group containing one or more heteroatoms selected from O, N, Si and S as heteroatoms, and the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 2 to 60. Examples of the heteroaryl group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, isothiophene Examples of the present invention include, but are not limited to, oxazolyl, thiadiazolyl, phenothiazinyl, and dibenzofuranyl.

[0056] In this specification, the aryl group in aralkyl, aralkenyl, alkylaryl, arylamine, and arylsilyl is the same as the examples of the above-mentioned aryl group. In this specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the examples of the above-mentioned alkyl group. In this specification, the heteroaryl group in heteroarylamine can be applied to the above-mentioned description of heteroaryl. In this specification, the alkenyl group in aralkenyl is the same as the examples of the above-mentioned alkenyl. In this specification, the arylene group is a divalent group, and the above-mentioned description of aryl can be applied. In this specification, the heteroarylene group is a divalent group, and the above-mentioned description of heteroaryl can be applied. In this specification, the hydrocarbon ring is not a monovalent group, but two substituents are combined, and the above-mentioned description of aryl or cycloalkyl can be applied. In this specification, the heterocycle is not a monovalent group, but two substituents are combined, and the above-mentioned description of heteroaryl can be applied.

[0057] A light emitting device is provided, comprising: an anode, a cathode disposed opposite to the anode, and a light emitting layer disposed between the anode and the cathode, wherein the light emitting layer contains a first compound represented by the chemical formula 1 and a second compound represented by the chemical formula 2.

[0058] The organic light-emitting device according to the present invention comprises two compounds having specific structures as host materials in the light-emitting layer, so that the efficiency, driving voltage and / or life characteristics of the organic light-emitting device can be improved.

[0059] Hereinafter, the present invention will be described in detail according to each structure.

[0060] Anode and cathode

[0061] As the above-mentioned anode material, in order to enable holes to be smoothly injected into the organic layer, a material with a large work function is preferably used. Specific examples of the above-mentioned anode material include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

[0062] In order to facilitate the injection of electrons into the organic layer, the cathode material is preferably a material with a small work function. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al, etc., but are not limited thereto.

[0063] Hole injection layer

[0064] The organic light emitting device according to the present invention may include a hole injection layer between the anode and a hole transport layer described later, as required.

[0065] The hole injection layer is located on the anode, is a layer for injecting holes from the anode, and contains a hole injection substance. As such a hole injection substance, it is preferably a compound that has the ability to transport holes, has the effect of injecting holes from the anode, has an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and has excellent thin film forming ability. In particular, it is preferred that the HOMO (highest occupied molecular orbital) of the hole injection substance is between the work function of the anode substance and the HOMO of the surrounding organic layer.

[0066] Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine organic matter, hexanitrile hexaazatriphenylene organic matter, quinacridone organic matter, perylene organic matter, anthraquinone, polyaniline and polythiophene conductive polymers, but are not limited to these.

[0067] Hole transport layer

[0068] The organic light-emitting device according to the present invention may include a hole transport layer between the anode and the light-emitting layer. The hole transport layer is a layer that receives holes from the anode or the hole injection layer formed on the anode and transports the holes to the light-emitting layer, and contains a hole transport substance. The hole transport substance is a substance that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer, and a substance with a large hole mobility is suitable. As specific examples, there are aromatic amine-based organic substances, conductive polymers, and block copolymers having both conjugated and non-conjugated parts, but are not limited to these.

[0069] Electron blocking layer

[0070] The organic light-emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light-emitting layer as required. The electron blocking layer is formed on the hole transport layer, preferably in contact with the light-emitting layer, and improves the hole-electron bonding rate by adjusting the hole mobility and preventing the excessive migration of electrons, thereby improving the efficiency of the organic light-emitting device. The electron blocking layer includes an electron blocking substance. As an example of such an electron blocking substance, an arylamine-based organic substance can be used, but it is not limited to this.

[0071] Luminescent layer

[0072] The organic light-emitting device according to the present invention includes a light-emitting layer between an anode and a cathode, and the light-emitting layer includes the first compound and the second compound as a host substance. Specifically, the first compound functions as an N-type host substance having a superior electron transport capability to a hole transport capability, and the second compound functions as a P-type host substance having a superior hole transport capability to an electron transport capability, thereby appropriately maintaining the ratio of holes to electrons in the light-emitting layer. Therefore, excitons emit light uniformly throughout the light-emitting layer, so that the luminous efficiency and life characteristics of the organic light-emitting device can be improved simultaneously.

[0073] Next, the first compound and the second compound will be described in sequence.

[0074] (First Compound)

[0075] The first compound is represented by the chemical formula 1. Specifically, the first compound is a compound in which a carbazole group and an N-containing six-membered heterocyclic group are simultaneously substituted in a dibenzofuran / dibenzothiophene core. Compared with a compound in which such substituents are not present at all, such a compound has a good intramolecular charge transfer, thereby having high molecular stability and effectively transporting holes and electrons. In addition, such an effect can be further maximized in the case where the second compound is used as the main body of the light-emitting layer as described later.

[0076] Furthermore, the first compound may contain at least one deuterium.

[0077] More specifically, in the above Chemical Formula 1, at least one of Ar1 and Ar2 is a C 6-60 Aryl; or C substituted with deuterium containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl, or

[0078] At least one of R1 to R3 is deuterium; C substituted by deuterium 6-60 Aryl; or C substituted with deuterium containing one or more heteroatoms selected from N, O and S 2-60 In the heteroaryl group, a+b+c may be 1 or more, or an integer from 1 to 14.

[0079] Alternatively, at least one of Ar1 and Ar2 is C substituted with deuterium. 6-60 Aryl; or C substituted with deuterium containing one or more heteroatoms selected from N, O and S 2-60 heteroaryl, and at least one of R1 to R3 is deuterium; C substituted by deuterium 6-60 Aryl; or C substituted with deuterium containing one or more heteroatoms selected from N, O and S 2-60 In the heteroaryl group, a+b+c may be 1 or more.

[0080] At this time, the first compound can be represented by the following chemical formula 1':

[0081] [Chemical Formula 1']

[0082]

[0083] In the above chemical formula 1',

[0084] R 21 To R 24 One of the The rest refer to the definition of R2 independently. 11 To R 14 One of the The rest are independently defined as R1, or

[0085] R 21 To R 24 Each independently refers to the definition of R2, R 14 for R 11 To R 13 One of the The rest are independently referred to the definition of R1.

[0086] In addition, when the first compound is represented by the chemical formula 1′, it may be more advantageous in terms of charge transfer within the molecule and molecular stability compared to a compound in which the carbazole group and the N-containing six-membered heterocyclic group are substituted at different positions.

[0087] More specifically, the first compound may be represented by any one of the following chemical formulas 1A' to 1E':

[0088] [Chemical Formula 1A']

[0089]

[0090] [Chemical Formula 1B']

[0091]

[0092] [Chemical formula 1C']

[0093]

[0094] [Chemical formula 1D']

[0095]

[0096] [Chemical Formula 1E']

[0097]

[0098] In the above chemical formulas 1A' to 1E',

[0099] X, X1 to X3, Ar1, Ar2, R1 to R3, a+b and c are the same as defined in the above Chemical Formula 1.

[0100] At this time, in the above chemical formulas 1A' to 1D', a and b are each an integer from 0 to 3,

[0101] In the above Chemical Formula 1E′, a is an integer of 0-2, and b is an integer of 0-4.

[0102] More specifically, the compound represented by the above Chemical Formula 1C' can be represented by the following Chemical Formula 1A (position 6 of the core), Chemical Formula 1B (position 7 of the core), Chemical Formula 1C (position 8 of the core), or Chemical Formula 1D (position 9 of the core) according to the substitution position of the N-containing six-membered heterocyclic group:

[0103] [Chemical Formula 1A]

[0104]

[0105] [Chemical formula 1B]

[0106]

[0107] [Chemical formula 1C]

[0108]

[0109] [Chemical formula 1D]

[0110]

[0111] In the above chemical formulas 1A to 1D,

[0112] a and b are each an integer from 0 to 3,

[0113] The remaining substituents are the same as those defined in the above Chemical Formula 1.

[0114] Preferably, X is O.

[0115] Preferably, X1 to X3 are all N, or

[0116] X1 and X2 are N, X3 is CH, or

[0117] X1 and X3 are N, X2 is CH, or

[0118] X1 is N, X2 and X3 are CH, or

[0119] X2 may be N, and X1 and X3 may be CH.

[0120] Preferably, Ar1 and Ar2 are each independently C 6-20 Aryl; or C containing 1 or 2 heteroatoms selected from N, O and S 2-20 Heteroaryl,

[0121] Here, the above Ar1 and Ar2 are unsubstituted or may be selected from deuterium, C 1-10 Alkyl and C 6-20 The aryl group is substituted by one or more substituents.

[0122] More preferably, Ar1 and Ar2 are each independently phenyl, biphenyl, naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, dibenzothiopheneyl, benzo Azolyl or benzothiazolyl,

[0123] Here, the above Ar1 and Ar2 are unsubstituted or may be selected from deuterium, C 1-10 Alkyl and C 6-20 The aryl group is substituted by one or more substituents.

[0124] For example, Ar1 and Ar2 can be any one selected from the following groups, but are not limited thereto:

[0125]

[0126]

[0127] In the above groups,

[0128] m is an integer of 0-7.

[0129] In addition, at least one of Ar1 and Ar2 may be

[0130] In addition, Ar1 and Ar2 may be the same as each other. Alternatively, Ar1 and Ar2 may be different.

[0131] Preferably, R1 to R3 may each independently be deuterium; unsubstituted or deuterium-substituted C 6-20 Aryl; or unsubstituted or deuterated C containing one heteroatom selected from N, O and S 2-20 Heteroaryl.

[0132] Preferably, R1 and R2 may each independently be hydrogen, deuterium, phenyl, phenyl substituted by 1 to 5 deuteriums, carbazolyl, dibenzofuranyl or dibenzothiophenyl.

[0133] In addition, R3 may be hydrogen, deuterium, unsubstituted or deuterium-substituted phenyl, unsubstituted or deuterium-substituted carbazolyl, unsubstituted or deuterium-substituted dibenzofuranyl, or unsubstituted or deuterium-substituted dibenzothienyl.

[0134] In addition, the substituents of the above chemical formula 1 It may be any one of the substituents represented by the following chemical formulae 3a to 3i:

[0135]

[0136] In the above chemical formulae 3a to 3i,

[0137] p is an integer from 0 to 7,

[0138] q is an integer from 0 to 8.

[0139] In addition, in the above chemical formula 1, a+b representing the total number of R1 and R2 may be 0, 1, 2, 3, 4, 5 or 6, and c representing the number of R3 may be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0140] Preferably, a+b is 0, 1, 2 or 6, and c can be 0, 1, 2 or 8. In this case, when a+b is 6, R1 and R2 can both be deuterium, and when c is 8, R3 can be deuterium.

[0141] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] On the other hand, as an example, the compound represented by the above Chemical Formula 1 can be produced by a production method as shown in the following Reaction Formula 1. The above production method can be further embodied in the production examples described below.

[0194] [Reaction 1]

[0195]

[0196] In the above reaction formula 3, X a and X' are each independently halogen, preferably, X a is fluorine, X' is bromine or chlorine, and the definitions of other substituents are the same as those described above.

[0197] Specifically, the compound represented by the above Chemical Formula 1 can be produced through Step 1-1 and Step 1-2.

[0198] The above step 1-1 is a step of preparing the intermediate compound A3 by Suzuki-coupling reaction of the starting materials A1 and A2. Such a Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used in the above Suzuki-coupling reaction can be appropriately changed.

[0199] In addition, the above step 1-2 is a step of preparing a compound represented by the above chemical formula 1 in which a carbazole group is introduced into the intermediate compound A3 by an amine substitution reaction with the intermediate compound A3 and the compound A4, and such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactive group used in the above amine substitution reaction can also be appropriately changed according to the technology known in the art.

[0200] Such a method for producing the compound represented by the above Chemical Formula 1 can be further embodied in the production examples described later.

[0201] (Second Compound)

[0202] The second compound is represented by the chemical formula 2. Specifically, the second compound is a compound in which two N atoms of the indolecarbazole core are substituted with Ar3 and Ar4 substituents, respectively. In particular, in the second compound, the hole characteristics of the indolecarbazole structure are excellent, so the Ar3 and Ar4 substituents are substituted with such an indolecarbazole structure as the center, so that the electron transport characteristics can be adjusted. Therefore, when the second compound is used together with the first compound in the light-emitting layer, the hole and electron transport characteristics can be variously adjusted, which is conducive to coordinating the charge balance in the light-emitting layer.

[0203] The second compound may be represented by any one of the following chemical formulas 2-1 to 2-5, depending on the position at which the benzene ring as the A ring is fused with two adjacent five-membered rings:

[0204] [Chemical formula 2-1]

[0205]

[0206] [Chemical formula 2-2]

[0207]

[0208] [Chemical formula 2-3]

[0209]

[0210] [Chemical formula 2-4]

[0211]

[0212] [Chemical formula 2-5]

[0213]

[0214] In the above chemical formulas 2-1 to 2-5,

[0215] R4 is each independently deuterium; substituted or unsubstituted C 6-20 Aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-20 Heteroaryl,

[0216] e is an integer from 0 to 4,

[0217] f is an integer from 0 to 2,

[0218] g is an integer from 0 to 4,

[0219] Ar3 and Ar4 are the same as defined in the above Chemical Formula 2.

[0220] Preferably, Ar3 and Ar4 may be hole transporting substituents. Specifically, Ar3 and Ar4 are each independently C 6-60 aryl, carbazolyl, dibenzofuranyl or dibenzothiophenyl,

[0221] Here, the above Ar3 and Ar4 may be unsubstituted or selected from deuterium, C 6-20 The aryl group, carbazolyl group, phenylcarbazolyl group, dibenzofuranyl group and dibenzothiophenyl group are substituted with one or more substituents selected from the group consisting of aryl group, carbazolyl group, phenylcarbazolyl group, dibenzofuranyl group and dibenzothiophenyl group.

[0222] More preferably, Ar3 and Ar4 are each independently phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl or dibenzothiophenyl.

[0223] Here, the above-mentioned Ar3 and Ar4 may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, phenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl and dibenzothiophenyl.

[0224] For example, Ar3 and Ar4 can each independently be any one selected from the following groups, but are not limited thereto:

[0225]

[0226] In addition, preferably, R4 can be deuterium; unsubstituted or deuterium-substituted C 6-20 Aryl; or unsubstituted or deuterated C containing one heteroatom selected from N, O and S 2-20 Heteroaryl.

[0227] Preferably, R4 can be deuterium, unsubstituted or deuterium-substituted C 6-20 aryl, unsubstituted or deuterium-substituted carbazolyl, unsubstituted or deuterium-substituted phenylcarbazolyl, unsubstituted or deuterium-substituted dibenzofuranyl, or unsubstituted or deuterium-substituted dibenzothiophenyl.

[0228] More preferably, R4 can be deuterium, unsubstituted or deuterium-substituted phenyl, unsubstituted or deuterium-substituted carbazolyl, unsubstituted or deuterium-substituted phenylcarbazolyl, unsubstituted or deuterium-substituted dibenzofuranyl, or unsubstituted or deuterium-substituted dibenzothiophenyl.

[0229] For example, R4 may be deuterium, or any one selected from the following groups, but is not limited thereto:

[0230]

[0231] Preferably, d may be 0, 1, 2 or 10. In this case, when d is 10, R4 may be deuterium.

[0232] Specifically, for example, in the above chemical formulas 2-1 to 2-5, e is 0, 1 or 4, f is 0, 1 or 2, and g can be 0, 1 or 4. In this case, when e is 4, f is 2, and g is 4, R4 can be deuterium.

[0233] In addition, in the above chemical formulas 2-1 to 2-5, e+f+g is the same as d, so e+f+g can be 0, 1, 2 or 10.

[0234] Representative examples of the compound represented by the above Chemical Formula 2 are shown below:

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] On the other hand, as an example, the compound represented by the above Chemical Formula 2 can be produced by a production method as shown in the following Reaction Formula 2. The above production method can be further embodied in the production examples described below.

[0252] [Reaction 2]

[0253]

[0254] In the above reaction formula 2, X" is a halogen, preferably bromine or chlorine, and the definitions of other substituents are the same as those described above.

[0255] Specifically, the compound represented by the above chemical formula 2 is produced by combining starting materials B1 and B2 through an amine substitution reaction. Such amine substitution reactions are each preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactive group used in the above amine substitution reaction can be appropriately changed, and the production method of the compound represented by chemical formula 2 can be more specifically described in the production examples described later.

[0256] In addition, the first compound and the second compound may be contained in the light-emitting layer at a weight ratio of 1:9 to 9:1. When the first compound is contained too little in the light-emitting layer, electron transfer in the light-emitting layer is not smooth, so that the balance of holes and electrons in the device as a whole is not coordinated, and thus there may be problems with the voltage, efficiency and life of the manufactured device. When the second compound is contained too little in the light-emitting layer compared with the first compound, there may be a problem of reduced life. For example, in the light-emitting layer, the weight ratio of the first compound to the second compound may be 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4 or 4:6 to 5:5.

[0257] On the other hand, the above-mentioned light-emitting layer may contain a dopant substance in addition to the above-mentioned two main substances. Such dopant substances include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are aromatic condensed ring derivatives having substituted or unsubstituted arylamino groups, such as pyrene, anthracene, The styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with one or more substituents selected from aryl, silyl, alkyl, cycloalkyl and arylamino. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetramine, etc., but not limited thereto. In addition, as a metal complex, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0258] At this time, the dopant material may be contained in the light-emitting layer in an amount of 1 to 25 wt % based on the total weight of the host material (the total weight of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2) and the dopant material.

[0259] Hole blocking layer

[0260] The organic light-emitting device according to the present invention may include a hole blocking layer between the light-emitting layer and the electron transport layer described later as needed. The hole blocking layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, and improves the efficiency of the organic light-emitting device by adjusting the electron mobility and preventing excessive migration of holes to increase the bonding rate between holes and electrons. The hole blocking layer contains a hole blocking substance. As examples of such a hole blocking substance, azine derivatives containing triazine, triazole derivatives, Compounds into which an electron-withdrawing group is introduced include, but are not limited to, oxadiazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, and the like.

[0261] Electron transport layer

[0262] The electron transport layer is formed between the light-emitting layer and the cathode, and plays the role of receiving electrons from the electron injection layer and transferring the electrons to the light-emitting layer. The electron transport layer contains an electron transport substance, which is a substance that can well receive electrons from the cathode and transfer them to the light-emitting layer, and a substance with a large electron mobility is suitable.

[0263] Specific examples of electron injection and transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, triazine derivatives, etc. Alternatively, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone and the like, and derivatives thereof, metal coordination compounds, and nitrogen-containing five-membered ring derivatives and the like can be used together, but are not limited thereto.

[0264] Electron transport and injection layers

[0265] The organic light emitting device according to the present invention may include an electron injection layer between the electron transport layer and the cathode as required. Alternatively, the organic light emitting device may include an electron transport and injection layer as required.

[0266] The electron transport and injection layer is a layer that injects electrons from the electrode and transfers the received electrons to the light-emitting layer while playing the role of an electron transport layer and an electron injection layer, and is formed on the light-emitting layer or the hole blocking layer. Such an electron injection and transport material is a material that receives electrons well from the cathode and transfers them to the light-emitting layer, and a material with high electron mobility is suitable. Specific examples of electron injection and transport materials include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, triazine derivatives, etc., but are not limited to these. Alternatively, it can also be combined with fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone and the like, and derivatives thereof, metal coordination compounds, or nitrogen-containing five-membered ring derivatives and the like can be used together, but are not limited thereto.

[0267] The electron transport and injection layer may also be formed as an independent layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light-emitting layer or the hole blocking layer, and as the electron transport material contained in the electron transport layer, the electron injection and transport material mentioned above can be used. In addition, the electron injection layer is formed on the electron transport layer, and as the electron injection material contained in the electron injection layer, LiF, NaCl, CsF, Li2O, BaO, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Oxadiazole, triazole, imidazole, benzimidazole, perylenetetracarboxylic acid, fluorenyl methane, anthrone, etc. and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, etc.

[0268] Examples of the metal coordination compounds include, but are not limited to, 8-hydroxyquinoline lithium, 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) gallium chloride, 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.

[0269] Organic light-emitting devices

[0270] The structure of the organic light emitting device according to the present invention is shown in Figure 1 . Figure 1The figure shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the above structure, the first compound and the second compound may be contained in the light-emitting layer.

[0271] Figure 2 The diagram shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport and injection layer 9, and a cathode 4. In the above structure, the first compound and the second compound may be contained in the light-emitting layer.

[0272] The organic light-emitting device according to the present invention can be manufactured by stacking the above-mentioned structures in sequence. In this case, it can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation (e-beam evaporation) to vapor-deposit a metal or a conductive metal oxide or an alloy thereof on a substrate to form an anode, and then forming the above-mentioned layers on the anode, and then vapor-depositing a substance that can be used as a cathode thereon to manufacture. In addition to this method, an organic light-emitting device can also be manufactured by vapor-depositing a cathode substance, an organic layer, and an anode substance on a substrate in sequence. In addition, the light-emitting layer can be formed not only by vacuum evaporation, but also by solution coating to form a main body and a dopant. Here, the so-called solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited to this.

[0273] In addition to these methods, an organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to this.

[0274] On the other hand, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type according to the materials used.

[0275] The production of the organic light-emitting device is specifically described in the following examples. However, the following examples are used to illustrate the present invention, and the scope of the present invention is not limited thereto.

[0276] [Synthesis example]

[0277] Synthesis Example 1: Synthesis of Compound 1-1

[0278]

[0279] Step 1) Synthesis of compound 1-1-a

[0280] Under a nitrogen atmosphere, 2-bromo-5-chlorophenol (20 g, 96.4 mmol) and (2,6-difluorophenyl)boric acid (15.2 g, 96.4 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, sodium carbonate (30.7 g, 289.2 mmol) was dissolved in 31 ml of water and added. After sufficient stirring, tetrakis(triphenyl-phosphine)palladium (3.3 g, 2.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. The obtained product was added to 464 mL of chloroform again and dissolved. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 1-1-a (16.5 g, 71%, MS: [M+H] + =241.6).

[0281] Step 2) Synthesis of compound 1-1-b

[0282] 1-1-a (15 g, 62.3 mmol) and potassium carbonate (25.8 g, 187 mmol) were added to 300 ml of dimethylformamide, stirred and refluxed. After reacting for 3 hours, the solid was cooled to room temperature and filtered. The solid was added to 413 mL of chloroform and dissolved, washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and 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 produce a white solid compound 1-1-b (10.7 g, 78%, MS: [M+H] + =221.6).

[0283] Step 3) Synthesis of compound 1-1-c

[0284] Under nitrogen atmosphere, 1-1-b (20 g, 90.6 mmol) and bis(pinacol)diboron (23 g, 90.6 mmol) were added to 400 ml of distilled water. alkane (Diox), stirring and reflux. Then, potassium triphosphate (57.7 g, 271.9 mmol) was added, and after sufficient stirring, dibenzylideneacetone palladium (1.6 g, 2.7 mmol) and tricyclohexylphosphine (1.5 g, 5.4 mmol) were added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. The obtained product was added to 283 mL of chloroform again and dissolved. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to produce a brown solid compound 1-1-c (22.6 g, 80%, MS: [M+H]+ =313.2).

[0285] Step 4) Synthesis of compound 1-1-d

[0286] Under nitrogen atmosphere, 1-1-c (20 g, 64.1 mmol) and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (22.9 g, 64.1 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, sodium carbonate (20.4 g, 192.2 mmol) was dissolved in 20 ml of water and added, and after sufficient stirring, tetrakis(triphenyl-phosphine)palladium (2.2 g, 1.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The obtained product was added to 647 mL of chloroform again and dissolved, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a yellow solid compound 1-1-d (22.3 g, 69%, MS: [M+H] + =505.6).

[0287] Step 5) Synthesis of compound 1-1

[0288] Under a nitrogen atmosphere, 1-1-d (15 g, 29.7 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (5.2 g, 29.7 mmol) were added to 300 ml of dimethylformamide, stirred and refluxed. Then, potassium carbonate (12.3 g, 89.2 mmol) was added, the temperature was raised and stirred. After reacting for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was added to 591 mL of chloroform and dissolved, washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and 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 produce a yellow solid compound 1-1 (11.4 g, 58%, MS: [M+H] + =663.8).

[0289] Synthesis Example 2: Synthesis of Compound 1-2

[0290]

[0291] In Synthesis Example 1, except that 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine was replaced with 9-(4-chloro-6-phenyl-1,3,5-triazine-2-yl)-9H-carbazole, a compound 1-2 (MS: [M+H]) was prepared by the same method as the method for preparing compound 1-1. + =662.3).

[0292] Synthesis Example 3: Synthesis of Compound 1-3

[0293]

[0294] In Synthesis Example 1, 2-bromo-5-chlorophenol, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-1-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 were replaced by 2-bromo-6-chlorophenol, 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine and 4-phenyl-9H-carbazole, respectively. Compound 1-3 (MS[M+H] + =646.2).

[0295] Synthesis Example 4: Synthesis of Compound 1-4

[0296]

[0297] In Synthesis Example 1, except that (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with (2,5-difluorophenyl)boric acid and 2-chloro-4,6-diphenyl-1,3,5-triazine, respectively, a compound 1-4 (MS[M+H] + =573.2).

[0298] Synthesis Example 5: Synthesis of Compound 1-5

[0299]

[0300] In Synthesis Example 1, except that 2-bromo-5-chlorophenol and (2,6-difluorophenyl)boric acid were replaced with 2-bromo-3-chlorophenol and (2,5-difluorophenyl)boric acid, respectively, Compound 1-5 (MS [M + H] + =663.2).

[0301] Synthesis Example 6: Synthesis of Compound 1-6

[0302]

[0303] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 were replaced with 2-bromo-3-chlorophenol, (2,4-difluorophenyl)boric acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole, respectively. Compound 1-6 (MS[M+H] + =646.2).

[0304] Synthesis Example 7: Synthesis of Compound 1-7

[0305]

[0306] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine were replaced with 2-bromo-3-chlorophenol, (2,4-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine, respectively. Compound 1-7 (MS[M+H]) was prepared by the same production method as that of compound 1-1. + =663.2).

[0307] Synthesis Example 8: Synthesis of Compound 1-8

[0308]

[0309] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with 2-bromo-3-chlorophenol, (2,4-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine, respectively. Compound 1-8 (MS[M+H]) was prepared by the same production method as that of compound 1-1. + =663.2).

[0310] Synthesis Example 9: Synthesis of Compound 1-9

[0311]

[0312] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 were replaced with 2-bromo-3-chloro-6-chlorophenol, (2-fluoro)boric acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole, respectively. Compound 1-9 (MS[M+H]) was prepared by the same production method as that of compound 1-1. + =646.2).

[0313] Synthesis Example 10: Synthesis of Compound 1-10

[0314]

[0315] In Synthesis Example 1, (2,6-difluorophenyl)boric acid, 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 were replaced with (2,4-difluorophenyl)boric acid, 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine and 3-phenyl-9H-carbazole, respectively. Compound 1-10 (MS[M+H] + =646.2).

[0316] Synthesis Example 11: Synthesis of Compound 1-11

[0317]

[0318] In Synthesis Example 1, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with (2,3-difluorophenyl)boric acid and 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine, respectively. Compound 1-11 (MS[M+H] + =648.2).

[0319] Synthesis Example 12: Synthesis of Compound 1-12

[0320]

[0321] In Synthesis Example 1, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with (2,3-difluorophenyl)boric acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine, respectively. Compound 1-12 (MS[M+H] + =648.2).

[0322] Synthesis Example 13: Synthesis of Compound 1-13

[0323]

[0324] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine, respectively. Compound 1-13 (MS[M+H]) was prepared by the same production method as that of compound 1-1. + =679.2).

[0325] Synthesis Example 14: Synthesis of Compound 1-14

[0326]

[0327] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 were replaced with 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boric acid, 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine and 4-phenyl-9H-carbazole, respectively. Compound 1-14 (MS [M + H] + =646.2).

[0328] Synthesis Example 15: Synthesis of Compound 1-15

[0329]

[0330] In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine were replaced with 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boric acid and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8, respectively. Compound 1-15 (MS[M+H] + =663.2).

[0331] Synthesis Example 16: Synthesis of Compound 2-1

[0332]

[0333] Step 1) Synthesis of compound 2-1-a

[0334] Under nitrogen atmosphere, 11,12-dihydroindole [2,3-a] carbazole (30 g, 117 mmol) and bromobenzene (18.4 g, 117 mmol) were added to 600 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (33.8 g, 351.1 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (1.8 g, 3.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. The obtained product was added to 389 mL of chloroform again and dissolved. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, 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 produce a yellow solid compound 2-1-a (30 g, 77%, MS: [M+H] + =333.4).

[0335] Step 2) Synthesis of compound 2-1

[0336] Under nitrogen atmosphere, 2-1-a (30 g, 90.2 mmol) and 4-chloro-1,1':3',1"-triphenyl-2",3",4",5",6"-d5 (23.2 g, 90.2 mmol) were added to 600 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (26 g, 270.7 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (1.4 g, 2.7 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. The obtained product was added to 511 mL of chloroform again and dissolved, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, 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 produce a white solid compound 2-1 (39.3 g, 77%, MS: [M+H] + =566.7).

[0337] Synthesis Example 17: Synthesis of Compound 2-2

[0338]

[0339] In Synthesis Example 16, except that 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were respectively replaced with 5,7-dihydroindole [2,3-b] carbazole, 4-chloro-1,1'-biphenyl-2',3',4',5',6'-d5 and 3-chloro-1,1':4',1"-terphenyl, a compound 2-2 (MS [M + H]) was prepared by the same preparation method as the preparation method of compound 2-1. + =642.8).

[0340] Synthesis Example 18: Synthesis of Compound 2-3

[0341]

[0342] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were replaced with 5,8-dihydroindole [2,3-c] carbazole, 4-chloro-1,1'-biphenyl and 4-chloro-1,1':3',1"-terphenyl, respectively. Compound 2-3 (MS [M + H] + =637.3).

[0343] Synthesis Example 19: Synthesis of Compound 2-4

[0344]

[0345] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were respectively replaced with 5,8-dihydroindole [2,3-c] carbazole-1,2,3,4,6,7,9,10,11,12-d10. Compound 2-4 (MS [M + H] + =561.2).

[0346] Synthesis Example 20: Synthesis of Compound 2-5

[0347]

[0348] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were replaced with 5,8-dihydroindole [2,3-c] carbazole, 3-bromodibenzo [b, d] furan and 4-chloro-1,1'-biphenyl-2',3',4',5',6'-d5, respectively. Compound 2-5 (MS [M + H] + =580.2).

[0349] Synthesis Example 21: Synthesis of Compound 2-6

[0350]

[0351] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were respectively replaced with 5,11-dihydroindole [3,2-b] carbazole and 3-bromo-1,1'-biphenyl. Compound 2-6 (MS [M + H] + =561.2).

[0352] Synthesis Example 22: Synthesis of Compound 2-7

[0353]

[0354] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were respectively replaced with 5,12-dihydroindole [3,2-a] carbazole and 4-bromo-1,1'-biphenyl. Compound 2-7 (MS [M + H] + =561.2).

[0355] Synthesis Example 23: Synthesis of Compound 2-8

[0356]

[0357] In Synthesis Example 16, 11,12-dihydroindole [2,3-a] carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2",3",4",5",6"-d5 were respectively replaced with 5,7-dihydroindole [2,3-b] carbazole and bromobenzene. Compound 2-8 (MS [M + H] + =561.2).

[0358] [Example]

[0359] Example 1

[0360] ITO (Indium Tin Oxide) The glass substrate coated with a film of a thickness of 10000 mm was placed in distilled water dissolved with a detergent and washed with ultrasonic waves. At this time, the detergent used a product of Fischer Co., and the distilled water used distilled water filtered twice by a filter manufactured by Millipore Co. After ITO was washed for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the distilled water washing was completed, ultrasonic washing was carried out with a solvent of isopropanol, acetone, and methanol and dried, and then transported to a plasma cleaning machine. In addition, after the above-mentioned substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

[0361] On the thus prepared ITO transparent electrode, the following HT-A compound and the following PD compound were added at a weight ratio of 95:5 and The hole injection layer was formed by thermal vacuum deposition of a thickness of 1000 nm, and then only the following HT-A compound was deposited at The hole transport layer was formed by evaporation of a thickness of 1000 nm. On the hole transport layer, the following HT-B compound was deposited at Thermal vacuum deposition is performed on a layer having a thickness of 1000 nm to form an electron blocking layer (electron suppression layer).

[0362] On the electron blocking layer, the above-produced compound 1-1 and compound 2-1 as the host compound and the following GD compound as the dopant compound were mixed at a weight ratio of 85:15 and The thickness of the compound 1-1 and the compound 2-1 was vacuum-deposited to form a light-emitting layer. At this time, the weight ratio of the compound 1-1 and the compound 2-1 was 1:1.

[0363] On the above-mentioned light-emitting layer, the following ET-A compound was On the hole blocking layer, the following ET-B compound and the following Liq compound were added at a weight ratio of 2:1 and Then, LiF and magnesium were deposited at a weight ratio of 1:1 and The electron transport and injection layer is formed by vacuum evaporation of a thickness of 1:1. On the electron transport and injection layer, magnesium and silver are deposited in a weight ratio of 1:4 and A cathode is formed by evaporation with a thickness of , thereby manufacturing an organic light-emitting device.

[0364]

[0365] In the above process, the evaporation rate of organic matter is maintained Lithium fluoride at the cathode maintains The evaporation rate of silver and magnesium is maintained The evaporation speed is 2×10 -7 ~5×10 -6 A support is provided to produce an organic light-emitting device.

[0366] Examples 2 to 15

[0367] An organic light-emitting device was manufactured by the same method as in Example 1, except that the compounds described in the following Table 1 were used instead of Compound 1.

[0368] At this time, the structures of the compounds used in Examples are summarized as follows.

[0369]

[0370]

[0371]

[0372] Comparative Examples 1 to 7

[0373] An organic light-emitting device was manufactured by the same method as in Example 1, except that the compounds described in the following Table 1 were used instead of Compound 1.

[0374] At this time, in the following Table 1, compounds H-2 and C1 are respectively shown below.

[0375]

[0376] Example

[0377] The voltage, efficiency, and life (T95) of the organic light-emitting devices manufactured in the above-mentioned examples and comparative examples were measured by applying current. The results are shown in Table 1 below. The voltage and efficiency were measured by applying 10 mA / cm 2 In addition, T95 in Table 1 below refers to the current density of 20 mA / cm 2 The time it takes for the initial brightness to drop to 95% is measured.

[0378] [Table 1]

[0379]

[0380]

[0381] As shown in Table 1 above, it can be seen that the organic light-emitting device of the embodiment using both the first compound and the second compound of the present invention as the main body shows excellent characteristics in terms of efficiency and life compared with the organic light-emitting devices of Comparative Examples 1 to 3 using only the above-mentioned first compound and the organic light-emitting devices of Comparative Examples 4 and 5 using neither the above-mentioned first compound nor the above-mentioned second compound.

[0382] In addition, it can be seen that although the organic light-emitting device of the above embodiment uses two types of hosts, it also shows high efficiency and excellent life compared with the organic light-emitting devices of Comparative Examples 6 and 7 that use other combinations of hosts instead of the combination of the above first compound and second compound.

[0383] This means that, considering that the luminous efficiency and lifespan characteristics of a general organic light-emitting device have a trade-off relationship with each other, the organic light-emitting device using the compound of the present invention shows significantly improved device characteristics compared to the comparative example device.

[0384] [Explanation of symbols]

[0385] 1: Substrate 2: Anode

[0386] 3: Light-emitting layer 4: Cathode

[0387] 5: Hole injection layer 6: Hole transport layer

[0388] 7: Electron blocking layer 8: Hole blocking layer

[0389] 9: Electron transport and injection layer.

Claims

1. An organic light-emitting device, wherein: include: anode; a cathode disposed opposite to the anode; as well as A light-emitting layer is provided between the anode and the cathode, The light-emitting layer includes a first compound represented by the following Chemical Formula 1 and a second compound represented by the following Chemical Formula 2: Chemical formula 1 In the chemical formula 1, X is O, X1 to X3 are all N, Ar1 is C substituted or unsubstituted with deuterium 6-20 Aryl, Ar2 is C substituted or unsubstituted with deuterium 6-20 Aryl; or C substituted or unsubstituted by deuterium containing 1 or 2 heteroatoms selected from N, O and S 2-20 Heteroaryl, R1 to R3 are each independently hydrogen; deuterium; or C substituted or unsubstituted by deuterium 6-20 Aryl, a+b is an integer from 0 to 6, c is an integer from 0 to 8, wherein at least one of Ar1 and Ar2 is C substituted with deuterium 6-20 aryl, or at least one of R1 to R3 is deuterium or C substituted by deuterium 6-20 Aryl, a+b+c is an integer from 1 to 14, Chemical formula 2 In the chemical formula 2, A is a benzene ring fused to two adjacent five-membered rings, Ar3 and Ar4 are each independently C substituted or unsubstituted with deuterium 6-20 aryl; or carbazolyl which may be substituted by deuterium or not; dibenzofuranyl which may be substituted by deuterium or not; or dibenzothiophenyl which may be substituted by deuterium or not, R4 is hydrogen or deuterium, and d is an integer from 0 to 10, When a, b, c and d are each 2 or more, the substituents in the brackets may be the same as or different from each other.

2. The organic light emitting device according to claim 1, wherein: The first compound is represented by any one of the following chemical formulas 1A' to 1E': Chemical formula 1A' Chemical formula 1B' Chemical formula 1C' Chemical formula 1D' Chemical formula 1E' In the chemical formulae 1A' to 1E', X, X1 to X3, Ar1, Ar2, R1 to R3, a+b and c are the same as defined in claim 1.

3. The organic light emitting device according to claim 1, wherein: Ar1 is phenyl, biphenyl, naphthyl or phenanthryl, Ar2 is phenyl, biphenyl, naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, dibenzothiopheneyl, benzo Azolyl or benzothiazolyl, wherein Ar1 and Ar2 are unsubstituted or substituted with deuterium.

4. The organic light emitting device according to claim 1, wherein: Ar1 is any one selected from the following groups: Ar2 is any one selected from the following groups: In the above groups, m is an integer of 0-7.

5. The organic light emitting device according to claim 1, wherein: R1 and R2 are each independently hydrogen, deuterium, phenyl, or phenyl substituted with 1 to 5 deuteriums.

6. The organic light emitting device according to claim 1, wherein: R3 is hydrogen, deuterium, or phenyl which is unsubstituted or substituted with deuterium.

7. The organic light emitting device according to claim 1, wherein: The substituent is any one of the substituents represented by the following chemical formulas 3a to 3f: In the chemical formulae 3a to 3f, p is an integer from 0 to 7.

8. The organic light emitting device according to claim 1, wherein: a+b is 0, 1, 2 or 6, c is 0, 1, 2 or 8.

9. The organic light emitting device according to claim 1, wherein: The first compound is any one selected from the following compounds:

10. The organic light emitting device according to claim 1, wherein: The second compound is represented by any one of the following chemical formulas 2-1 to 2-5: Chemical formula 2-1 Chemical formula 2-2 Chemical formula 2-3 Chemical formula 2-4 Chemical formula 2-5 In the chemical formulas 2-1 to 2-5, R4 is each independently deuterium, e is an integer from 0 to 4, f is an integer from 0 to 2, g is an integer of 0 to 4, and Ar3 and Ar4 are the same as defined in claim 1.

11. The organic light emitting device according to claim 1, wherein: Ar3 and Ar4 are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl or dibenzothiophenyl, wherein Ar3 and Ar4 are unsubstituted or substituted with deuterium.

12. The organic light emitting device according to claim 1, wherein: d is 0, 1, 2 or 10.

13. The organic light emitting device according to claim 1, wherein: The second compound is any one selected from the following compounds:

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