Compound and organic light-emitting device comprising same

Abstract

The present specification relates to compounds of Chemical Formulae 1 to 4 and an organic light emitting device comprising the same.

Description

Technical Field

[0001] This application claims the priority of Korean Patent Application No. 10-2023-0102846 filed with the Korean Patent Office on August 7, 2023 and Korean Patent Application No. 10-2024-0090217 filed with the Korean Patent Office on July 9, 2024, the entire contents of which are incorporated into this specification.

[0002] The present invention relates to a compound and an organic light-emitting device including the same. Background Art

[0003] Generally speaking, the phenomenon of organic light emitting refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic light emitting device using the phenomenon of organic light emitting generally has a structure including an anode and a cathode and an organic layer located between them. Here, in order to improve the efficiency and stability of the organic light emitting device, the organic layer is mostly formed by a multilayer structure composed of different substances, for example, it can be formed by a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. For the structure of such an organic light emitting device, 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 re-transition to the ground state, light is emitted.

[0004] There is a continuous demand for the development of new materials for organic light-emitting devices as described above. Summary of the invention

[0005] Technical issues

[0006] The present specification provides a compound and an organic light-emitting device including the same.

[0007] Solution to the problem

[0008] One embodiment of the present specification provides a compound of any one of the following Chemical Formulas 1 to 4.

[0009] [Chemical formula 1]

[0010]

[0011] [Chemical formula 2]

[0012]

[0013] [Chemical formula 3]

[0014]

[0015] [Chemical formula 4]

[0016]

[0017] In the above chemical formulas 1 to 4,

[0018] X1 is O or S,

[0019] Ar is an aromatic group having 18 or less carbon atoms which is substituted or unsubstituted with deuterium, R1 is independently hydrogen, deuterium or phenyl, R is the following chemical formula 5 or 6, a is an integer from 0 to 9,

[0020] [Chemical formula 5]

[0021]

[0022] [Chemical formula 6]

[0023]

[0024] In the above chemical formulas 5 and 6,

[0025] X2 is O or S,

[0026] B is a benzene ring,

[0027] R2 and R3 are each independently hydrogen, deuterium or phenyl,

[0028] b is an integer from 0 to 10,

[0029] c is an integer from 0 to 8,

[0030] represents a site connected to the chemical formulae 1 to 4,

[0031] However, at least one of R1 to R3 is deuterium.

[0032] In addition, another embodiment of the present specification provides an organic light-emitting device,

[0033] comprising: a first electrode; a second electrode; and one or more organic layers disposed between the first electrode and the second electrode,

[0034] At least one of the organic layers contains any one of the compounds of Chemical Formulas 1 to 4.

[0035] Effects of the Invention

[0036] The compound according to one embodiment of the present specification is used in an organic light-emitting device, which can reduce the driving voltage of the organic light-emitting device and improve the light efficiency. In addition, the thermal stability of the compound can be used to improve the life characteristics of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1An example of an organic light-emitting device according to an embodiment of the present specification is illustrated.

[0038] Figure 2 An example of an organic light-emitting device according to an embodiment of the present specification is illustrated.

[0039] [Explanation of symbols]

[0040] 1: Substrate

[0041] 2: First electrode

[0042] 3: Second electrode

[0043] 4: Luminous layer

[0044] 5: Hole injection layer

[0045] 6: Hole transport layer

[0046] 7: Hole regulation layer

[0047] 8: Electronic adjustment layer

[0048] 9: Electron transport layer

[0049] 10: Electron injection layer

[0050] 11: Overlay DETAILED DESCRIPTION

[0051] Next, this specification is described in more detail.

[0052] One embodiment of the present specification provides a compound of any one of the above Chemical Formulas 1 to 4.

[0053] In the present specification, the term "a combination thereof" included in the expression of Markush form means a mixture or combination of one or more components selected from the expression of Markush form, and means that one or more components selected from the above components are included.

[0054] In the present specification, examples of substituents are described below, but are not limited thereto.

[0055] In this manual, Indicates the connected part.

[0056] The term "substituted" mentioned above means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent. The substituted position is not limited as long as it is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted. When there are more than two substitutions, the two or more substituents may be the same or different from each other.

[0057] In the present specification, the term "substituted or unsubstituted" refers to a group selected from deuterium, a halogen group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, Arylthio The group may be substituted with one or more substituents selected from the group consisting of alkenyl, haloalkyl, haloalkoxy, arylalkyl, silyl, boron, amine, aryl, condensed ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and heterocyclic group, or may be substituted with a substituent formed by connecting two or more of the substituents listed above, or may not have any substituent.

[0058] In this specification, two or more substituents are linked to each other, which means that the hydrogen of any substituent is linked to another substituent. For example, two substituents can be linked to each other to form a phenyl group and a naphthyl group. In addition, the three substituents connected include not only (substituent 1)-(substituent 2)-(substituent 3) connected continuously, but also (substituent 2) and (substituent 3) connected to (substituent 1). For example, phenyl, naphthyl and isopropyl can be connected to form The above definition also applies to 4 or more substituents connected together.

[0059] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0060] 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 30. Specific examples 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.

[0061] In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 30 carbon atoms, and specifically includes 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, adamantyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]octyl, and norbornyl, but is not limited thereto.

[0062] In this specification, the alkoxy group may be straight chain, branched chain or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but preferably the number of carbon atoms is 1 to 30. Specifically, it may be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, a n-pentoxy group, a neopentoxy group, an isopentyl group, a n-hexyl group, a 3,3-dimethylbutoxy group, a 2-ethylbutoxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a benzyloxy group, a p-methylbenzyloxy group, etc., but is not limited thereto.

[0063] In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include 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.

[0064] In the present specification, the above-mentioned halogenated alkyl group refers to an alkyl group in the definition of the above-mentioned alkyl group substituted with at least one halogen group.

[0065] In the present specification, the above-mentioned halogenated alkoxy group means that at least one halogen group is substituted in place of the hydrogen of the alkoxy group in the definition of the above-mentioned alkoxy group.

[0066] In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0067] When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 6 to 30. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

[0068] When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 10 to 30. Specifically, the polycyclic aryl group may be naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, phenanthrenyl, perylene, yl, fluorenyl, etc., but are not limited to these.

[0069] In the present specification, the substituted aryl group may include a structure in which an aliphatic hydrocarbon ring is fused in the aryl group. According to one embodiment, the substituted aryl group may include a tetrahydronaphthyl group, and more specifically, may include (1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthyl), but is not limited thereto.

[0070] In the present specification, the fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

[0071] When the above fluorenyl group is substituted or forms a ring,

[0072]

[0073] etc., but not limited thereto.

[0074] In this specification, "adjacent" groups may refer to substituents substituted on atoms directly connected to the atom substituted by the substituent, substituents closest to the substituent in stereostructure, or other substituents substituted on the atom substituted by the substituent. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as "adjacent" groups to each other.

[0075] In the present specification, an arylalkyl group means that the above-mentioned alkyl group is substituted with an aryl group, and the aryl group and the alkyl group of the above-mentioned arylalkyl group can be the same as those exemplified above for the aryl group and the alkyl group.

[0076] In the present specification, an aryloxy group refers to a group in which the alkyl group of the alkoxy group in the definition of the above-mentioned alkoxy group is replaced by an aryl group. Examples of the aryloxy group include, but are not limited to, a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, a p-tert-butylphenoxy group, a 3-biphenyloxy group, a 4-biphenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methyl-1-naphthyloxy group, a 5-methyl-2-naphthyloxy group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-phenanthranyl group, a 3-phenanthranyl group, and a 9-phenanthranyl group.

[0077] In the present specification, the alkyl group of the alkylthio group is the same as the examples of the alkyl group described above. Specifically, examples of the alkylthio group include, but are not limited to, a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, and the like.

[0078] In the present specification, the aryl group in the arylthio group is the same as exemplified in the above-mentioned aryl group. Specific examples of the arylthio group include, but are not limited to, a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.

[0079] In the present specification, the heterocyclic group contains one or more non-carbon atoms, i.e., heteroatoms. Specifically, the heteroatoms may include one or more atoms selected from O, N, Se, S, etc., including aromatic heterocyclic groups or aliphatic heterocyclic groups. The aromatic heterocyclic group may be represented by a heteroaryl group. The number of carbon atoms in the heterocyclic group is not particularly limited, but preferably the number of carbon atoms is 2 to 30. The heterocyclic group may be a monocyclic or polycyclic group. Examples of heterocyclic groups include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthridine, phenanthroline, isothiophene Azolyl, thiadiazolyl, dibenzofuranyl, dibenzothioyl, phenanthroline Thiazole (phenoxathiine), phen The present invention also includes, but is not limited to, phenoxazine, phenothiazine, decahydrobenzocarbazolyl, hexahydrocarbazolyl, dihydrobenzoazasilyl, dihydroindenocarbazolyl, spirofluorenylxanthenyl, spirofluorenylthioxanthenyl, tetrahydronaphthothienyl, tetrahydronaphthofuranyl, tetrahydrobenzothienyl and tetrahydrobenzofuranyl.

[0080] In the present specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, etc. The alkyl group in the alkylsilyl group may be the same as the examples given above for the alkyl group, the aryl group in the arylsilyl group may be the same as the examples given above for the aryl group, the alkyl group and the aryl group in the alkylarylsilyl group may be the same as the examples given above for the alkyl group and the aryl group, and the heteroaryl group in the heteroarylsilyl group may be the same as the examples given above for the heterocyclic group.

[0081] In this specification, the boron group can be -BY 100 Y 101 , the above Y 100 and Y 101The same or different, each independently can be selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted monocyclic or polycyclic cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted linear or branched alkyl having 1 to 30 carbon atoms, substituted or unsubstituted monocyclic or polycyclic aryl having 6 to 30 carbon atoms, and substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms. The above-mentioned boryl group specifically includes dimethylboryl, diethylboryl, tert-butylmethylboryl, diphenylboryl, etc., but is not limited thereto.

[0082] In the present specification, the amino group can be selected from -NH2, alkylamino, N-alkylarylamino, arylamino, N-arylheteroarylamino, N-alkylheteroarylamino and heteroarylamino, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amino group include methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, anthracenylamino, 9-methyl-anthrylamino, diphenylamino, ditolylamino, N-phenyltolylamino, N-phenylbiphenylamino, N-phenylnaphthylamino, N-biphenylnaphthylamino, N-naphthylfluorenylamino, N-phenylphenanthrenylamino, N-biphenylphenanthrenylamino, N-phenylfluorenylamino, N-phenylterphenylamino, N-phenanthrenylfluorenylamino, N-biphenylfluorenylamino, etc., but are not limited thereto.

[0083] In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted on the N of the amine group. The alkyl group and the aryl group in the above-mentioned N-alkylarylamine group are the same as the examples of the alkyl group and the aryl group described above.

[0084] In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group or a heteroaryl group is substituted on the N of the amine group. The aryl group and the heteroaryl group in the N-arylheteroarylamine group are the same as the examples of the aryl group and the heterocyclic group described above.

[0085] In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted on the N of the amine group. The alkyl group and the heteroaryl group in the above-mentioned N-alkylheteroarylamine group are the same as the examples of the alkyl group and the heterocyclic group mentioned above.

[0086] In this specification, examples of alkylamino groups include substituted or unsubstituted monoalkylamino groups or substituted or unsubstituted dialkylamino groups. The alkyl group in the above-mentioned alkylamino groups may be a straight-chain or branched alkyl group. The alkylamino group containing two or more of the above-mentioned alkyl groups may contain a straight-chain alkyl group, a branched alkyl group, or may contain a straight-chain alkyl group and a branched alkyl group at the same time. For example, the alkyl group in the above-mentioned alkylamino group may be selected from the examples of the above-mentioned alkyl groups.

[0087] In this specification, examples of heteroarylamine groups include substituted or unsubstituted monoheteroarylamine groups, or substituted or unsubstituted diheteroarylamine groups. The heteroarylamine groups containing two or more of the above heteroaryl groups may contain monocyclic heteroaryl groups, polycyclic heteroaryl groups, or may contain both monocyclic heteroaryl groups and polycyclic heteroaryl groups. For example, the heteroaryl groups in the above heteroarylamine groups may be selected from the examples of the above heterocyclic groups.

[0088] In this specification, the alkyl group in N-alkylarylamine, alkylthio and N-alkylheteroarylamine is the same as the alkyl group exemplified above. Specifically, as the alkylthio, there are methylthio, ethylthio, tert-butylthio, hexylthio, octylthio, etc., but it is not limited thereto.

[0089] In the present specification, the aryl groups in the aryloxy group, arylthio group, N-arylalkylamine group and N-arylheteroarylamine group are the same as the examples of the aryl groups described above. Specifically, as the aryloxy group, there are phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-phenanthrenyl group, 3-phenanthrenyl group, 9-phenanthrenyl group, etc., and as the arylthio group, there are phenylthio group, 2-methylphenylthio group, 4-tert-butylphenylthio group, etc., but it is not limited thereto.

[0090] In the present specification, the hydrocarbon ring group can be an aromatic hydrocarbon ring group, an aliphatic hydrocarbon ring group, or a condensed ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and can be selected from the examples of the above-mentioned cycloalkyl group, aryl group, and combinations thereof. The above-mentioned hydrocarbon ring groups include phenyl, cyclohexyl, adamantyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]octyl, tetrahydronaphthyl, tetrahydroanthracenyl, 1,2,3,4-tetrahydro-1,4-methylenenaphthyl, 1,2,3,4-tetrahydro-1,4-ethylenenaphthyl, spirocyclopentanefluorenyl, spiroadamantanefluorenyl and spirocyclohexanefluorenyl, but are not limited thereto.

[0091] In the present specification, in the phrase “bonds with adjacent groups to form a ring”, “adjacent” has the same meaning as defined above, and the “ring” refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

[0092] In the present specification, the hydrocarbon ring may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensed ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and except for not being the above-mentioned monovalent group, may be selected from the above-mentioned cycloalkyl group, aryl group, and examples of combinations thereof, wherein the above-mentioned hydrocarbon rings include benzene, cyclohexane, adamantane, bicyclo[2.2.1]heptane, bicyclo[2.2.1]octane, tetrahydronaphthalene, tetrahydroanthracene, 1,2,3,4-tetrahydro-1,4-methylenenaphthalene and 1,2,3,4-tetrahydro-1,4-ethylenenaphthalene, spirocyclopentanefluorene, spiroadamantanefluorene and spirocyclohexanefluorene, but are not limited thereto.

[0093] In the present specification, the heterocycle contains one or more non-carbon atoms, i.e., heteroatoms. Specifically, the heteroatoms may contain one or more atoms selected from O, N, Se, S, etc. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic. The aromatic heterocycle may be selected from the examples of heteroaryl groups in the heterocyclic group except that it is not monovalent.

[0094] In the present specification, an aliphatic heterocycle refers to an aliphatic ring containing one or more heteroatoms. Examples of aliphatic heterocycles include oxirane, tetrahydrofuran, 1,4-dihydrofuran, Examples of the present invention include, but are not limited to, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azacyclooctane, thiocane, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran.

[0095] In the present specification, examples of the aliphatic or aromatic / aliphatic condensed heterocyclic ring include tetrahydrobenzonaphthothiophene and tetrahydrobenzonaphthofuran, but are not limited thereto.

[0096] In the present specification, an arylene group refers to a group having two bonding positions on an aryl group, that is, a divalent group. The above description of the aryl group is applicable to these groups except that they are each a divalent group.

[0097] In the present specification, a divalent heterocyclic group refers to a group having two bonding positions on a heterocyclic group, that is, a divalent group. Except that each of them is a divalent group, the above description of the heterocyclic group is applicable.

[0098] Unless otherwise defined in this specification, all technical terms and scientific terms used in this specification have the same meaning as those generally understood by those skilled in the art. Methods and materials similar to or equivalent to the description in this specification can be used for the implementation or test of embodiments of the present invention, but suitable methods and materials are described later. All publications, patent applications, patents and other references mentioned in this specification are included in this specification as a whole as a reference, and in the case of conflict, if no specific passage is mentioned, the present specification including the definition takes precedence. In addition, materials, methods and embodiments are only illustrative and not intended to be limited.

[0099] Next, the compounds of the above Chemical Formulae 1 to 4 are described in detail.

[0100] At least one of R1 to R3 in the present specification is deuterium, and thus the compounds of the above Chemical Formulas 1 to 4 contain at least one deuterium.

[0101] According to one embodiment of the present specification, the above “comprising at least one deuterium” means that any one or more of the hydrogen atoms at the substitutable positions are substituted with deuterium.

[0102] According to one embodiment of the present specification, the deuterium substitution rates of the compounds of Chemical Formulae 1 to 4 are each independently 0.01% to 100%.

[0103] According to one embodiment of the present specification, the deuterium substitution rates of the compounds of the above Chemical Formulae 1 to 4 are each independently 0.1% to 100%.

[0104] According to one embodiment of the present specification, the deuterium substitution rates of the compounds of the above Chemical Formulae 1 to 4 are each independently 1% to 100%.

[0105] According to one embodiment of the present specification, the deuterium substitution rates of the compounds of Chemical Formulae 1 to 4 are each independently 40% to 99%.

[0106] According to one embodiment of the present specification, when the compounds of the above chemical formulas 1 to 4 contain deuterium, they have the following effects. Specifically, the physical and chemical properties such as the bond length of the chemical bond related to deuterium are different from those of hydrogen. Compared with the CH bond, the stretching amplitude of the CD bond is smaller, so the van der Waals radius of deuterium is smaller than that of hydrogen. Generally, it can be shown that the CD bond is shorter and stronger than the CH bond. Therefore, when the hydrogen at the substitutable position of the above chemical formulas 1 to 4 is replaced by deuterium, the energy of the ground state is reduced, and the bond length of deuterium and carbon becomes shorter, so the molecular hardcore volume is reduced, so the electrical polarizability can be reduced, and the intermolecular interaction is weakened, so that the film volume can be increased. In addition, such characteristics can produce the effect of reducing the crystallinity of the film, that is, the amorphous state, which can usually effectively improve the life and driving characteristics of the organic light-emitting device, and the heat resistance can be further improved compared with the existing organic light-emitting device.

[0107] In the present specification, "X% deuterated", "deuteration degree X%" or "deuterium substitution rate X%" means that X% of the hydrogen atoms at substitutable positions in the structure are substituted with deuterium. For example, when the structure is dibenzofuran, "25% deuterated" the dibenzofuran, "deuteration degree 25%" of the dibenzofuran or "deuterium substitution rate 25%" of the dibenzofuran means that 2 of the 8 hydrogen atoms at substitutable positions of the dibenzofuran are substituted with deuterium.

[0108] In this specification, the "degree of deuteration" or "deuterium substitution rate" can be determined by nuclear magnetic resonance spectroscopy ( 1 The presence of the peptides can be confirmed by known methods such as H NMR, TLC / MS (Thin-Layer Chromatography / Mass Spectrometry) or GC / MS (Gas Chromatography / Mass Spectrometry).

[0109] Specifically, by nuclear magnetic resonance spectroscopy ( 1 When analyzing the "deuteration degree" or "deuterium substitution rate" by H NMR, DMF (dimethylformamide) can be added as an internal standard. 1 The integration ratio on H NMR is used to calculate the deuteration degree or deuterium substitution rate from the integrated amount of the total peak.

[0110] According to one embodiment of the present specification, Ar is a phenyl group which may be substituted by deuterium, a biphenyl group which may be substituted by deuterium, or a terphenyl group which may be substituted by deuterium.

[0111] According to one embodiment of the present specification, X1 is O.

[0112] According to one embodiment of the present specification, X1 is S.

[0113] According to one embodiment of the present specification, X2 is O.

[0114] According to one embodiment of the present specification, X2 is S.

[0115] In this specification, D represents deuterium.

[0116] According to one embodiment of the present specification, the chemical formula 1 is any one selected from the following compounds.

[0117]

[0118]

[0119]

[0120]

[0121] According to one embodiment of the present specification, the chemical formula 2 is any one selected from the following compounds.

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] According to one embodiment of the present specification, the chemical formula 3 is any one selected from the following compounds.

[0128]

[0129]

[0130]

[0131]

[0132] According to one embodiment of the present specification, the chemical formula 4 is any one selected from the following compounds.

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] The compounds of Chemical Formulas 1 to 4 according to one embodiment of the present specification can be produced by the methods of the production examples described below.

[0141] The present specification provides an organic light-emitting device including the above-mentioned compound.

[0142] In the present specification, when it is mentioned that a certain component is located “on” another component, it not only includes the case where the certain component is in contact with the other component, but also includes the case where other components exist between the two components.

[0143] In the present specification, when a part is indicated to “include / comprise” a certain component, unless there is a particular description to the contrary, it means that other components may be further included, rather than excluding other components.

[0144] In this specification, the above-mentioned "layer" is interchangeable with the "film" mainly used in this technical field, and refers to a coating covering the target area. The size of the above-mentioned "layer" is not limited, and the sizes of each "layer" can be the same or different. According to one embodiment, the size of the "layer" can be equal to the size of the entire device, can be equivalent to the size of a specific functional area, or can be as small as a single sub-pixel.

[0145] In this specification, the meaning of specific substance A contained in layer B includes i) the case where one or more substances A are contained in one layer B, and ii) the case where layer B is composed of one or more layers and substance A is contained in one or more layers of the multiple layers B.

[0146] In this specification, the meaning of a specific substance A being contained in layer C or layer D refers to all of the following situations: i) being contained in one or more layers among one or more layers C, or ii) being contained in one or more layers among one or more layers D, or iii) being contained in one or more layers C and one or more layers D, respectively.

[0147] One embodiment of the present specification provides an organic light-emitting device, comprising: a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers contains any one of the compounds of Chemical Formulas 1 to 4.

[0148] The organic layer of the organic light-emitting device of the present specification may be formed by a single-layer structure or a multi-layer structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, etc. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

[0149] According to one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound.

[0150] According to one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound as a main body of the light-emitting layer. In this case, the light-emitting layer further includes a dopant. Based on 100 parts by weight of the main body, the content of the dopant may include 1 part by weight to 60 parts by weight, preferably, 1 part by weight to 10 parts by weight.

[0151] According to one embodiment of the present specification, the dopant is a metal coordination compound.

[0152] According to one embodiment of the present specification, the dopant is a platinum coordination compound.

[0153] According to one embodiment of the present specification, the dopant is an iridium complex.

[0154] According to one embodiment of the present specification, the dopant is represented by the following chemical formula D-1 or D-2, but is not limited thereto.

[0155] [Chemical formula D-1]

[0156]

[0157] [Chemical formula D-2]

[0158]

[0159] In the above chemical formulas D-1 and D-2,

[0160] M is a transition metal,

[0161] A1, A3, A5, A6, K1, K2 and K3 are the same as or different from each other, and are each independently a direct bond, O, S, a divalent ester group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted divalent alkenyl group, a substituted or unsubstituted divalent allyl group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

[0162] A2 and A4 are the same as or different from each other, and are each independently a direct bond, N, a substituted or unsubstituted trivalent alkylene group, a substituted or unsubstituted trivalent aryl group, or a substituted or unsubstituted trivalent heteroaryl group,

[0163] n is 1 or 2. When n is 2, the structures in the brackets are the same as or different from each other.

[0164] According to one embodiment of the present specification, the above-mentioned M is iridium or platinum.

[0165] According to one embodiment of the present specification, the dopant may be selected from the following structural formulas, but is not limited thereto.

[0166]

[0167]

[0168]

[0169]

[0170] According to one embodiment of the present specification, the compound is a p-type host, and the light-emitting layer may further include an n-type host. In this case, the n-type host may use a material known in the art.

[0171] According to one embodiment of the present specification, the above-mentioned organic light-emitting device also includes one or more of a hole transport layer, a hole injection layer, an electron blocking layer, a hole injection and transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection layer.

[0172] According to one embodiment of the present specification, the organic layer includes an electron blocking layer, and the electron blocking layer may include the compound.

[0173] According to one embodiment of the present specification, the electron blocking layer and the light-emitting layer may contain the compound.

[0174] According to one embodiment of the present specification, the first electrode is an anode or a cathode.

[0175] According to one embodiment of the present specification, the second electrode is a cathode or an anode.

[0176] According to one embodiment of the present specification, the organic light emitting device may be a (normal type) organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

[0177] According to one embodiment of the present specification, the organic light emitting device may be an organic light emitting device of a reverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate.

[0178] For example, the structure of an organic light-emitting device according to one embodiment of the present specification is shown in Figure 1 and 2 . The above Figure 1 and Figure 2 An organic light emitting device is exemplified, and is not limited thereto.

[0179] Figure 1 exemplifies the structure of an organic light-emitting device in which a first electrode 2, a light-emitting layer 4, and a second electrode 3 are sequentially stacked on a substrate 1. The above-mentioned compound is contained in the light-emitting layer.

[0180] Figure 2 exemplifies the structure of an organic light-emitting device in which a first electrode 2, a hole injection layer 5, a hole transport layer 6, a hole adjustment layer 7, a light-emitting layer 4, an electron adjustment layer 8, an electron transport layer 9, an electron injection layer 10, a second electrode 3 and a capping layer 11 are sequentially stacked on a substrate 1. The above compound is contained in the light-emitting layer.

[0181] The organic light-emitting device of the present specification can be manufactured using materials and methods known in the art, except that the light-emitting layer and / or the electron blocking layer include the above compound, ie, the compounds of the above Chemical Formulae 1 to 4.

[0182] When the organic light-emitting device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

[0183] For example, the organic light-emitting device of the present specification can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. In this case, the device can be manufactured as follows: a metal or a conductive metal oxide or an alloy thereof is evaporated on a substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer is formed on the anode, and then a substance that can be used as a cathode is evaporated on the organic layer. In addition to this method, an organic light-emitting device can also be manufactured by sequentially evaporating a second electrode substance, an organic layer, and a first electrode substance on a substrate.

[0184] In addition, the compounds represented by the above chemical formulas 1 to 4 can be used to form an organic layer by not only vacuum evaporation but also solution coating when manufacturing an organic light-emitting device. 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 thereto.

[0185] In addition to these methods, the organic light-emitting device can also be manufactured by sequentially vapor-depositing the second electrode material, the organic material layer, and the first electrode material on the substrate. However, the manufacturing method is not limited to this.

[0186] As the first electrode material, in order to smoothly inject holes into the organic layer, a material with a large work function is preferred. For example, there are 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, etc., but are not limited thereto.

[0187] As the second electrode material, in order to facilitate electron injection into the organic layer, a material with a small work function is preferably used, for example, 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 not limited thereto.

[0188] The hole injection layer is a layer that plays a role in making the injection of holes from the anode to the light-emitting layer smooth. The hole injection material is a material that can receive holes well from the anode at a low voltage. The HOMO (highest occupied molecular orbital) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer. As specific examples of hole injection materials, there are metal porphyrines, oligothiophenes, arylamine organics, hexanitrile hexaazatriphenylene organics, quinacridone organics, perylene organics, anthraquinones, polyaniline and polythiophene conductive polymers, but are not limited to this. The thickness of the hole injection layer can be 1nm to 150nm. When the thickness of the hole injection layer is more than 1nm, it has the advantage of preventing the hole injection characteristics from being reduced. When it is less than 150nm, it has the advantage of preventing the driving voltage from rising when the thickness of the hole injection layer is too thick to improve the migration of holes.

[0189] In one embodiment of the present specification, the hole injection layer may contain one or more N-containing polycyclic compounds containing a cyano group or an amine compound containing a carbazole group. At this time, the N-containing polycyclic compound may be 1,4,5,8,9,11-hexanitrile hexaazatriphenylene (1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile) (HATCN). According to one example, the hole transport layer may contain the above-mentioned compound alone, or may contain two or more of the above-mentioned compounds. According to another example, the above-mentioned HATCN can be vapor-deposited as a first hole transport layer, and on the above-mentioned first hole transport layer, the above-mentioned amine compound containing a carbazole group is vapor-deposited as a second hole transport layer.

[0190] The hole transport layer can play a role in smoothing the transport of holes. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer, and a material with a large hole mobility is suitable. As specific examples, there are arylamine organic substances, conductive polymers, and block copolymers with both conjugated parts and non-conjugated parts, but are not limited to these.

[0191] In one embodiment of the present specification, the hole transport layer may include an amine compound containing a carbazole group.

[0192] A hole buffer layer may be further disposed between the hole injection layer and the hole transport layer, and may include hole injection or transport materials known in the art.

[0193] The electron blocking layer is a layer that prevents electrons from flowing from the light-emitting layer into the anode and regulates the flow of holes flowing into the light-emitting layer, thereby regulating the performance of the entire device. As the electron blocking substance, preferably, the following compound: a compound that prevents the flow of electrons from the light-emitting layer to the anode and has the ability to regulate the flow of holes injected into the light-emitting layer or the light-emitting material. In one embodiment, as the electron blocking layer, an arylamine-based organic substance can be used, but it is not limited thereto.

[0194] In one embodiment of the present specification, the electron blocking layer may include an amine compound containing a carbazole group. According to an example, the carbazole group and the amine group of the compound may be connected by an o-biphenylene group.

[0195] The hole blocking layer is a layer that blocks holes from flowing from the light-emitting layer into the cathode and regulates the electrons flowing into the light-emitting layer, thereby regulating the performance of the entire device. As the hole blocking substance, preferably, the following compound: a compound that prevents the flow of holes from the light-emitting layer into the cathode and has the ability to regulate the electrons injected into the light-emitting layer or the light-emitting material. As the hole blocking substance, a suitable substance can be used according to the composition of the organic layer used in the device. Specifically, Examples of the compound include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and aluminum complexes.

[0196] In one embodiment of the present specification, the hole blocking layer may include a compound in which a structure containing an N ring is connected directly or via a linking group to a spiro[fluorene-9,9'-xanthene] structure.

[0197] The above-mentioned electron transport layer can play a role in making the transmission of electrons smooth. The electron transport material is a material that can receive electrons well from the cathode and transfer them to the light-emitting layer, and is suitable for materials with high electron mobility. As specific examples, there are the above-mentioned compounds or Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, etc., but are not limited to this. The thickness of the electron transport layer can be 1nm to 50nm. When the thickness of the electron transport layer is more than 1nm, it has the advantage of preventing the electron transport characteristics from being reduced. When it is less than 50nm, it has the advantage of preventing the driving voltage from rising in order to improve the migration of electrons when the thickness of the electron transport layer is too thick.

[0198] In one embodiment of the present specification, the electron transport layer may include a compound containing an N ring and CN, and may also include an n-type dopant or an organic metal compound. According to an example, the n-type dopant or the organic metal compound may be LiQ.

[0199] The electron injection layer can play a role in facilitating the injection of electrons. As the electron injection material, the following compounds are preferred: compounds that have the ability to transport electrons, have the effect of injecting electrons from the cathode, have an excellent electron injection effect on the light-emitting layer or the light-emitting material, prevent the excitons generated in the light-emitting layer from migrating to the hole injection layer, and have excellent thin film forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Examples include, but are not limited to, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, and derivatives thereof, metal coordination compounds, and nitrogen-containing five-membered ring derivatives.

[0200] In one embodiment of the present specification, the electron injection layer may include lithium fluoride (LiF).

[0201] 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.

[0202] 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.

[0203] The organic light-emitting device according to the present specification can be included in various electronic devices for use. For example, the electronic device can be a display panel, a touch panel, a solar module, a lighting device, etc., but is not limited thereto.

[0204] Modes for Carrying Out the Invention

[0205] Below, in order to specifically describe this specification, examples and comparative examples will be cited for detailed description. However, the examples and comparative examples of this specification can be deformed into various forms, and it is not interpreted that the scope of this specification is limited to the examples and comparative examples described in detail below. The examples and comparative examples of this specification are provided to more completely describe this specification to those skilled in the art.

[0206] <Example>

[0207] <Synthesis Example 1> Synthesis of Compound 1

[0208] 1) Synthesis of intermediate 1-1

[0209]

[0210] Under nitrogen atmosphere, 12-(3-bromophenyl-2,4,6-d3)-3-chloro-12H-benzofuro[2,3-a]carbazole-1,4,5,6,8,10-d (20 g, 43.9 mmol) and [1,1'-biphenyl]-3-ylboronic acid (8.7 g, 43.9 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, potassium carbonate (18.2 g, 131.6 mmol) dissolved in 60 ml of water was added, and after sufficient stirring, tetrakis(triphenylphosphine)palladium (1.5 g, 1.3 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature and the generated solid was filtered. The solid was dissolved in 464 mL of chloroform and washed twice with water. The organic layer was separated and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered and the filtrate was distilled under reduced pressure. The concentrated compound was purified by recrystallization from chloroform and ethyl acetate to produce a white solid compound 1-1 (13.9 g, 60%, MS: [M+H] + =530.1).

[0211] 2) Synthesis of Compound 1

[0212]

[0213] Under a nitrogen atmosphere, compound 1-1 (25 g, 47.3 mmol) and 9H-carba zole (7.9 g, 47.3 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (13.6 g, 141.8 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.7 g, 1.4 mmol) was 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. It was again added to 935 mL of chloroform to dissolve, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, 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 (19 g, 61%, MS: [M+H] + =660.8).

[0214] <Synthesis Example 2> Synthesis of Compound 2

[0215] 1) Synthesis of intermediate 2-1

[0216]

[0217] Under nitrogen atmosphere, 3-chloro-12H-benzofuro[2,3-a]carbazole-1,4,5,6,8,10-d6 (25 g, 84 mmol) and 4-bromo-1,1'-biphenyl (19.6 g, 84 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24.2 g, 251.9 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. The mixture was again put into 1133 mL of chloroform to dissolve, washed twice with water, separated the organic layer, added with anhydrous magnesium sulfate, stirred and 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 2-1 (25.7 g, 68%, MS: [M+H] + =451).

[0218] 2) Synthesis of Compound 2

[0219]

[0220] Under nitrogen atmosphere, compound 2-1 (25 g, 55.6 mmol) and 12H-benzofuro[3,2-a]carbazole (12H-benzofuro[3,2-a]carbazole) (14.3 g, 55.6 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (16 g, 166.7 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.9 g, 1.7 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. It was added again to 1118 mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 2 (18.6 g, 50%, MS: [M+H] + =671.8).

[0221] <Synthesis Example 3> Synthesis of Compound 3

[0222] 1) Synthesis of intermediate 3-1

[0223]

[0224] Under nitrogen atmosphere, 9-chloro-12H-benzofuro[3,2-a]carbazole-1,2,3,4,6,7,8,10,11-d9 was added to

[0225] (25g, 83.1mmol) and 3-bromo-1,1':3',1"-terphenyl (3-bromo-1,1':3',1"-terphenyl) (25.7g, 83.1mmol) were added to 500ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24g, 249.3mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8g, 2.5mmol) 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. It was added again to 1319mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 3-1 (27.7g, 63%, MS: [M+H] + =530.1).

[0226] 2) Synthesis of Compound 3

[0227]

[0228] Under nitrogen atmosphere, compound 3-1 (25 g, 47.3 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (8.3 g, 47.3 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (13.6 g, 141.8 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.7 g, 1.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again added to 947 mL of chloroform to dissolve, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 3 (15.8 g, 50%, MS: [M+H] +=668.9).

[0229] <Synthesis Example 4> Synthesis of Compound 4

[0230] 1) Synthesis of intermediate 4-1

[0231]

[0232] Under nitrogen atmosphere, 9-chloro-12H-benzo[4,5]thieno[3,2-a]carbazole (25 g, 81.2 mmol) and 2-bromo-1,1':4',1"-terphenyl (25.1 g, 81.2 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (23.4 g, 243.7 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. The mixture was again put into 1289 mL of chloroform to dissolve, 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 white solid compound 4-1 (30.1 g, 70%, MS: [M+H] + =530.1).

[0233] 2) Synthesis of compound 4

[0234]

[0235] Under nitrogen atmosphere, compound 4-1 (25 g, 46.6 mmol) and 12H-benzofuro[3,2-a]carbazole-2,4,6,7,9,11-d6 (12H-benzofuro[3,2-a]carbazole-2,4,6,7,9,11-d6) (12.3 g, 46.6 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (13.4 g, 139.9 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.7 g, 1.4 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again added to 1067 mL of chloroform to dissolve, 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 white solid compound 4 (28.1 g, 79%, MS: [M+H] + =764).

[0236] <Synthesis Example 5> Synthesis of Compound 5

[0237] 1) Synthesis of intermediate 5-1

[0238]

[0239] Under nitrogen atmosphere, 11-chloro-8H-benzofuro[2,3-c]carbazole-2,4,6,7,9,12-d6 (25 g, 84 mmol) and 1-bromobenzene-2,4,6-d3 (13.4 g, 84 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24.2 g, 251.9 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. The mixture was again put into 949 mL of chloroform to dissolve, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 5-1 (15.8 g, 50%, MS: [M+H] + =377.9).

[0240] 2) Synthesis of Compound 5

[0241]

[0242] Under nitrogen atmosphere, compound 5-1 (25 g, 66.3 mmol) and 12H-benzofuro[3,2-a]carbazole (17.1 g, 66.3 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (19.1 g, 199 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (1 g, 2 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. It was added again to 1189 mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 5 (29.7 g, 75%, MS: [M+H] + =598.7).

[0243] <Synthesis Example 6> Synthesis of Compound 6

[0244] 1) Synthesis of intermediate 6-1

[0245]

[0246] Under nitrogen atmosphere, 11-chloro-8H-benzo[4,5]thieno[2,3-c]carbazole-2,4,6,7,9,12-d6 (25 g, 79.7 mmol) and 3-bromo-1,1'-biphenyl (18.6 g, 79.7 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (23 g, 239 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.7 g, 2.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. The mixture was again put into 1114 mL of chloroform to dissolve, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 6-1 (21.5 g, 58%, MS: [M+H] + =467).

[0247] 2) Synthesis of Compound 6

[0248]

[0249] Under nitrogen atmosphere, compound 6-1 (25 g, 53.6 mmol) and 9H-carbazole-1,3,4,5,6,8-d6 (9H-carbazole-1,3,4,5,6,8-d6) (9.3 g, 53.6 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (15.5 g, 160.9 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.8 g, 1.6 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. It was again added to 970 mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 6 (16.8 g, 52%, MS: [M+H] + =603.8).

[0250] <Synthesis Example 7> Synthesis of Compound 7

[0251] 1) Synthesis of intermediate 7-1

[0252]

[0253] Under nitrogen atmosphere, 2-chloro-5H-benzofuro[3,2-c]carbazole-1,3,4,6,7,8,9,10,11-d9 (25 g, 83.1 mmol) and 5'-bromo-1,1':3',1"-terphenyl (25.7 g, 83.1 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24 g, 249.3 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again put into 1319 mL of chloroform to dissolve, washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 7-1 (32.1 g, 73%, MS: [M+H] + =530.1).

[0254] 2) Synthesis of compound 7

[0255]

[0256] Under a nitrogen atmosphere, 7-1 (25 g, 47.3 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (8.3 g, 47.3 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (13.6 g, 141.8 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.7 g, 1.4 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. It was again added to 947 mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 7 (16.1 g, 51%, MS: [M+H] + =668.9).

[0257] <Synthesis Example 8> Synthesis of Compound 8

[0258] 1) Synthesis of intermediate 8-1

[0259]

[0260] Under nitrogen atmosphere, 2-chloro-5H-benzofurano[3,2-c]carbazole-1,3,4,6,7,8,9,10,11-d9 (25 g, 83.1 mmol) and 3-bromo-1,1'-biphenyl (19.4 g, 83.1 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24 g, 249.3 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again added to 1129 mL of chloroform to dissolve, 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 white solid compound 8-1 (20.7 g, 55%, MS: [M+H] + =454).

[0261] 2) Synthesis of Compound 8

[0262]

[0263] Under nitrogen atmosphere, compound 8-1 (25 g, 55.2 mmol) and 12H-benzofuro[3,2-a]carbazole-1,2,3,4,6,7,8,9,10,11-d10 (14.8 g, 55.2 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (15.9 g, 165.6 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.8 g, 1.7 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. The mixture was again put into 1132 mL of chloroform to dissolve, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 8 (27.6 g, 73%, MS: [M+H] + =684.9).

[0264] <Synthesis Example 9> Synthesis of Compound 9

[0265] 1) Synthesis of intermediate 9-1

[0266]

[0267] Under nitrogen atmosphere, 9-chloro-12H-benzofurano[3,2-a]carbazole-1,2,3,4,6,7,8,10,11-d9 (25 g, 83.1 mmol) and 1-bromobenzene-2,3,4,5,6-d5 (13.5 g, 83.1 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24 g, 249.3 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. The mixture was again put into 952 mL of chloroform to dissolve, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 9-1 (19.4 g, 61%, MS: [M+H] + =382.9).

[0268] 2) Synthesis of compound 9

[0269]

[0270] Under nitrogen atmosphere, 9-1 (25 g, 65.5 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (11.5 g, 65.5 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (18.9 g, 196.4 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (1 g, 2 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer was filtered to remove the salt, and the filtered organic layer was distilled. It was again added to 1023 mL of chloroform to dissolve, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 9 (25.2 g, 74%, MS: [M+H] + =521.7).

[0271] <Synthesis Example 10> Synthesis of Compound 10

[0272] 1) Synthesis of intermediate 10-1

[0273]

[0274] Under nitrogen atmosphere, 9-chloro-12H-benzofurano[3,2-a]carbazole-1,2,3,4,6,7,8,10,11-d9 (25 g, 83.1 mmol) and 3-bromo-1,1'-biphenyl (19.4 g, 83.1 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24 g, 249.3 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again added to 1129 mL of chloroform to dissolve, 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 white solid compound 10-1 (23.7 g, 63%, MS: [M+H] + =454).

[0275] 2) Synthesis of compound 10

[0276]

[0277] Under a nitrogen atmosphere, 10-1 (25 g, 55.2 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (9.7 g, 55.2 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (15.9 g, 165.6 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.8 g, 1.7 mmol) was added. After reacting for 3 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. It was again added to 980 mL of chloroform to dissolve, washed with water twice, and 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 ethyl acetate to produce a white solid compound 10 (16.3 g, 50%, MS: [M+H] + =592.8).

[0278] <Synthesis Example 11> Synthesis of Compound 11

[0279]

[0280] Under a nitrogen atmosphere, 8-1 (25 g, 55.2 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (9.7 g, 55.2 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (15.9 g, 165.6 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.8 g, 1.7 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. It was again added to 980 mL of chloroform to dissolve, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 11 (20.6 g, 63%, MS: [M+H] + =592.8).

[0281] <Synthesis Example 12> Synthesis of Compound 12

[0282] 1) Synthesis of intermediate 12-1

[0283]

[0284] Under nitrogen atmosphere, 2-chloro-5H-benzofurano[3,2-c]carbazole-1,3,4,6,7,8,9,10,11-d9 (25 g, 83.1 mmol) and 1-bromobenzene-2,3,4,5,6-d5 (13.5 g, 83.1 mmol) were added to 500 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (24 g, 249.3 mmol) was added, and after sufficient stirring, (bis(diphenylphosphino)ferrocene)palladium dichloride (1.8 g, 2.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer was filtered to remove salt, and the filtered organic layer was distilled. It was again added to 952 mL of chloroform to dissolve, 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 white solid compound 12-1 (22.9 g, 72%, MS: [M+H] + =382.9).

[0285] 2) Synthesis of compound 12

[0286]

[0287] Under a nitrogen atmosphere, 12-1 (25 g, 65.5 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (11.5 g, 65.5 mmol) were added to 500 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (18.9 g, 196.4 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (1 g, 2 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. It was again added to 1023 mL of chloroform and dissolved. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound 12 (22.8 g, 67%, MS: [M+H] + =521.7).

[0288] <Example 1>

[0289] ITO (indium tin oxide) is used 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.

[0290] On the ITO transparent electrode prepared as the anode, the following compound HT1 and the following compound HI1 were mixed in a ratio of 98:2 (molar ratio) and The following compound HT1 was vacuum-deposited on the hole injection layer. Then, on the hole transport layer, a film with a thickness of The compound 1 synthesized in the above Synthesis Example 1 was vacuum-deposited to form an electron blocking layer. Next, on the above electron blocking layer, a mixture of the following compound BH (n-type) and the compound 1 synthesized in the above Synthesis Example 1 at a weight ratio of 1:1 and the following compound BD at a weight ratio of 88:12 were vacuum-deposited to form an electron blocking layer. On the above-mentioned light-emitting layer, a film thickness of The following compound BH (n-type) was vacuum-deposited to form a hole blocking layer. Next, the following compound ET1 and the following compound LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form a hole blocking layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added with The thickness of the aluminum A cathode is formed by evaporation with a thickness of .

[0291]

[0292] In the above process, the evaporation rate of organic matter is maintained Lithium fluoride at the cathode maintains The evaporation speed of aluminum is maintained The evaporation speed is 2×10 -7 ~5×10 -6 A support is provided to produce an organic light-emitting device.

[0293] <Example 2 to Example 12>

[0294] An organic light-emitting device was manufactured by the same method as in Example 1, except that Compounds 2 to 12 manufactured in Synthesis Examples 2 to 12 were used instead of Compound 1.

[0295] <Comparative Examples 1 to 5>

[0296] An organic light-emitting device was manufactured by the same method as in Example 1, except that the compound described in Table 1 below was used instead of Compound 1. The compounds BH1 to BH5 used in Table 1 below are as follows.

[0297]

[0298] <Experimental example>

[0299] When current was applied to the organic light emitting devices manufactured in the above examples and comparative examples, voltage, efficiency, color coordinates and lifetime were measured, and the results are shown in the following Table 1. T90 refers to the time required for the luminance to decrease from the initial luminance (1600 nits) to 90%.

[0300] [Table 1]

[0301]

[0302] As shown in Table 1 above, the organic light-emitting devices of Examples 1 to 2, in which the compounds of the present invention, in which a carbazole group is bonded to the R position of a carbazole fused with a heteroaryl group, Ar is substituted by an aromatic group, and Ar is substituted by one or more deuteriums, are used as p-type hosts of the electron blocking layer and the light-emitting layer, show excellent characteristics in terms of efficiency, driving voltage and stability of the organic light-emitting device.

[0303] In contrast, the compounds of Comparative Examples 1 to 5 are structures in which the carbazole group is bonded to a position other than the R position (BH1, BH3); or R1 is substituted by a specific functional group other than hydrogen, deuterium or phenyl (BH2); or Ar is a heteroaryl group (BH1, BH3); or the compound does not contain deuterium (BH4, BH5). The organic light-emitting devices using the above compounds show increased voltage, reduced efficiency and stability (lifespan) compared to the organic light-emitting devices of Examples 1 to 12 using the compounds of Chemical Formula 1 of the present application.

Claims

1. Any one of the following chemical formulas 1 to 4: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] In the chemical formulas 1 to 4, X1 is O or S, Ar is an aryl group having 18 or less carbon atoms which is substituted or unsubstituted with deuterium, and R1 is each independently hydrogen, deuterium or phenyl. R is the following chemical formula 5 or chemical formula 6, a is an integer from 0 to 9, [Chemical formula 5] [Chemical formula 6] In the chemical formulas 5 and 6, X2 is O or S, B is a benzene ring, R2 and R3 are each independently hydrogen, deuterium or phenyl, b is an integer from 0 to 10, c is an integer from 0 to 8, represents a site connected to the chemical formulae 1 to 4, However, at least one of R1 to R3 is deuterium.

2. The compound according to claim 1, wherein The Ar is a phenyl group which may be substituted by deuterium, a biphenyl group which may be substituted by deuterium, or a terphenyl group which may be substituted by deuterium.

3. The compound according to claim 1, wherein The chemical formula 1 is any one selected from the following compounds:

4. The compound according to claim 1, wherein The chemical formula 2 is any one selected from the following compounds:

5. The compound according to claim 1, wherein The chemical formula 3 is any one selected from the following compounds:

6. The compound according to claim 1, wherein The chemical formula 4 is any one selected from the following compounds:

7. An organic light-emitting device, wherein: include: a first electrode, a second electrode, and one or more organic layers provided between the first electrode and the second electrode, One or more of the organic layers contains the compound according to any one of claims 1 to 6.

8. The organic light emitting device according to claim 7, wherein: The organic layer includes a light-emitting layer, and the light-emitting layer contains the compound.

9. The organic light emitting device according to claim 8, wherein: The light-emitting layer includes the compound as a host and further includes a dopant.

10. The organic light emitting device according to claim 9, wherein: The compound is a p-type host, The light-emitting layer further comprises an n-type host.

11. The organic light emitting device according to claim 8, wherein: The organic layer further includes one or more of a hole transport layer, a hole injection layer, an electron blocking layer, a hole injection and transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection layer.

12. The organic light emitting device according to claim 7, wherein: The organic layer includes an electron blocking layer, and the electron blocking layer includes the compound.

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