Heterocyclic compound and organic light-emitting device comprising same

Abstract

Disclosed are a heterocyclic compound of Chemical Formula 1 and an organic light-emitting device comprising the same. When the heterocyclic compound is used in an organic light emitting device, the driving voltage of the device can be reduced, the luminous efficiency of the device can be improved, and the thermal stability of the heterocyclic compound can be improved to improve the lifespan characteristics of the device.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0040927 filed in the Korean Intellectual Property Office on March 26, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present specification relates to a heterocyclic compound and an organic light-emitting device including the same. Background Art

[0004] A light-emitting device is a self-luminous display device and has the advantages of a wide viewing angle, excellent contrast, and a fast response speed.

[0005] An organic light-emitting device has a structure in which an organic thin film is interposed between two electrodes. When a voltage is applied to an organic light-emitting device having this structure, electrons and holes injected from the two electrodes combine to form pairs in the organic thin film, then annihilate and emit light. The organic thin film can be composed of a single layer or multiple layers, as desired.

[0006] If necessary, the material used for the organic thin film may have a light-emitting function. For example, a compound that can independently constitute a light-emitting layer may be used as a material for the organic thin film, or a compound that can serve as a host or dopant in a host-dopant light-emitting layer may be used. Furthermore, compounds that can perform the following functions, such as hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection, may also be used as materials for the organic thin film.

[0007] To improve the performance, lifetime, or efficiency of organic light-emitting devices, there is a continuous need to develop materials for organic thin films.

[0008] [Related technical literature]

[0009] [Patent Document]

[0010] (Patent Document 1) U.S. Patent No. 4,356,429 Summary of the Invention

[0011] The present invention is directed to providing a heterocyclic compound and an organic light-emitting device comprising the same.

[0012] An exemplary embodiment of the present invention provides a heterocyclic compound represented by the following Chemical Formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] X is O; or S,

[0017] Ra and Rb are the same as or different from each other and are each independently a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0018] L1 to L3 are the same as or different from each other and are each independently a direct bond; or a substituted or unsubstituted C6 to C60 arylene group,

[0019] Each of l1 to l3 is an integer from 0 to 4, and

[0020] When each of l1 to l3 is an integer of 2 or greater, the substituents in the brackets are the same as or different from each other,

[0021] R1 to R6 are the same as or different from each other and are each independently hydrogen; deuterium; a cyano group; a halogen group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted phosphine oxide group.

[0022] a is an integer from 0 to 4,

[0023] Each of b and c is an integer from 0 to 3,

[0024] Each of d and e is an integer from 0 to 5,

[0025] f is an integer from 0 to 2, and

[0026] When each of a, b, c, d, e, and f is an integer of 2 or greater, the substituents in the brackets are the same as or different from each other.

[0027] Another exemplary embodiment provides an organic light-emitting device including: a first electrode; a second electrode disposed to face the first electrode; and an organic material layer having one or more layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layer contain the above-mentioned heterocyclic compound.

[0028] The heterocyclic compound according to an exemplary embodiment of the present application is a tertiary amine represented by Chemical Formula 1, wherein the first substituent is a tricyclic heteroaryl group containing a heteroatom O or S (represented by X) and directly connected to the N atom of the amine, the second substituent has an aryl group or heteroaryl group consisting of a terminal group Ra connected to the N atom of the amine through a linking group (represented by L1), and the third substituent has a terminal carbazolyl group connected to the N atom of the amine through a linking group (represented by L3), and two benzene rings are connected to specific positions on the benzene ring on the other side of the benzene ring connected to the N atom around the carbazolyl group.

[0029] As represented by the above Chemical Formula 1, the first substituent regulates the hole transport rate, the second substituent regulates structural stability and charge balance, and the third substituent regulates the hole transport rate of carbazole having strong hole characteristics, so that the present invention can be used as an electron blocking layer and a hole transport layer.

[0030] As a result, when the heterocyclic compound is used in an organic light-emitting device, the driving voltage of the device can be reduced, the luminous efficiency of the device can be improved, and the thermal stability of the heterocyclic compound can be improved to improve the lifespan characteristics of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figures 1 to 5 1 and 2 are diagrams each exemplarily illustrating a stack structure of an organic light emitting device according to an exemplary embodiment of the present specification. DETAILED DESCRIPTION

[0032] Hereinafter, this specification will be described in more detail.

[0033] <Definition>

[0034] In the present specification, when a part “includes” one constituent element, unless otherwise specifically described, this does not mean that other constituent elements are excluded but means that other constituent elements may be further included.

[0035] In this specification, chemical formula or structural formula This refers to the location where bonding is to take place.

[0036] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited as long as the position is a position where a hydrogen atom is substituted (i.e., a position where a substituent can be substituted), and when two or more substitutions are made, the two or more substituents may be the same as or different from each other.

[0037] In the present specification, "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, a halogen group, a C1 to C60 straight or branched alkyl group, a C2 to C60 straight or branched alkenyl group, a C2 to C60 straight or branched alkynyl group, a C3 to C60 monocyclic or polycyclic cycloalkyl group, a C2 to C60 monocyclic or polycyclic heterocycloalkyl group, a C6 to C60 monocyclic or polycyclic aryl group, a C2 to C60 monocyclic or polycyclic heteroaryl group, a silyl group, a phosphine oxide group, and an amino group, or unsubstituted or substituted with a substituent in which two or more substituents selected from the exemplified substituents are linked together.

[0038] In this specification, "when no substituent is shown in a chemical formula or a structure of a compound" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( 2 H) or tritium corresponds to an isotope of hydrogen, and thus can be interpreted as a concept included in hydrogen unless it is explicitly excluded.

[0039] That is, in the present application, according to Chem. Commun., 2014, 50, 14870, deuterium exhibits an effect equivalent to that of hydrogen in terms of driving voltage, luminous efficiency and service life, or exhibits an improved effect in some evaluation criteria, and since the effect falls within the range that a person skilled in the art can predict to have an equivalent effect without conducting specific experiments, as long as deuterium (an isotope of hydrogen) is not explicitly excluded, it is interpreted as a concept included in hydrogen.

[0040] According to one exemplary embodiment of the present specification, "when no substituent is shown in a chemical formula or a structure of a compound," it may mean that all positions accessible to substituents are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be deuterium as an isotope. In this case, the deuterium content may be 0% to 100%.

[0041] According to an exemplary embodiment of the present specification, in the case where “no substituent is shown in the chemical formula or structure of the compound”, when the deuterium content is 0%, the hydrogen content is 100%, and all substituents do not explicitly exclude deuterium such as hydrogen, and hydrogen and deuterium can be mixed and used in the compound.

[0042] According to an exemplary embodiment of the present specification, deuterium is one of the isotopes of hydrogen, is an element having a deuteron consisting of one proton and one neutron as a nucleus, and can be represented by hydrogen-2, and the element symbol can also be represented by D or 2 H.

[0043] According to an exemplary embodiment of the present specification, isotopes mean atoms having the same atomic number (Z) but different mass numbers (A), and may also be interpreted as elements having the same number of protons but different numbers of neutrons.

[0044] According to an exemplary embodiment of the present specification, when the total number of substituents of the base compound is defined as T1 and the number of specific substituents among the substituents is defined as T2, the content T% of the specific substituent may be defined as T2 / T1×100=T%.

[0045] That is, when When the phenyl group represented by is taken as an example, herein, when the total number of substituents that the phenyl group may have is 5 (T1 in the formula) and the number of deuterium atoms in the substituent is 1 (T2 in the formula), a deuterium content of 20% can be represented by 20%. That is, a deuterium content of 20% in the phenyl group can be represented by the following structural formula.

[0046]

[0047] In addition, according to an exemplary embodiment of the present specification, “a phenyl group having a deuterium content of 0%” may mean a phenyl group that does not include a deuterium atom, that is, a phenyl group having five hydrogen atoms.

[0048] In the present specification, the cyano group may mean -CN.

[0049] In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

[0050] In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be substituted with another substituent. The number of carbon atoms in the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof 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, 5-methylhexyl and the like, but are not limited thereto.

[0051] In this specification, alkenyl includes a straight chain or branched chain with 2 to 60 carbon atoms, and can be substituted with another substituent. The number of carbon atoms of the alkenyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Its 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-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, but are not limited thereto.

[0052] In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted with another substituent. The number of carbon atoms in the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

[0053] In this specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but are not limited thereto.

[0054] In this specification, cycloalkyl includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be substituted with another substituent. Here, polycyclic means a group in which a cycloalkyl is directly connected or fused to another cyclic group. Here, the other cyclic group may also be a cycloalkyl, but may also be another cyclic group, such as a heterocycloalkyl, an aryl, a heteroaryl, etc. The number of carbon atoms in the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof include 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, but are not limited thereto.

[0055] In this specification, heterocycloalkyl contains O, S, Se, N or Si as heteroatoms, including monocyclic or polycyclic rings with 2 to 60 carbon atoms, and may be substituted with other substituents. Here, polycyclic means a group in which the heterocycloalkyl is directly connected or fused to another cyclic group. Here, the other cyclic group may also be a heterocycloalkyl, but may also be another cyclic group, such as a cycloalkyl, an aryl, a heteroaryl, etc. The number of carbon atoms in the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

[0056] In this specification, aryl includes monocyclic or polycyclic rings having 6 to 60 carbon atoms, and may be substituted with another substituent. Here, polycyclic means a group in which an aryl group is directly connected to or fused with another cyclic group. Here, the other cyclic group may also be an aryl group, but may also be another cyclic group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, etc. Aryl includes a spirocyclic group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of aryl include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenyl, phenanthrenyl, peryl, fluoranthenyl, triphenylene, phenanthrenyl, pyrenyl, tetraphenyl, pentacene, fluorenyl, indenyl, acenaphthenyl, benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, and condensed cyclic groups thereof, but are not limited thereto.

[0057] In the present specification, the terphenyl group may be selected from the following structures.

[0058]

[0059] In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

[0060] When the fluorenyl group is substituted, the substituent may be selected from the following structures, but is not limited thereto.

[0061]

[0062] In this specification, heteroaryl contains S, O, Se, N or Si as a heteroatom, including monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a heteroaryl is directly connected or fused to another cyclic group. Here, the other cyclic group may also be a heteroaryl, but may also be another cyclic group such as a cycloalkyl, a heterocycloalkyl, an aryl, etc. The number of carbon atoms in the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, Azolyl, iso Azolyl, thiazolyl, isothiazolyl, triazolyl, furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazine, thiazine, di dioxynyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinazolinyl group, isoquinazolinyl, quinozolilyl group, naphthyridinyl, acridinyl, phenanthridinyl, imidazopyridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, benzothiazolyl, benzo oxazolyl, benzimidazolyl, benzothiophenyl, benzofuranyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenazinyl, dibenzothiophenyl, spirobis(dibenzothiophenyl), dihydrophenazinyl, phen azinyl, phenanthridinyl, imidazopyridinyl, thienyl, indolo[2,3-a]carbazolyl, indolo[2,3-b]carbazolyl, dihydroindolinyl, 10,11-dihydro-dibenzo[b,f]azepinyl, 9,10-dihydroacridinyl, phenanthrazinyl group), phenothiathiazinyl group, phthalazinyl, naphthyridinyl, phenanthroline, benzo[c][1,2,5]thiadiazolyl, 2,3-dihydrobenzo[b]thienyl, 2,3-dihydrobenzofuranyl, 5,10-dihydrodibenzo[b,e][1,4]azasilyl, pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]indazolyl, pyrido[1,2-a]imidazo[1,2-e]dihydroindole, 5,11-dihydroindeno[1,2-b]carbazolyl, etc., but are not limited thereto.

[0063] In the present specification, when a substituent is a carbazolyl group, it means that it is bonded to nitrogen or carbon of carbazole.

[0064] In the present specification, when a carbazolyl group is substituted, another substituent may be substituted via nitrogen or carbon of the carbazole.

[0065] In this specification, the benzocarbazolyl group may be any of the following structures.

[0066]

[0067] In this specification, the dibenzocarbazolyl group may be any of the following structures.

[0068]

[0069] In the present specification, the naphthobenzofuranyl group may be any of the following structures.

[0070]

[0071] In the present specification, the naphthobenzothienyl group may be any of the following structures.

[0072]

[0073] In the present specification, a silyl group contains Si and is a substituent directly connected to the Si atom as a group, and is represented by -Si(R101)(R102)(R103), and R101 to R103 are the same as or different from each other and may each independently be a substituent consisting of at least one of the following: hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group.

[0074] Specific examples of the silyl group include (trimethylsilyl), (triethylsilyl), (tert-butyldimethylsilyl), (vinyldimethylsilyl), (propyldimethylsilyl), (triphenylsilyl), (diphenylsilyl), (phenylsilyl) and the like, but not limited thereto.

[0075] In this specification, the phosphine oxide group is represented by -P(=O)(R104)(R105), and R104 and R105 are the same as or different from each other and may each independently be a substituent consisting of at least one of the following: hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. Specifically, the phosphine oxide group may be substituted with an alkyl group or an aryl group, and the above examples may be applied to alkyl groups and aryl groups. Examples of the phosphine oxide group include a dimethylphosphine oxide group, a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, and the like, but are not limited thereto.

[0076] In the present specification, an amine group is represented by -N(R106)(R107), and R106 and R107 are the same or different from each other and may each independently be a substituent consisting of at least one of the following: hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. The amine group may be selected from the group consisting of -NH2; a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 30. Specific examples of amino groups include methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamino, anthrylamino, 9-methyl-anthrylamino, diphenylamino, phenylnaphthylamino, ditolylamino, phenyltolylamino, triphenylamino, biphenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenyltriphenyleneamino, biphenyltriphenyleneamino, etc., but are not limited thereto.

[0077] In the present specification, the above examples of the aryl group can be applied to the arylene group, except that the arylene group is divalent.

[0078] In the present specification, the above examples of the heteroaryl group can be applied to the heteroarylene group, except that the heteroarylene group is divalent.

[0079] In this specification, an "adjacent" group may refer to a substituent that replaces an atom directly connected to the atom substituted by the corresponding substituent, a substituent that is spatially located closest to the corresponding substituent, or another substituent that replaces the atom substituted by the corresponding substituent. For example, two substituents substituted at the ortho position of a benzene ring and two substituents substituted at the same carbon in an aliphatic ring can be interpreted as groups that are "adjacent" to each other.

[0080] The hydrocarbon ring and heterocyclic ring that the adjacent groups can form include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic heterocyclic ring, and an aromatic heterocyclic ring, and the structures exemplified by the above-mentioned cycloalkyl group, aryl group, heterocycloalkyl group, and heteroaryl group can each be applied to the ring, except that the ring is not a monovalent group.

[0081] In an exemplary embodiment of the present specification, a group not represented by a substituent or a group represented by hydrogen may mean all groups that can be substituted with deuterium. That is, it may indicate that hydrogen (H) or deuterium (D) may be substituted with each other.

[0082] In general, compounds bonded to hydrogen and compounds substituted with deuterium exhibit differences in thermodynamic behavior. This is because the mass of a deuterium atom is twice that of hydrogen, but due to the difference in atomic mass, deuterium is characterized by even lower vibrational energy.

[0083] Furthermore, the single bond dissociation energy between carbon and deuterium is higher than that between carbon and hydrogen. Therefore, the deuterium-substituted structure has the effect of increasing the thermal stability of the molecule and improving the service life of the device by utilizing the increased thermal stability.

[0084] When the compound is deposited on a silicon wafer, the deuterium-containing material tends to accumulate, reducing the distance between molecules. Furthermore, when the surface of the film is observed using an atomic force microscope (AFM), it can be confirmed that the film made of the deuterium-containing compound is deposited with a more uniform surface without any aggregated parts.

[0085] <Heterocyclic Compounds>

[0086] Hereinafter, the heterocyclic compound according to the present specification will be described.

[0087] The heterocyclic compound according to an exemplary embodiment of the present specification may be represented by the following Chemical Formula 1.

[0088] [Chemical Formula 1]

[0089]

[0090] In Chemical Formula 1, the description of each substituent is the same as described above.

[0091] The heterocyclic compound represented by the above formula 1 is a tertiary amine and includes a first substituent around the N of the amine The second substituent and the third substituent

[0092] As represented by Chemical Formula 1, the first substituent controls the hole transport rate, the second substituent regulates structural stability and charge balance, and the third substituent controls the hole transport rate of carbazole, which has strong hole-transporting properties. In summary, when used in an electron blocking layer and / or a hole transport layer, the heterocyclic compound is used to improve electron blocking and / or hole transport properties.

[0093] According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-4.

[0094] [Chemical Formula 1-1]

[0095]

[0096] [Chemical formula 1-2]

[0097]

[0098] [Chemical formula 1-3]

[0099]

[0100] [Chemical formula 1-4]

[0101]

[0102] In Chemical Formulas 1-1 to 1-4, each of X, Ra, Rb, L1 to L3, 11 to 13, R1 to R6, a, b, c, d, e, and f is the same as defined in Chemical Formula 1.

[0103] According to an exemplary embodiment of the present specification, Chemical Formula 1-1 may be represented by any one of the following Chemical Formulas 1-11 to 1-14.

[0104] [Chemical Formula 1-11]

[0105]

[0106] [Chemical formula 1-12]

[0107]

[0108] [Chemical Formula 1-13]

[0109]

[0110] [Chemical Formula 1-14]

[0111]

[0112] In Chemical Formulas 1-11 to 1-14, the description of each substituent is the same as described above.

[0113] According to an exemplary embodiment of the present specification, Chemical Formula 1-2 may be represented by any one of the following Chemical Formulas 1-21 to 1-24.

[0114] [Chemical Formula 1-21]

[0115]

[0116] [Chemical formula 1-22]

[0117]

[0118] [Chemical Formula 1-23]

[0119]

[0120] [Chemical formula 1-24]

[0121]

[0122] In Chemical Formulas 1-21 to 1-24, the description of each substituent is the same as described above.

[0123] According to an exemplary embodiment of the present specification, Chemical Formula 1-3 may be represented by any one of the following Chemical Formulas 1-31 to 1-34.

[0124] [Chemical Formula 1-31]

[0125]

[0126] [Chemical formula 1-32]

[0127]

[0128] [Chemical Formula 1-33]

[0129]

[0130] [Chemical Formula 1-34]

[0131]

[0132] In Chemical Formulas 1-31 to 1-34, the description of each substituent is the same as described above.

[0133] According to an exemplary embodiment of the present specification, Chemical Formula 1-4 may be represented by any one of the following Chemical Formulas 1-41 to 1-44.

[0134] [Chemical Formula 1-41]

[0135]

[0136] [Chemical formula 1-42]

[0137]

[0138] [Chemical formula 1-43]

[0139]

[0140] [Chemical formula 1-44]

[0141]

[0142] In Chemical Formulas 1-41 to 1-44, the description of each substituent is the same as described above.

[0143] When used in an organic light-emitting device, the heterocyclic compound according to the exemplary embodiment may have low driving voltage, high luminous efficiency, and / or long lifespan characteristics.

[0144] According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other and may be each independently a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group containing at least one heteroatom selected from N, O, and S.

[0145] According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other and may be each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group containing at least one heteroatom selected from N, O, and S.

[0146] According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other and may each independently be a C6 to C30 aryl group which is substituted or unsubstituted with one or more substituents selected from deuterium and an alkyl group; or a C2 to C30 heteroaryl group which contains at least one heteroatom selected from N, O and S and is unsubstituted or substituted with one or more substituents selected from deuterium and an alkyl group.

[0147] According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and may each independently be a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted phenanthrenyl group; a substituted or unsubstituted triphenylene group; a substituted or unsubstituted fluorenyl group; a substituted or unsubstituted spirobifluorenyl group; a substituted or unsubstituted dibenzofuranyl group; a substituted or unsubstituted naphthobenzofuranyl group; a substituted or unsubstituted dibenzothienyl group; a substituted or unsubstituted naphthobenzothienyl group; or a substituted or unsubstituted carbazolyl group.

[0148] According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other and may each independently be an unsubstituted or deuterium-substituted phenyl group; an unsubstituted or deuterium-substituted biphenyl group; an unsubstituted or deuterium-substituted terphenyl group; an unsubstituted or deuterium-substituted naphthyl group; an unsubstituted or deuterium-substituted phenanthrenyl group; an unsubstituted or deuterium-substituted triphenylene group; a fluorenyl group that is unsubstituted or substituted with one or more substituents selected from deuterium, an alkyl group, and an aryl group; a spirobifluorenyl group that is unsubstituted or deuterium-substituted; a dibenzofuranyl group that is unsubstituted or deuterium-substituted; a naphthobenzofuranyl group that is unsubstituted or deuterium-substituted; a dibenzothienyl group that is unsubstituted or deuterium-substituted; a naphthobenzothienyl group that is unsubstituted or deuterium-substituted; or a carbazolyl group that is unsubstituted or substituted with one or more substituents selected from deuterium, an aryl group, and a heteroaryl group.

[0149] According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and may each independently be a direct bond; or a substituted or unsubstituted C6 to C40 arylene group.

[0150] According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and may each independently be a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.

[0151] According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and may each independently be a direct bond; or an unsubstituted or deuterium-substituted C6 to C30 arylene group.

[0152] According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and may each independently be a direct bond; or a substituted or unsubstituted phenylene group.

[0153] According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and may each independently be a direct bond; or an unsubstituted or deuterium-substituted phenylene group.

[0154] According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and may each independently be a direct bond; or an unsubstituted or deuterium-substituted phenylene group.

[0155] According to an exemplary embodiment of the present specification, L3 may be a direct bond.

[0156] According to an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other and may each independently be hydrogen; deuterium; a cyano group; a halogen group; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C2 to C40 heterocycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted phosphine oxide group.

[0157] According to an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other and may each independently be hydrogen; deuterium; a cyano group; a halogen group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted phosphine oxide group.

[0158] According to an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other and may each independently be hydrogen; deuterium; a cyano group; a halogen group; a C1 to C30 alkyl group which is unsubstituted or substituted with deuterium; a C3 to C30 cycloalkyl group which is unsubstituted or substituted with deuterium; a C2 to C30 heterocycloalkyl group which is unsubstituted or substituted with one or more substituents selected from an alkyl group, an aryl group, and a heteroaryl group; or a phosphine oxide group which is unsubstituted or substituted with one or more substituents selected from an alkyl group, an aryl group, and a heteroaryl group.

[0159] According to an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other and may each independently be hydrogen; deuterium; a halogen group; an unsubstituted or deuterium-substituted C1 to C30 alkyl group; an unsubstituted or deuterium-substituted C3 to C30 cycloalkyl group; or an unsubstituted or deuterium-substituted C2 to C30 heterocycloalkyl group.

[0160] According to an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and may each independently be hydrogen; or deuterium.

[0161] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 1% to 100%.

[0162] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 10% to 100%.

[0163] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 20% to 100%.

[0164] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 30% to 100%.

[0165] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 60% to 100%.

[0166] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other and may each independently be 0% or 80% to 100%.

[0167] According to an exemplary embodiment of the present specification, deuterium contents of the heterocyclic compounds represented by Chemical Formula 1 are the same as or different from each other, and may each independently be 0% or 90% to 100%.

[0168] According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds.

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] As long as the unique characteristics of the heterocyclic compound represented by Chemical Formula 1 are maintained, various substituents other than the structure exemplified above can be introduced to synthesize heterocyclic compounds with added characteristics of the introduced substituents. For example, by introducing substituents commonly used in hole injection layer materials, hole transport layer materials, hole transport auxiliary layer materials, light-emitting layer materials, electron transport layer materials, electron transport auxiliary layer materials, and electron blocking layer materials used during the manufacture of organic light-emitting devices into the core structure, materials that meet the conditions required for each organic material layer can be synthesized.

[0179] Furthermore, by introducing various substituents into the heterocyclic compound structure represented by Chemical Formula 1, the energy band gap can be finely adjusted, and at the same time, the characteristics at the interface between organic materials can be improved and the use of the material can be diversified.

[0180] <Organic Light-Emitting Device>

[0181] An organic light-emitting device according to an exemplary embodiment of the present specification is an organic light-emitting device including: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, and one or more layers in the organic material layer may contain the above-mentioned heterocyclic compound (represented by Chemical Formula 1).

[0182] According to an exemplary embodiment of the present specification, the organic material layer further includes at least one of a hole transport layer and an electron blocking layer, and at least one of the hole transport layer and the electron blocking layer may include a heterocyclic compound (represented by Chemical Formula 1).

[0183] According to an exemplary embodiment of the present specification, the organic material layer further includes a hole transport layer, and the hole transport layer may include a heterocyclic compound (represented by Chemical Formula 1).

[0184] According to an exemplary embodiment of the present specification, the organic material layer further includes an electron blocking layer, and the electron blocking layer may include a heterocyclic compound (represented by Chemical Formula 1).

[0185] According to an exemplary embodiment of the present specification, the organic material layer further includes a light emitting layer, and the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1.

[0186] In another exemplary embodiment of the present specification, the light emitting layer may include a heterocyclic compound represented by Chemical Formula 1 as a host.

[0187] According to an exemplary embodiment of the present specification, the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1 as a red host.

[0188] According to an exemplary embodiment of the present specification, the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1 as a green host.

[0189] According to an exemplary embodiment of the present specification, the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1 as a blue host.

[0190] According to an exemplary embodiment of the present specification, the first electrode may be a positive electrode, and the second electrode may be a negative electrode.

[0191] According to an exemplary embodiment of the present specification, the first electrode may be a negative electrode, and the second electrode may be a positive electrode.

[0192] According to an exemplary embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the blue organic light emitting device.

[0193] According to an exemplary embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the green organic light emitting device.

[0194] According to an exemplary embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the red organic light emitting device.

[0195] The organic material layer of the organic light-emitting device of the present specification may also have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present specification 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, etc. as organic material layers. However, the structure of the organic light-emitting device is not limited thereto and may include fewer or more organic material layers.

[0196] According to an exemplary embodiment of the present specification, the organic material layer may include an iridium-based dopant.

[0197] According to an exemplary embodiment of the present specification, as the iridium-based dopant, Ir(ppy) 3 , which is a green phosphorescent dopant, may be used, but the iridium-based dopant is not limited thereto.

[0198] According to an exemplary embodiment of the present specification, as an iridium-based dopant, (piq)2(Ir)(acac), which is a red phosphorescent dopant, may be used, but the iridium-based dopant is not limited thereto.

[0199] In the organic light-emitting device of the present specification, as a positive electrode material, a material having a relatively high work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer can be used. Specific examples of the positive electrode material include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and the like, but are not limited thereto.

[0200] In the organic light-emitting device of the present specification, as the negative electrode material, a material having a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of the negative electrode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structured materials such as LiF / Al or LiO2 / Al; and the like, but are not limited thereto.

[0201] In the organic light-emitting device of the present specification, as the hole injection material, a well-known hole injection material can also be used, and for example: phthalocyanine compounds, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429; or starburst-type amine derivatives described in the document [Advanced Material, 6, page 677 (1994)], such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4',4"-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB); polyaniline / dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) which is a soluble conductive polymer; polyaniline / camphorsulfonic acid; or polyaniline / poly(4-styrene-sulfonate); and the like.

[0202] In the organic light-emitting device of the present specification, as the hole transport material, pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. can be used, and low molecular weight materials or polymer materials can also be used.

[0203] In the organic light-emitting device of this specification, as the electron transport material, Diazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc., and low molecular weight materials and polymer materials can also be used.

[0204] In the organic light-emitting device of the present specification, as the electron injection material, for example, LiF is representatively used in the art, but the present specification is not limited thereto.

[0205] In the organic light-emitting device of the present specification, as the light-emitting material, a material that emits red, green, or blue light can be further used, and if necessary, two or more light-emitting materials can be mixed and used. In this case, the two or more light-emitting materials are deposited and used as separate supply sources, or are pre-mixed and deposited and used as a single supply source. In addition, a fluorescent material can also be used as the light-emitting material, but it can also be used as a phosphorescent material. As the light-emitting material, a material that emits light by combining holes and electrons injected from the positive electrode and the negative electrode can also be used alone, but it is also possible to use a material in which a host material and a dopant material participate in light emission together.

[0206] When the host of the light-emitting material is mixed and used, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, two or more types of materials selected from N-type host materials or P-type host materials may be used as host materials for the light-emitting layer.

[0207] The organic light emitting device according to an exemplary embodiment of the present specification may be a top emission type, a bottom emission type, or a dual emission type according to materials to be used.

[0208] The heterocyclic compound according to an exemplary embodiment of the present specification may function even in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like, based on principles similar to those applied to organic light-emitting devices.

[0209] The organic light-emitting device of the present specification may further include one or two or more layers selected from the following: a light-emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

[0210] Figures 1 to 3 The stacking order of electrodes and organic material layers of an organic light-emitting device according to an exemplary embodiment of the present specification is illustrated. However, the scope of the present application is not intended to be limited by these drawings, and the structure of an organic light-emitting device known in the art may also be applied to the present application.

[0211] according to Figure 1 , shows an organic light emitting device in which a positive electrode 200, an organic material layer 300, and a negative electrode 400 are sequentially stacked on a substrate 100. However, the organic light emitting device is not limited to such a structure, and as Figure 2 As shown, an organic light emitting device in which a negative electrode, an organic material layer, and a positive electrode are sequentially stacked on a substrate can also be realized. The composition for an organic light emitting device can be contained in an organic material layer 300, and the organic material layer 300 can be one layer or more layers.

[0212] Figure 3 The case where the positive electrode 200 is provided on the substrate 100 and the organic material layer is provided between the positive electrode 200 and the negative electrode 400 in the multilayer structure is illustrated. Figure 3 The organic light emitting device may include a hole injection layer 301, a hole transport layer 302, a light emitting layer 304, an electron transport layer 305 and an electron injection layer 306 as organic material layers, and according to Figure 4 The organic light emitting device may further include an electron blocking layer 303 between the hole transport layer 302 and the light emitting layer 304. The heterocyclic compound (represented by Chemical Formula 1) may be included in the hole transport layer 302 and / or the electron blocking layer 303.

[0213] The scope of the present application is not limited to the stacked structure described above, and if necessary, other layers except the hole transport layer and / or the electron blocking layer may be omitted, and another necessary functional layer may be further added.

[0214] An organic light emitting device according to an exemplary embodiment of the present specification includes: a first electrode; a first stack disposed on the first electrode and including a first light emitting layer; a second stack disposed on the first stack and including a second light emitting layer; and a second electrode disposed on the second stack.

[0215] according to Figure 5 , when the first electrode on the substrate is a positive electrode, the first stack is arranged on the positive electrode, the second stack is arranged on the first stack, and the second electrode on the second stack can be a negative electrode. The first stack sequentially includes a first hole transport layer, a first stack light-emitting layer (also referred to as a first light-emitting layer) and a first electron transport layer, and the second stack may sequentially include a second hole injection layer, a second hole transport layer, a second stack light-emitting layer (also referred to as a second light-emitting layer), a second electron transport layer and a second electron injection layer. The N-type charge generation layer may be between the first stack and the second stack. Here, the heterocyclic compound represented by Chemical Formula 1 may be included in the second hole transport layer. Alternatively, the heterocyclic compound represented by Chemical Formula 1 may be included in the second electron injection layer.

[0216] In addition, the first stack and the second stack may each independently further include one or more of the above-mentioned hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.

[0217] The heterocyclic compound represented by Chemical Formula 1 may be used to form an organic material layer of an organic light-emitting device, and may more preferably be particularly used as an electron blocking or hole transporting material.

[0218] If necessary, when different types of compounds other than the heterocyclic compound represented by Chemical Formula 1 are mixed to form a mixture, the mixture may be in a pre-mixed form, and the materials in a powdered state may be mixed before forming the organic material layer of the organic light-emitting device, and compounds that are liquid at or above a suitable temperature may be mixed. The composition is solid at a temperature equal to or lower than the melting point of each material and can be maintained in a liquid phase when the temperature is adjusted.

[0219] The heterocyclic compound represented by Chemical Formula 1 may additionally include materials well known in the art, such as solvents and additives.

[0220] <Method for Manufacturing Organic Light-Emitting Device>

[0221] In an exemplary embodiment of the present specification, a method for manufacturing an organic light-emitting device is provided, the method including: preparing a substrate; forming a first electrode on the substrate; forming an organic material layer having one or more layers on the first electrode; and forming a second electrode on the organic material layer, wherein the formation of the organic material layer includes forming an organic material layer having one or more layers by using a heterocyclic compound (represented by the above Chemical Formula 1) according to an exemplary embodiment of the present specification.

[0222] According to an exemplary embodiment of the present specification, in the formation of the organic material layer, the heterocyclic compound represented by Chemical Formula 1 may be formed using a thermal vacuum deposition method.

[0223] An organic light emitting device according to an exemplary embodiment of the present specification may be manufactured by using typical manufacturing methods and materials of an organic light emitting device, except that the above-mentioned heterocyclic compound is used to form an organic material layer.

[0224] Specifically, when manufacturing an organic light-emitting device, the organic material layer can be formed not only by vacuum deposition but also by solution coating. In this article, solution coating means spin coating, dip coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited thereto.

[0225] Hereinafter, the present specification will be described in more detail through examples, but these examples are provided only for illustrating the present application and are not intended to limit the scope of the present application.

[0226] Preparation example.

[0227] [Preparation Example 1] Preparation of Compound 001

[0228]

[0229] 1) Preparation of compound 001-P3

[0230] 2-Bromo-4-chloro-1-nitrobenzene (50 g, 211.46 mmol, 1 eq), [1,1':3',1"-terphenyl]-5'-ylboronic acid (60.86 g, 222.03 mmol, 1.05 eq), Pd(PPh3)4 (12.22 g, 10.57 mmol, 0.05 eq), K2CO3 (73.06 g, 528.65 mmol, 2.5 eq), 1,4-dichloro-1-nitrobenzene (50 g, 211.46 mmol, 1 ...60.86 g, 222.03 mmol, 1.05 eq), Pd(PPh3)4 (12.22 g, 10.57 mmol, 0.05 eq), K2CO3 (73.06 g, 528.65 mmol, 2.5 eq), 1,4-dichloro-1-nitrobenzene (50 g, 211.46 mmol, 1 eq), 1,4-dichloro-1-nitrobenzene ( Alkane (600 ml) and water (150 ml) were put into a vessel, and the resulting mixture was stirred at 120°C for 6 hours.

[0231] After the reaction was terminated by adding water, extraction was performed using MC and water. Thereafter, moisture was removed using MgSO4. The residue was separated by silica gel column to obtain 65 g of compound 001-P3 with a yield of 79.67%.

[0232] 2) Preparation of Compound 001-P2

[0233] Compound 001-P3 (65 g, 168.46 mmol, 1 equivalent), triphenylphosphine (110.47 g, 421.16 mmol, 2.5 equivalents) and 1,2-dichlorobenzene (650 ml) were put into a container, and the resulting mixture was stirred at 180° C. for 4 hours.

[0234] After the reaction was terminated by adding water, extraction was performed using MC and water. Thereafter, moisture was removed using MgSO4. The residue was separated by silica gel column to obtain 39 g of compound 001-P2 with a yield of 65.43%.

[0235] 3) Preparation of Compound 001-P1

[0236] Compound 001-P2 (39 g, 110.22 mmol, 1 equivalent), iodobenzene (A) (68.14 g, 330.66 mmol, 3 equivalents), P(t-Bu)3 (2.14 mL, 4.41 mmol, 0.04 equivalents), Pd2(dba)3 (2.51 g, 2.74 mmol, 0.02 equivalents), NaOtBu (21.18 g, 220.44 mmol, 2 equivalents) and xylene (400 ml) were placed in a container, and the resulting mixture was stirred at 140°C for 1 hour.

[0237] After the reaction was terminated by adding water, extraction was performed using MC and water. Thereafter, moisture was removed using MgSO4. The residue was separated by silica gel column to obtain 34 g of compound 001-P1 with a yield of 71.75%.

[0238] 4) Preparation of Compound 001

[0239] Compound 001-P1 (10 g, 23.26 mmol, 1 equiv), N-phenyldibenzo[b,d]thiophene-4-amine (B) (6.79 g, 24.42 mmol, 1.05 equiv), XPhos (0.45 g, 0.93 mmol, 0.04 equiv), Pd2(dba)3 (0.53 g, 0.58 mmol, 0.02 equiv), NaOtBu (4.47 g, 46.52 mmol, 2 equiv) and xylene (100 ml) were placed in a container, and the resulting mixture was stirred at 140°C for 1 hour.

[0240] After the reaction was terminated by adding water, extraction was performed with MC and water. Thereafter, moisture was removed with MgSO4. The residue was separated by silica gel column to obtain 11.8 g of compound 001 with a yield of 75.85%.

[0241] Each compound was synthesized in the same manner as in Preparation Example 1 above using Intermediate A in Table 1 below and Intermediate B in Table 1 below instead of iodobenzene (A) and 2-N-phenyldibenzo[b,d]thiophene-4-amine (B), respectively.

[0242] [Table 1]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249] [Preparation Example 2] Preparation of Compound 149

[0250]

[0251] Compound 001 (10 g, 14.95 mmol) is added into 50 mL C6D6, and the resulting mixture is purged with nitrogen for 2 hours. 9.41 mL trifluoromethanesulfonic acid (104.66 mmol, 7 equivalents) is added dropwise thereto by a syringe, and the reaction mixture is heated under reflux for 2 hours. After the temperature is cooled to room temperature, 50 mL deuterium oxide is added for extraction, and the organic layer is dried with anhydrous MgSO4, then concentrated using a rotary evaporator. After this, the resulting product is passed through vinyl acetate (EA) slurry to obtain compound 149 (8 g, 76.33%).

[0252] The compounds in Table 2 below were synthesized in the same manner as in Preparation Example 2 above, except for the reaction temperature, time, and equivalents of trifluoromethanesulfonic acid described in Preparation Example 2 above.

[0253] [Table 2]

[0254] Compound number Reaction temperature Reaction time Trifluoromethanesulfonic acid equivalent Yield 157 RT 1HR 5 equivalents 68％ 159 Reflow 2HR 7 equivalents 77％ 160 Reflow 2HR 3 equivalents 70％

[0255] The compounds were prepared in the same manner as in the Preparation Examples, and the synthesis determination results thereof are shown in Tables 3 and 4. Table 3 shows 1Table 4 shows the measured values ​​of H NMR (CDCl 3 , 400 MHz) and the measured values ​​of field desorption mass spectrometry (FD-MS).

[0256] [Table 3]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] [Table 4]

[0263]

[0264]

[0265] Experimental example.

[0266] <Experimental Example 1>

[0267] 1) Manufacturing of organic light-emitting devices

[0268] Comparative Example 1

[0269] A transparent electrode ITO film obtained from OLED glass (manufactured by Samsung-Corning Co., Ltd.) was ultrasonically cleaned using trichloroethylene, acetone, ethanol, and distilled water for 5 minutes each, followed by placement in isopropyl alcohol, storage, and subsequent use. Next, the ITO substrate was placed in a substrate holder of a vacuum deposition apparatus, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in the vacuum deposition apparatus's cell.

[0270]

[0271] Then, the air in the chamber is evacuated until the vacuum level in the chamber reaches 10 -6 Then, a current is applied to the cell to evaporate 2-TNATA to deposit a thickness of 100 nm on the ITO substrate. A hole injection layer with a thickness of 1000 nm was deposited on the hole injection layer by placing the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) into another unit in a vacuum deposition apparatus and applying a current to the unit to evaporate NPB. hole transport layer.

[0272]

[0273] The hole injection layer and the hole transport layer are formed as described above, and then a blue light-emitting material having the following structure is deposited thereon as a light-emitting layer. Specifically, a blue light-emitting host material H1 is vacuum-deposited on a unit in a vacuum deposition device to a thickness of A dopant material D1 emitting blue light is vacuum deposited thereon in an amount of 5% based on the host material.

[0274]

[0275] Subsequently, a compound having the following structural formula E1 as an electron transport layer is deposited to a thickness of

[0276]

[0277] By depositing lithium fluoride (LiF) as an electron injection layer to a thickness of And the thickness of the Al negative electrode is to manufacture OLED devices.

[0278] At the same time, all the organic compounds required to make the OLED device are made in 10 -8 Support up to 10 -6 The product is purified by vacuum sublimation under a support and used in the manufacture of OLEDs.

[0279] Comparative Examples 2 to 7 and Examples 1 to 42

[0280] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the heterocyclic compounds in Table 5 below were used instead of NPB used in forming the hole transport layer in Experimental Example 1.

[0281] 2) Evaluation of organic light-emitting devices

[0282] For the organic light emitting device manufactured as described above, electroluminescence (EL) characteristics were measured using M7000 manufactured by McScience Inc., and the measurement results were analyzed at a reference luminance of 700 cd / m 2 The life measurement device (M6000) manufactured by McScience Inc. was used to measure T 95 The driving voltage, luminous efficiency, color coordinates (CIE) and service life of the blue organic light emitting device manufactured according to the present invention were measured and the results are shown in Table 5 below.

[0283] [Table 5]

[0284]

[0285]

[0286]

[0287] The structures of comparative compounds A to F are as follows.

[0288]

[0289] As can be seen from the results in Table 5, the organic light-emitting devices using the heterocyclic compounds of the present invention as hole transport materials have low driving voltages and significantly improved luminous efficiency and lifetimes compared to Comparative Examples 1 to 7. In particular, it can be seen that the lifetimes of the organic light-emitting devices of Examples 1 to 42 are significantly improved by 16.6% or more compared to Comparative Examples 1 to 7.

[0290] The reason for this result is that Compound A used in Comparative Example 2 has an amine structure different from that of the present invention and does not have a substituent containing a heteroatom (O or S). In addition, the four phenyl groups are substituted based on the benzene rings at both ends of the carbazole group, which makes the hole-transporting properties higher than desired. For this reason, it is impossible to achieve a hole mobility suitable for the device proposed by the present invention. Unlike Comparative Example 6, in which the substituents are located at the 2- and 4-positions, the present invention has a skeleton in which the substituents are located at the 1- and 3-positions, and has the advantage of exhibiting suitable physical properties as a hole transport layer by easily achieving a hole mobility more suitable than when used as a material for the organic light-emitting device of the present invention.

[0291] In addition, Comparative Examples 3 and 4 are different from the heterocyclic compound of the present invention in terms of the type of substituents (the heterocyclic compound of the present invention includes dibenzofuranyl and / or dibenzothiophene as substituents); in addition, Comparative Example 5 has a symmetrical dicarbazole structure, but is not an amine; Comparative Example 6 has the position of two phenyl groups substituted on carbazole outside the structure of the present invention; and Comparative Example 7 is different from the heterocyclic compound of the present invention in that the dibenzofuranyl and / or dibenzothiophene group is directly bonded to the benzene ring on the other side of the carbazole where the two phenyl groups are substituted, so the compound is not an amine. The heterocyclic compound specified in the present invention can achieve hole mobility at a rate suitable for the device by suitable bond lengths and strengths of the first to third substituents, thereby effectively transporting holes by forming a more stable compound without decomposing or destroying the compound. In addition, when the compound of Comparative Example 5 is used to form a film on a device, the film-forming properties deteriorate, so that there is a disadvantage that the device properties may be significantly deteriorated due to difficulty in forming a uniform film.

[0292] Therefore, it was confirmed that the heterocyclic compound of the present invention enhanced electron transport characteristics or stability and was thus excellent in all device characteristics such as driving, efficiency, and lifespan.

[0293] <Experimental Example 2>

[0294] 1) Manufacturing of organic light-emitting devices

[0295] Comparative Example 8

[0296] A transparent electrode ITO film obtained from OLED glass (manufactured by Samsung-Corning Co., Ltd.) was ultrasonically cleaned using trichloroethylene, acetone, ethanol, and distilled water for 5 minutes each, followed by placement in isopropyl alcohol, storage, and subsequent use. Next, the ITO substrate was placed in a substrate holder of a vacuum deposition apparatus, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in the vacuum deposition apparatus's cell.

[0297]

[0298] Then, the air in the chamber is evacuated until the vacuum level in the chamber reaches 10 -6 Then, a current is applied to the cell to evaporate 2-TNATA to deposit a thickness of 100 nm on the ITO substrate. A hole injection layer with a thickness of 1000 nm was deposited on the hole injection layer by placing the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) into another unit in a vacuum deposition apparatus and applying a current to the unit to evaporate NPB. Subsequently, 1,3,5-tris(3-pyridyl-3-phenyl)benzene (TmPyPB) was used to form a hole transport layer with a thickness of electron blocking layer.

[0299]

[0300] The electron blocking layer is formed as described above, and then a blue light emitting material having the following structure is deposited thereon as a light emitting layer. Specifically, a blue light emitting host material H1 is vacuum deposited on a unit in a vacuum deposition device to a thickness of A dopant material D1 emitting blue light is vacuum deposited thereon in an amount of 5% based on the host material.

[0301]

[0302] Subsequently, a compound having the following structural formula E1 as an electron transport layer is deposited to a thickness of

[0303]

[0304] By depositing lithium fluoride (LiF) as an electron injection layer to a thickness of And the thickness of the Al negative electrode is At the same time, all the organic compounds required to manufacture the OLED device are made in 10 -8 Support up to 10 -6 The product is purified by vacuum sublimation under a support and used in the manufacture of OLEDs.

[0305] Comparative Examples 9 to 14 and Examples 43 to 84

[0306] An organic light emitting device was manufactured in the same manner as in Comparative Example 8, except that in Experimental Example 2, a heterocyclic compound shown in Table 6 below was used to form a film having a thickness of The electron blocking layer is replaced by a thickness of And contains an electron blocking layer of TmPyPB.

[0307] 2) Evaluation of organic light-emitting devices

[0308] For the organic light emitting device manufactured as described above, electroluminescence (EL) characteristics were measured using M7000 manufactured by McScience Inc., and the measurement results were analyzed at a reference luminance of 700 cd / m 2 The life measurement device (M6000) manufactured by McScience Inc. was used to measure T 95 .

[0309] The driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the blue organic light emitting device manufactured according to the present invention were measured and the results are shown in Table 6 below.

[0310] [Table 6]

[0311]

[0312]

[0313]

[0314]

[0315] The structures of comparative compounds A to F are as follows.

[0316]

[0317] As can be seen from the results in Table 6, the organic light-emitting devices using the electron-blocking material for blue organic light-emitting devices of the present invention have lower driving voltages and improved service life and luminous efficiency compared to Comparative Examples 8 to 14. In particular, it can be seen that the service life of the organic light-emitting devices of Examples 43 to 84 is significantly improved by 27.7% or more compared to Comparative Examples 8 to 14.

[0318] In addition, unlike Comparative Example 9 having a 4-substituted structure of a benzene ring based on a carbazole group, the heterocyclic compound of the present invention has a 3-substituted structure of a benzene ring based on a carbazole group, and unlike Comparative Example 13 having a skeleton in which substituents are located at the 2- and 4-positions, the compound of the present invention has a skeleton in which substituents are located at the 1- and 3-positions, and therefore has the advantage that the LUMO energy level can be adjusted to a level that is more suitable for the electron blocking layer in the device proposed by the present invention.

[0319] In addition, Comparative Example 12 has a symmetrical structure and has a disadvantage in that, when preparing an electron blocking layer, it is not easy to form a uniform film because the crystallinity is too high, so the device characteristics may be significantly deteriorated. Although Comparative Examples 10, 11, and 14 have asymmetrical structures, compared with the heterocyclic compounds specified in the present invention and the compounds bonded to substituents such as amino groups and aryl groups, electron and hole mobilities suitable for devices used in the present invention cannot be achieved.

[0320] Furthermore, when electrons fail to bind in the light-emitting layer and pass through the hole transport layer to the positive electrode, the efficiency and lifespan of the OLED device decrease. Using a compound with high LUMO and T1 energy levels as an electron blocking layer to prevent this phenomenon increases the probability that electrons that pass through the light-emitting layer to the positive electrode will form excitons in the light-emitting layer. These results confirm that the heterocyclic compounds of the present invention excel in all aspects of drive, efficiency, and lifespan.

[0321] The present invention is not limited to the embodiments described, but can be prepared in various forms, and those skilled in the art will understand that the present invention can be implemented in another specific form without changing the technical spirit or basic characteristics of the present invention. Therefore, it should be understood that the above embodiments are only illustrative in all aspects and not restrictive.

Claims

1. A heterocyclic compound represented by the following Chemical Formula 1: [Chemical Formula 1] in, In Chemical Formula 1, X is O; or S, Ra and Rb are the same as or different from each other and are each independently a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, L1 to L3 are the same as or different from each other and are each independently a direct bond; or a substituted or unsubstituted C6 to C60 arylene group, Each of l1 to l3 is an integer from 0 to 4, and When each of l1 to l3 is an integer of 2 or greater, the substituents in the brackets are the same as or different from each other, R1 to R6 are the same as or different from each other and are each independently hydrogen; deuterium; a cyano group; a halogen group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted phosphine oxide group. a is an integer from 0 to 4, Each of b and c is an integer from 0 to 3, Each of d and e is an integer from 0 to 5, f is an integer from 0 to 2, and When each of a, b, c, d, e, and f is an integer of 2 or greater, the substituents in the brackets are the same as or different from each other.

2. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4: [Chemical Formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] In Chemical Formulas 1-1 to 1-4, Each of X, Ra, Rb, L1 to L3, 11 to 13, R1 to R6, a, b, c, d, e, and f is the same as defined in Chemical Formula 1.

3. The heterocyclic compound according to claim 1, wherein Ra and Rb are the same as or different from each other and are each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group containing at least one heteroatom selected from N, O and S. 4 . The heterocyclic compound according to claim 1 , wherein L 1 to L 3 are the same as or different from each other and are each independently a direct bond; or a substituted or unsubstituted C 6 to C 30 arylene group. The heterocyclic compound according to claim 1 , wherein R 1 to R 6 are the same as or different from each other and are each independently hydrogen; or deuterium. The heterocyclic compound according to claim 1 , wherein the deuterium content of the heterocyclic compound represented by Chemical Formula 1 is 0%, or 1% to 100%.

7. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

8. An organic light-emitting device, comprising: a first electrode; a second electrode disposed facing the first electrode; as well as an organic material layer having one or more layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the heterocyclic compound according to any one of claims 1 to 7. 9 . The organic light-emitting device according to claim 8 , wherein the organic material layer further comprises at least one of a hole transport layer and an electron blocking layer, and at least one of the hole transport layer and the electron blocking layer comprises the heterocyclic compound.

10. The organic light-emitting device according to claim 8, wherein the organic light-emitting device further comprises one or two or more layers selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

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