Heterocyclic compound and organic light-emitting device comprising same

Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1 having a specific structure, and an organic light-emitting device comprising same. The heterocyclic compound according to the present embodiment can lower the driving voltage of the device, improve luminous efficiency, and improve lifespan characteristics of the device.

Description

Heterocyclic compound and organic light-emitting device containing the same

[0001] The present specification relates to a heterocyclic compound and an organic light-emitting device comprising the same.

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0082137, filed with the Korean Intellectual Property Office on June 26, 2023, the entire contents of which are incorporated herein by reference.

[0003] Organic light-emitting diodes are a type of self-luminous display device that have the advantages of a wide viewing angle, excellent contrast, and fast response speed.

[0004] Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light-emitting device of this structure, electrons and holes injected from the two electrodes combine in the organic thin film, forming pairs and then disappearing, emitting light. The organic thin film may be composed of a single layer or multiple layers, as needed.

[0005] The material of the organic thin film may have a light-emitting function as needed. For example, the organic thin film material may be a compound that can form a light-emitting layer on its own, or a compound that can act as a host or dopant in a host-dopant light-emitting layer. In addition, the material of the organic thin film may be a compound that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection.

[0006] To improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of materials for organic thin films is continuously required.

[0007] [Prior Art Literature]

[0008] (Patent Document 1) U.S. Patent No. 4,356,429

[0009] The present specification provides a heterocyclic compound and an organic light-emitting device including the same.

[0010] One embodiment of the present specification provides a heterocyclic compound represented by the following chemical formula 1.

[0011] [Chemical Formula 1]

[0012]

[0013] In the above chemical formula 1,

[0014] X1 and X2 are the same or different from each other, and are each independently O; or S,

[0015] R1 to R3 are the same or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)RR'; and -SiRR'R",

[0016] R, R' and R" are the same or different from each other, and each independently represents a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0017] L1 to L4 are the same or different from each other, and each independently represents a direct bond; or a substituted or unsubstituted C6 to C60 arylene group,

[0018] Ar1 to Ar3 are the same or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0019] a is an integer from 0 to 3,

[0020] b is 0 or 1,

[0021] c is an integer from 0 to 4,

[0022] m, n, j, and k are each integers from 0 to 4,

[0023] p, q and r are integers from 1 to 4, respectively,

[0024] When each of a, c, m, n, j, k, p, q and r is 2 or more, the substituents within the parentheses are the same or different.

[0025] Another embodiment of the present specification provides an organic light-emitting device comprising a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers comprises at least one heterocyclic compound represented by the chemical formula 1.

[0026] The heterocyclic compound described herein, when used in an organic light-emitting device, can lower the driving voltage of the device, improve the luminous efficiency, and enhance the lifespan characteristics of the device. Specifically, the heterocyclic compound of the present invention is a 5-ring heterocyclic compound having a specific fused structure represented by Chemical Formula 1 ( ) as a core structure, and two substituents, one of the 1st to 4th carbons of the terminal ring. The first substituent (arylamine group) represented by and the 9th or 10th carbon of the central ring It is characterized by an asymmetric structure in which a second substituent, represented by , is connected.

[0027] As described above, the heterocyclic compound according to the present specification has a structural feature in which the arylamine group corresponding to the first substituent is bonded to one of the carbons 1 to 4 of the core, thereby having an appropriate HOMO level property, thereby delocalizing the energy level, thereby stabilizing the HOMO energy while effectively preventing electrons from flowing over from the opposite side of the electron transport layer, and controlling the band gap and T1 (energy level of triplet state) value through excellent hole transport characteristics, thereby controlling the hole transport ability and electron blocking ability, thereby lowering the operating voltage of the device and improving the light efficiency.

[0028] In addition, the structure corresponding to the second substituent at the 9th or 10th carbon atom in the center of the core (Ar3 is an aryl group or heteroaryl group) is a substituent that pushes electrons through excellent electron donating group characteristics, making the ring electron-rich and giving it excellent electron injection characteristics.

[0029] Figures 1 to 4 are drawings each exemplifying a laminated structure of an organic light-emitting device according to one embodiment of the present specification.

[0030] [Explanation of symbols]

[0031] 100: Substrate

[0032] 200: Bipolar

[0033] 300: Organic layer

[0034] 301: Hole injection layer

[0035] 302: Hole transport layer

[0036] 303: Electronic barrier layer

[0037] 304: Emissive layer

[0038] 305: Electron transport layer

[0039] 306: Electron injection layer

[0040] 400: Cathode

[0041] Hereinafter, the present specification will be described in more detail.

[0042] In this specification, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0043] In this specification, the chemical formula means the position where it is combined.

[0044] The term "substitution" above means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of substitution is not limited as long as it is a position where a hydrogen atom is replaced, i.e. a position where a substituent can be replaced, and when two or more are replaced, the two or more substituents may be the same or different from each other.

[0045] In this specification, "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a C1 to C60 alkyl group; a C2 to C60 alkenyl group; a C2 to C60 alkynyl group; a C3 to C60 cycloalkyl group; a C2 to C60 heterocycloalkyl group; a C6 to C60 aryl group; a C2 to C60 heteroaryl group; a silyl group; a phosphine oxide group; and an amine group, or a substituent in which two or more substituents selected from the above substituents are linked.

[0046] In this specification, "when no substituent is indicated in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, deuterium ( 2 H, Deuterium) is an isotope of hydrogen, so some hydrogen atoms may be deuterium.

[0047] In this specification, "when no substituent is indicated in the chemical formula or compound structure" may mean that all positions that can be substituted are hydrogen or deuterium. That is, in the case of deuterium, it is an isotope of hydrogen, and some hydrogen atoms may be the isotope deuterium, and in this case, the deuterium content may be 0% to 100%.

[0048] In one embodiment of the present application, in the case where "no substituent is indicated in the chemical formula or compound structure", if the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents are hydrogen, etc., and deuterium is not explicitly excluded, hydrogen and deuterium may be used in combination in the compound.

[0049] In one embodiment of the present application, deuterium is an element having a deuteron, which is one of the isotopes of hydrogen and is composed of one proton and one neutron, as its nucleus, and can be expressed as hydrogen-2, and its element symbol is D or 2 It can also be written as H.

[0050] In one embodiment of the present application, an isotope means an atom having the same atomic number (Z) but a different mass number (A). An isotope can also be interpreted as an element having the same number of protons but a different number of neutrons.

[0051] In one embodiment of the present application, the meaning of the content T% of a specific substituent can be defined as T2 / T1×100 = T% when the total number of substituents that the basic compound can have is defined as T1, and the number of specific substituents among them is defined as T2.

[0052] That is, in one example, In the phenyl group represented by , the content of deuterium of 20% means that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and if the number of deuterium among them is 1 (T2 in the formula), it can be expressed as 20%. In other words, the content of deuterium of 20% in the phenyl group can be expressed by the structural formula below.

[0053]

[0054] Additionally, in one embodiment of the present application, the term “phenyl group having a deuterium content of 0%” may mean a phenyl group that does not contain deuterium atoms, i.e., has 5 hydrogen atoms.

[0055] In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

[0056] In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The alkyl group may have 1 to 60 carbon atoms, specifically 1 to 40 carbon atoms, and more specifically 1 to 20 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, Examples include, but are not limited to, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0057] In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include, but are not limited to, a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, and a styrenyl group.

[0058] In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkynyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms.

[0059] In the present specification, the alkoxy group may be straight-chain, branched-chain, or cyclic. The carbon number of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but is not limited thereto.

[0060] In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, etc. The cycloalkyl group may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, and more specifically 5 to 20 carbon atoms. Specifically, there are, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.

[0061] In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a heteroatom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, etc. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 20 carbon atoms.

[0062] In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means a group in which an aryl group is directly connected to or condensed with another ring group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, etc. The aryl group includes a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the above aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, and condensed ring groups thereof.

[0063] In this specification, the terphenyl group may be selected from the following structures.

[0064]

[0065] In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be combined with each other to form a ring.

[0066] When the above fluorenyl group is substituted, the following structures may be exemplified, but are not limited thereto.

[0067]

[0068] In the present specification, the heteroaryl group includes S, O, Se, N or Si as a heteroatom, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic ring means a group in which a heteroaryl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, etc. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms.Specific examples of the above heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a diazinyl group, an oxazinyl group, a thiazinyl group, a deoxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a quinozolinyl group, a naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridinyl group, a diazanaphthalenyl group, Triazindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilole group, spirobi(dibenzosilole) group, dihydrophenazinyl group, phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10,11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, Examples thereof include, but are not limited to, a phthalazinyl group, a naphthyridinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, a 2,3-dihydrobenzo[b]thiophene group, a 2,3-dihydrobenzofuran group, a 5,10-dihydrodibenzo[b,e][1,4]azasilinyl group, a pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group, a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, and a 5,11-dihydroindeno[1,2-b]carbazolyl group.

[0069] In the present specification, a silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, 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 composed of at least one of 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.

[0070] A specific example of a cylinder is (trimethylsilyl group), (triethylsilyl group), (t-butyldimethylsilyl group), (vinyldimethylsilyl group), (propyldimethylsilyl group), (triphenylsilyl group), (diphenylsilyl group), (phenylsilyl group), but is not limited thereto.

[0071] In the present 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 can each independently be a substituent composed of at least one of 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, it can be substituted with an alkyl group or an aryl group, and the above-described examples can be applied to the alkyl group and the aryl group. For example, the phosphine oxide group includes, but is not limited to, a dimethylphosphine oxide group, a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, etc.

[0072] In the present specification, the amine group is represented by -N(R106)(R107), and R106 and R107 are the same as or different from each other, and can each independently be a substituent composed of at least one of 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 can 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 is not particularly limited, but is preferably 1 to 30. Specific examples of the above amine group include, but are not limited to, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylenylamine group, and a biphenyltriphenylenylamine group.

[0073] In the present specification, the arylene group may be applied to the examples of the aryl group described above, except that it is a divalent group.

[0074] In the present specification, the heteroarylene group may be applied to the examples of the heteroaryl group described above, except that it is a divalent group.

[0075] One embodiment of the present specification provides a heterocyclic compound represented by the following chemical formula 1.

[0076] [Chemical Formula 1]

[0077]

[0078] In the above chemical formula 1,

[0079] X1 and X2 are the same or different from each other, and are each independently O; or S,

[0080] R1 to R3 are the same or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)RR'; and -SiRR'R",

[0081] R, R' and R" are the same or different from each other, and each independently represents a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0082] L1 to L4 are the same or different from each other, and each independently represents a direct bond; or a substituted or unsubstituted C6 to C60 arylene group,

[0083] Ar1 to Ar3 are the same or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0084] a is an integer from 0 to 3,

[0085] b is 0 or 1,

[0086] c is an integer from 0 to 4,

[0087] m, n, j, and k are each integers from 0 to 4,

[0088] p, q and r are integers from 1 to 4, respectively,

[0089] When each of a, c, m, n, j, k, p, q and r is 2 or more, the substituents within the parentheses are the same or different.

[0090] In one embodiment of the present specification, the chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-4.

[0091] [Chemical Formula 1-1]

[0092]

[0093] [Chemical Formula 1-2]

[0094]

[0095] [Chemical Formula 1-3]

[0096]

[0097] [Chemical Formula 1-4]

[0098]

[0099] In the above chemical formulas 1-1 to 1-4,

[0100] X1, X2, R1 to R3, L1 to L4, Ar1 to Ar3, a, b, c, m, n, j, k, p, q and r are the same as defined in the above chemical formula 1.

[0101] In one embodiment of the present specification, the chemical formula 1 may be represented by the following chemical formula 1-5 or 1-6.

[0102] [Chemical Formula 1-5]

[0103]

[0104] [Chemical Formula 1-6]

[0105]

[0106] In the above chemical formulas 1-5 and 1-6,

[0107] X1, X2, R1 to R3, L1 to L4, Ar1 to Ar3, a, c, m, n, j, k, p, q and r are the same as defined in the above chemical formula 1.

[0108] In one embodiment of the present specification, R1 to R3 are the same or different from each other, and each independently may be selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C2 to C40 alkenyl group; a substituted or unsubstituted C2 to C40 alkynyl group; a substituted or unsubstituted C1 to C40 alkoxy group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C2 to C40 heterocycloalkyl group; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; -P(=O)RR'; and -SiRR'R".

[0109] In one embodiment of the present specification, R1 to R3 are the same or different from each other, and each independently may be selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C2 to C20 alkenyl group; a substituted or unsubstituted C2 to C20 alkynyl group; a substituted or unsubstituted C1 to C20 alkoxy group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; a substituted or unsubstituted C6 to C20 aryl group; a substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)RR'; and -SiRR'R".

[0110] In one embodiment of the present specification, R1 to R3 are the same or different from each other, and each independently may be selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C2 to C20 alkenyl group; a substituted or unsubstituted C2 to C20 alkynyl group; a substituted or unsubstituted C1 to C20 alkoxy group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; -P(=O)RR'; and -SiRR'R".

[0111] In one embodiment of the present specification, R1 to R3 are the same or different from each other, and each independently may be hydrogen or deuterium.

[0112] In one embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently may be a direct bond; or a substituted or unsubstituted C6 to C40 arylene group.

[0113] In one embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently may be a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.

[0114] In one embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently may be a direct bond; or a C6 to C20 arylene group substituted or unsubstituted with deuterium.

[0115] In one embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently may be a direct bond; or a phenylene group substituted or unsubstituted with deuterium.

[0116] In one embodiment of the present specification, Ar1 to Ar3 may be the same as or different from each other, and may each independently be a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.

[0117] In one embodiment of the present specification, Ar1 to Ar3 may be the same as or different from each other, and may each independently be a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.

[0118] In one embodiment of the present specification, Ar1 to Ar3 may be the same as or different from each other, and may each independently be a C6 to C30 aryl group substituted or unsubstituted with deuterium; or a C2 to C30 heteroaryl group substituted or unsubstituted with deuterium.

[0119] In one embodiment of the present specification, Ar1 and Ar2 may be the same as or different from each other, and each independently be a phenyl group unsubstituted or substituted with deuterium; a biphenyl group unsubstituted or substituted with deuterium; a terphenyl group unsubstituted or substituted with deuterium; a naphthyl group unsubstituted or substituted with deuterium; an anthracenyl group unsubstituted or substituted with deuterium; a phenanthrenyl group unsubstituted or substituted with deuterium; a fluorenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, a methyl group, and a phenyl group; a spirobifluorenyl group unsubstituted or substituted with deuterium; a dibenzofuran group unsubstituted or substituted with deuterium; or a dibenzothiophene group unsubstituted or substituted with deuterium.

[0120] In one embodiment of the present specification, Ar3 may be a phenyl group substituted or unsubstituted with deuterium; a biphenyl group substituted or unsubstituted with deuterium; a terphenyl group substituted or unsubstituted with deuterium; a naphthyl group substituted or unsubstituted with deuterium; a dibenzofuran group substituted or unsubstituted with deuterium; or a dibenzothiophene group substituted or unsubstituted with deuterium.

[0121] In one embodiment of the present specification, R, R' and R" may be the same as or different from each other, and may each independently be a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.

[0122] In one embodiment of the present specification, R, R' and R" may be the same as or different from each other, and may each independently be a substituted or unsubstituted C1 to C20 alkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0123] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 0% to 100%.

[0124] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 0%.

[0125] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 30% to 100%.

[0126] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 50% to 100%.

[0127] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 70% to 100%.

[0128] In one embodiment of the present specification, the deuterium content of the chemical formula 1 may be 100%.

[0129] In one embodiment of the present specification, the deuterium content of the heterocyclic compound of the chemical formula 1 satisfies the above range, and the photochemical characteristics of the compound not containing deuterium and the compound containing deuterium are almost similar, but when deposited on a thin film, the material containing deuterium tends to be packed with a narrower intermolecular distance.

[0130] Accordingly, by fabricating an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage, it can be confirmed that among the heterocyclic compounds of chemical formula 1 of the present invention, the compound containing deuterium exhibits much more balanced charge transport characteristics than the compound not containing deuterium.

[0131] Additionally, when looking at the surface of a thin film using an atomic force microscope (AFM), it can be confirmed that the thin film made of a compound containing deuterium is deposited on a more uniform surface without any aggregated areas.

[0132] Additionally, since the single bond dissociation energy of carbon and deuterium is higher than the single bond dissociation energy of carbon and hydrogen, when the deuterium content of the heterocyclic compound of chemical formula 1 of the present invention corresponds to a compound satisfying the above range, the stability of the entire molecule increases, thereby further improving the device lifespan.

[0133] In one embodiment of the present specification, the chemical formula 1 may be represented by any one of the following.

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] In addition, by introducing various substituents into the structure of the heterocyclic compound of the above chemical formula 1, it is possible to synthesize a compound having the unique characteristics of the introduced substituent. For example, by introducing a substituent mainly used in materials used in a hole transport layer, a hole transport auxiliary layer, and / or a light-emitting layer used in the manufacture of an organic light-emitting device into the core structure, it is possible to synthesize a material that satisfies the conditions required for each layer.

[0162] In addition, by introducing various substituents into the structure of the above chemical formula 1, it is possible to finely control the energy band gap, while improving the properties at the interface between organic substances and diversifying the uses of the material.

[0163] In another embodiment of the present specification, an organic light-emitting device is provided, comprising: a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers comprises at least one of the above-described heterocyclic compounds.

[0164] In one embodiment of the present specification, the organic layer includes at least one layer of a hole transport layer, a hole transport auxiliary layer, and an electron blocking layer, and at least one layer of the hole transport layer, the hole transport auxiliary layer, and the electron blocking layer may include at least one type of the heterocyclic compound.

[0165] In one embodiment of the present specification, the organic layer includes a hole transfer layer (HTL), and the hole transfer layer may include one or more types of the heterocyclic compound.

[0166] In one embodiment of the present specification, the organic layer includes a hole transport auxiliary layer (prime HTL), and the hole transport auxiliary layer may include one or more types of the heterocyclic compound.

[0167] In one embodiment of the present specification, the organic layer includes an electron blocking layer (EBL), and the electron blocking layer may include one or more types of the heterocyclic compound.

[0168] In one embodiment of the present specification, the organic layer includes an emission layer (EML), and the emission layer may include one or more types of the heterocyclic compound.

[0169] In one embodiment of the present specification, the light-emitting layer includes a host material, and the host material may include one or more types of the heterocyclic compound.

[0170] In one embodiment of the present specification, the light-emitting layer includes a red host material, and the red host material may include one or more of the heterocyclic compounds.

[0171] In one embodiment of the present specification, the light-emitting layer includes a green host material, and the green host material may include one or more of the heterocyclic compounds.

[0172] In one embodiment of the present specification, the light-emitting layer includes a blue host material, and the blue host material may include one or more of the heterocyclic compounds.

[0173] In one embodiment of the present specification, the light-emitting layer includes a P-type host material, and the P-type host material may include one or more of the heterocyclic compounds.

[0174] In one embodiment of the present specification, the organic light-emitting device may further include 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.

[0175] In one embodiment of the present specification, the organic light-emitting device may further include one layer 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.

[0176] In one embodiment of the present specification, the organic light-emitting device may further include 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.

[0177] The organic layer of the organic light-emitting device of the present invention may be formed as a single layer structure, but may also be formed as a multilayer structure in which two or more organic layers are laminated. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light-emitting layer, an electron transport layer, an electron transport auxiliary layer, an electron injection layer, etc. as the organic layers. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

[0178] In one embodiment of the present specification, the first electrode may be an anode, and the second electrode may be a cathode.

[0179] In another embodiment of the present specification, the first electrode may be a cathode and the second electrode may be an anode.

[0180] An organic light-emitting device according to one embodiment of the present specification can be manufactured using a conventional method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using a heterocyclic compound represented by the above chemical formula 1.

[0181] The heterocyclic compound represented by the above chemical formula 1 can be formed into an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution coating method refers to, but is not limited to, spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc.

[0182] In another embodiment of the present specification, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by the chemical formula 1 may be used as a material of the red organic light-emitting device. For example, the heterocyclic compound represented by the chemical formula 1 may be included in a hole transport layer, a hole transport auxiliary layer, an electron blocking layer, or a light-emitting layer of the red organic light-emitting device.

[0183] In another embodiment of the present specification, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by the chemical formula 1 may be used as a material of the green organic light-emitting device. For example, the heterocyclic compound represented by the chemical formula 1 may be included in a hole transport layer, a hole transport auxiliary layer, an electron blocking layer, or a light-emitting layer of the green organic light-emitting device.

[0184] In one embodiment of the present specification, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by the chemical formula 1 may be used as a material of the blue organic light-emitting device. For example, the heterocyclic compound represented by the chemical formula 1 may be included in a hole transport layer, a hole transport auxiliary layer, an electron blocking layer, or a light-emitting layer of the blue organic light-emitting device.

[0185] The organic light-emitting device of the present invention may further include one or more organic layers selected from the group consisting of a light-emitting layer, a hole injection layer, an electron injection layer, an electron transport layer, and a hole blocking layer.

[0186] The stacking order of electrodes and organic layers of an organic light-emitting device according to one embodiment of the present disclosure is exemplified in Figures 1 to 4. 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.

[0187] According to FIG. 1, an organic light-emitting device is illustrated in which an anode (200), an organic layer (300), and a cathode (400) are sequentially laminated on a substrate (100). However, the present invention is not limited to this structure, and an organic light-emitting device in which a cathode, an organic layer, and an anode are sequentially laminated on a substrate, as shown in FIG. 2, may also be implemented.

[0188] FIG. 3 and FIG. 4 illustrate a case where the organic layer is multilayer. The organic light-emitting device according to FIG. 3 sequentially includes an anode (200), a hole injection layer (301), a hole transport layer (302), an electron blocking layer (303), a light-emitting layer (304), an electron transport layer (305), an electron injection layer (306), and a cathode (400) on a substrate (100), and FIG. 4 is an example of a 2-stack tandem structure, in which an N-type charge generation layer is interposed between a first stack composed of a first hole transport layer, a first stack light-emitting layer, and a first electron transport layer, and a second stack composed of a second hole transport layer, a second stack light-emitting layer, a second electron transport layer, and a second electron injection layer, wherein the second hole transport layer may include a heterocyclic compound according to the present invention.

[0189] However, the scope of the present application is not limited by such a laminated structure, and layers other than the light-emitting layer may be omitted as needed, and other necessary functional layers may be added.

[0190] For example, the organic layer may further include a hole transport auxiliary layer (not shown), and the hole transport auxiliary layer may be included between the hole transport layer (302) and the electron blocking layer (303) based on the laminated structure.

[0191] The organic layer containing the heterocyclic compound of the above chemical formula 1 may additionally contain other substances as needed.

[0192] In an organic light-emitting device according to one embodiment of the present specification, materials other than the heterocyclic compound of the above chemical formula 1 are exemplified below, but these are only for exemplification and are not intended to limit the scope of the present application, and may be replaced with materials known in the art.

[0193] Materials having a relatively large work function can be used as the anode material, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of the anode material include, but are not limited to, 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; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

[0194] Materials with relatively low work functions can be used as cathode materials, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF / Al or LiO2 / Al.

[0195] As the hole injection material, a known hole injection material may be used, for example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or a starburst amine derivative described in the literature [Advanced Material, 6, p. 677 (1994)], such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), a soluble conductive polymer such as polyaniline / dodecylbenzenesulfonic acid, or Poly(3,4-ethylenedioxythiophene) / Poly(4-styrenesulfonate), polyaniline / camphor sulfonic acid, or polyaniline / poly(4-styrenesulfonate) can be used.

[0196] In addition to the compound represented by the above chemical formula 1, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, etc. may be used as a hole transport material, and a low-molecular-weight or high-molecular-weight material may also be used.

[0197] As the electron transport material, metal complexes of oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, etc. can be used, and not only low molecular weight substances but also high molecular weight substances can be used.

[0198] For example, LiF is a representative material used in the art, but the present application is not limited thereto.

[0199] In addition to the compound represented by the above chemical formula 1, a red, green, or blue light-emitting material may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed and used. At this time, two or more light-emitting materials may be deposited and used as individual sources, or may be premixed and deposited and used as a single source. In addition, a fluorescent material may be used as the light-emitting material, but it may also be used as a phosphorescent material. A material that emits light by combining holes and electrons injected from the anode and cathode, respectively, may be used as the light-emitting material, but materials in which both the host material and the dopant material participate in light emission may also be used.

[0200] When using a mixture of hosts for light-emitting materials, 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, either N-type host materials or P-type host materials, may be selected and used as the host materials for the light-emitting layer.

[0201] An organic light-emitting device according to one embodiment of the present specification may be a front-emitting, back-emitting, or double-sided emitting device depending on the material used.

[0202] The heterocyclic compound according to one embodiment of the present specification can function in organic electronic devices, including organic solar cells, organic photoconductors, organic transistors, etc., by a similar principle to that applied to organic light-emitting devices.

[0203] In addition, by introducing various substituents into the heterocyclic compound structure of the above chemical formula 1, the energy band gap can be finely controlled, and on the other hand, the properties at the interface between organic substances can be improved and the uses of the material can be diversified.

[0204] In one embodiment of the present specification, a composition for forming an organic layer including the heterocyclic compound is provided.

[0205] In one embodiment of the present specification, a method for manufacturing an organic light-emitting device is provided, comprising: a step of preparing a substrate; a step of forming a first electrode on the substrate; a step of forming one or more organic layers on the first electrode; and a step of forming a second electrode on the organic layer, wherein the step of forming the organic layer includes a step of forming one or more organic layers using an organic layer-forming composition including a heterocyclic compound represented by the chemical formula 1.

[0206] In one embodiment of the present specification, a method for manufacturing an organic light-emitting device is provided, wherein the step of forming the organic layer comprises pre-mixing a heterocyclic compound represented by the chemical formula 1 and forming the organic layer using a thermal vacuum deposition method.

[0207] The above pre-mixed means that the heterocyclic compound represented by the above chemical formula 1 and the additional compound are first mixed in one container before being deposited on the organic layer.

[0208] The premixed material may be referred to as a composition for forming an organic layer according to one embodiment of the present specification.

[0209] Hereinafter, the present specification will be described in more detail through examples, but these are only intended to illustrate the present application and are not intended to limit the scope of the present application.

[0210] Example.

[0211] [Manufacturing example]

[0212] [Manufacturing Example 1] Preparation of Compound 001

[0213]

[0214] 1) Preparation of compound 001-P4

[0215] Dibenzofuran-4-ol (A) (50 g, 271.46 mmol, 1 eq, 001-P5), iodine monochloride (44.07 g, 271.46 mmol, 1 eq, iCl), acetic acid (400 ml) were placed in a round flask, and HCl (67 ml) was added while stirring. After stirring for 36 hours at room temperature, distilled water was added and filtered to obtain 51 g of compound 001-P4 with a yield of 84.18%.

[0216] 2) Preparation of compound 001-P3

[0217] Compound 001-P4 (51 g, 164.47 mmol, 1 eq), Phenylboronic Acid (B) (20.46 g, 164.47 mmol, 1 eq), Pd(PPh3)4 (9.5 g, 8.22 mmol, 0.05 eq), K2CO3 (34.1 g, 246.7 mmol, 1.5 eq), 1,4-dioxane (500 ml), and water (150 ml) were added and stirred at 100°C for 6 h. The organic layer was extracted using MC and water, and then moisture was removed with MgSO4. After separation using a silica gel column, 40 g of compound 001-P3 was obtained in a yield of 93.4%.

[0218] 3) Preparation of compound 001-P2

[0219] Compound 001-P3 (40 g, 153.67 mmol, 1 eq), 1-Bromo-3-chloro-2-fluoro benzene (C) (35.91 g, 169.04 mmol, 1.1 eq), and Cs2CO3 (100.14 g, 307.35 mmol, 2 eq) were added to DMA (400 ml) and stirred for 3 hours. After completion of the reaction, the mixture was separated using a silica gel column to obtain 56 g of compound 001-P2 in a yield of 81%.

[0220] 4) Preparation of compound 001-P1

[0221] Compound 001-P2 (56 g, 124.52 mmol, 1 eq), Cs2CO3 (81.14 g, 249.04 mmol, 2 eq), Pd(OAc)2 (81.14 g, 249.04 mmol, 0.05 eq), and PPh3 (3.27 g, 12.45 mmol, 0.1 eq) were added to NMP (600 ml) and stirred under reflux for 2 hr. After completion of the reaction, water was added to precipitate a solid, which was filtered. The obtained solid was dissolved in dichloromethane and separated through a silica gel column to obtain 15 g of compound 001-P1 with a yield of 32.6%.

[0222] 5) Preparation of compound 001

[0223] Compound 001-P1 (10 g, 27.1 mmol, 1 eq), N-phenylaniline (D) (4.59 g, 27.1 mmol, 1 eq), Pd2(dba)3 (1.24 g, 1.36 mmol, 0.05 eq), Xphos (1.29 g, 2.7 mmol, 0.1 eq), NaOtBu (3.91 g, 40.6 mmol, 1.5 eq), and toluene (100 ml) were added and stirred at 100°C for 4 h. After completion of the reaction, the mixture was concentrated and separated using a silica gel column to obtain 8.5 g of compound 001 in a yield of 62.5%.

[0224] In the above Preparation Example 1, the compound was synthesized using the same method as described above, using intermediate A of Table 1 below instead of dibenzofuran-4-ol (A), intermediate B of Table 1 below instead of Phenylboronic Acid (B), intermediate C of Table 1 below instead of 1-bromo-3-chloro-2-fluoro benzene (C), and intermediate D of Table 1 below instead of N-phenylaniline (D).

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231] [Manufacturing Example 2] Preparation of Compound 041

[0232]

[0233] In Manufacturing Example 2, compound 041 was synthesized using the same method as Manufacturing Example 1, except that the following method was included.

[0234] Compound 041-P1 (10 g, 27.1 mmol, 1 eq), N-(3-phenylphenyl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]dibenzofuran-4-amine (D) (15.3 g, 28.47 mmol, 1.05 eq), Pd2(dba)3 (1.24 g, 1.36 mmol, 0.05 eq), Xphos (1.29 g, 2.7 mmol, 0.1 eq), NaOtBu (3.91 g, 40.6 mmol, 1.5 eq), and Xylene (100 ml) were added and stirred at 100°C for 6 h. The organic layer was extracted using MC and water, and then the moisture was removed with MgSO4. Compound 041 13 g was obtained with a yield of 64.4% by separation using a silica gel column.

[0235] In the above Preparation Examples 1 and 2, the compounds were synthesized in the same manner using Intermediate A of Table 2 below instead of dibenzofuran-4-ol (A), Intermediate B of Table 2 below instead of Phenylboronic Acid (B), Intermediate C of Table 2 below instead of 2-bromo-4-chloro-1-fluoro benzene (C), and Intermediate D of Table 2 below instead of N-(3-phenylphenyl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]dibenzofuran-4-amine (D).

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243] [Manufacturing Example 3] Preparation of Compound 497

[0244]

[0245] Compound 001 (5 g, 9.97 mmol) was added to 650 mL of C6D and purged with nitrogen for 2 hours. 6.27 mL of trifluoromethanesulfonic acid (69.7 mmol, 7 eq) was added dropwise via a syringe, and the reaction mixture was refluxed and heated for 2 hours. After cooling to room temperature, 50 mL of deuterated water was added for extraction, and the organic layer was dried over anhydrous MgSO4 and concentrated using a rotary evaporator. Compound 497 (4.3 g, 84.7%) was obtained through an ethylene acetate (EA) slurry.

[0246] Except for the reaction temperature and time and the equivalent amount of trifluoromethanesulfonic acid described in Manufacturing Example 3, the compounds in Table 3 below were synthesized using the same method as Manufacturing Example 3.

[0247] Compound number Reaction temperature Reaction time Trifluoroacetic acid Equivalent yield 498 RT 2 HR 5 eq 85% 499 Reflux 2 HR 7 eq 88% 500 Reflux 2 HR 3 eq 79% 501 Reflux 2 HR 7 eq 86% 502 Reflux 2 HR 3 eq 79% 519 Reflux 2 HR 7 eq 81% 520 RT 2 HR 5 eq 86% 521 Reflux 2 HR 7 eq 83% 522 RT 2 HR 5 eq 82%

[0248] Compounds were manufactured using the same method as the above manufacturing examples, and the results of their synthesis are shown in Tables 4 and 5 below.

[0249] Table 4 below 1 The values ​​are measured by H NMR (DMSO, 300 MHz), and Table 5 below is measured by FD-mass spectrometry (FD-MS: Field desorption mass spectrometry).

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261] [Experimental Example]

[0262] Experimental Example 1

[0263] 1) Fabrication of organic light-emitting devices

[0264] A transparent electrode ITO thin film obtained from OLED glass (manufactured by Samsung Corning) was ultrasonically cleaned sequentially using trichloroethylene, acetone, ethanol, and distilled water for 5 minutes each, and then stored in isopropanol before use. Next, the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added to the cell in the vacuum deposition equipment.

[0265]

[0266] Then the vacuum level inside the chamber is 10 -6 After evacuating to reach 10 torr, a current was applied to the cell to evaporate 2-TNATA and deposit a 600 Å thick hole injection layer on an ITO substrate. N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was added to another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate it and deposit a 300 Å thick hole transport layer on the hole injection layer.

[0267]

[0268] After forming the hole injection layer and the hole transport layer in this way, a blue light-emitting material having the following structure was deposited as a light-emitting layer thereon. Specifically, a blue light-emitting host material, H1, was vacuum-deposited to a thickness of 200 Å in one cell within a vacuum deposition device, and a blue light-emitting dopant material, D1, was vacuum-deposited thereon at a thickness of 5% relative to the host material.

[0269]

[0270] Next, a compound of the following structural formula E1 was deposited as an electron transport layer with a thickness of 300 Å.

[0271]

[0272] An OLED device was fabricated by depositing lithium fluoride (LiF) as an electron injection layer with a thickness of 10 Å and using an Al cathode with a thickness of 1,000 Å. Meanwhile, all organic compounds required for fabricating an OLED device were each 10 Å thick. -8 ~10 -6 It was purified by vacuum sublimation under 10 torr and used in OLED production.

[0273] An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds shown in Table 6 were used instead of NPB used in forming the hole transport layer in Experimental Example 1. The electroluminescence (EL) characteristics of the organic light-emitting device manufactured as described above were measured using M7000 from MacScience, and the reference luminance was determined to be 700 cd / m using the lifespan measuring equipment (M6000) manufactured by MacScience based on the measurement results. 2 When, T 95 was measured.

[0274] The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the blue organic light-emitting device manufactured according to the present invention were as shown in Table 6.

[0275] No. Compound (hole transport layer material) Driving voltage (V) Luminous efficacy (cd / A) CIE (x, y) Lifetime (T 95) Example 10014.816.84(0.134, 0.100)88 Example 20074.886.86(0.133, 0.100)81 Example 30304.846.81(0.134, 0.101)86 Example 40484.836.79(0.133, 0.100)83 Example 50704.836.76(0.133, 0.101)88 Example 60964.846.85(0.133, 0.101)84 Example 71064.866.84(0.133, 0.102)87 Example 81114.846.83(0.133, 0.100)83 Example 91404.856.86(0.134, 0.100)86 Example 101584.866.90(0.133, 0.101)88 Example 111694.886.88(0.133, 0.100)90 Example 121904.876.86(0.133, 0.101)88 Example 132094.906.81(0.133, 0.100)87 Example 142314.886.86(0.133, 0.100)91 Example 152524.816.88(0.134, 0.100)91 Example 162624.846.91(0.133, 0.100)86 Example 172884.876.76(0.133, 0.101)89 Example 183184.906.85(0.134, 0.100)84 Example 193324.816.82(0.133, 0.100)86 Example 203514.836.88(0.134, 0.100)88 Example 213694.916.90(0.133, 0.101)89 Example 223944.886.79(0.133, 0.100)85 Example 234054.846.77(0.133, 0.101)89 Example 244264.846.81(0.133, 0.100)84 Example 254484.916.88(0.134, 0.100)86 Example 264634.906.88(0.133, 0.100)88 Example 274744.826.86(0.133, 0.100)90 Example 284814.846.81(0.133, 0.100)81 Example 294954.816.86(0.133, 0.100)91 Example 304974.886.84(0.133, 0.101)93 Example 314984.846.86(0.134, 0.101)91Example 325194.846.90(0.133, 0.100)93Example 335204.836.90(0.133, 0.101)92Example 345224.826.84(0.133, 0.100)93Comparative Example 1NPB5.486.03(0.134, 0.100)60Comparative Example 2Comparative Compound A5.106.15(0.134, 0.100)61Comparative Example 3Comparative Compound B5.036.42(0.133, 0.100)71Comparative Example 4Comparative Compound C5.146.21(0.133, 0.101)60Comparative Example 5Comparative Compound D5.136.22(0.133, 0.100)62Comparative Example 6Comparative Compound E5.186.18(0.133, 0.100)64Comparative Example 7Comparative Compound F5.116.23(0.133, 0.100)61Comparative Example 8Comparative Compound G5.146.20(0.133, 0.101)61Comparative Example 9Comparative Compound H5.026.38(0.133, 0.101)73.

[0276]

[0277] As can be seen from the results in Table 6 above, the organic light-emitting device using the hole transport layer material of the blue organic light-emitting device of the present invention has a lower driving voltage and significantly improved luminous efficiency and lifespan compared to Comparative Examples 1 to 9.

[0278] Comparative Example 1 does not have a core structure of a 5-ring heterocycle, and Comparative Example 4 has an amine structure in which two 5-ring heterocycles are connected to triphenylene, corresponding to a monosubstituted structure centered on one 5-ring heterocycle. Both compounds of Comparative Examples 1 and 4 have in common that they are symmetrical, and this structure has the disadvantage that when forming a film on a device, the film-forming properties are poor, making it difficult to form a uniform film, and thus the device properties may be significantly reduced.

[0279] Comparative examples 2 and 7 are single-substituted structures centered on a 5-ring heterocycle, and it is difficult to form structures of various shapes due to the absence of a second substituent, making it difficult to control suitable physicochemical properties (especially suitable hole mobility) depending on the device.

[0280] Comparative Example 3 is a structure in which an arylamine substituent is positioned in the middle ring of a 5-ring heterocycle, and since the arylamine substituent is not positioned in the linear structural direction in the terminal ring as in the present invention, it cannot implement hole mobility suitable for the device presented in the present invention.

[0281] Comparative examples 5 and 6 are structures using a carbazole substituent and a triazine substituent, respectively, and the device characteristics as a hole transport layer are not excellent because a substituent rich in electrons rather than holes is used.

[0282] Comparative Example 8 is a structure in which two arylamine groups are connected to the terminal of a 5-ring heterocyclic structure. Due to the absence of the second substituent, the excellent electron donating group characteristic provided by the second substituent is excluded, so not only is the hole mobility aimed for by the present invention not realized, but the hole characteristic is increased more than necessary, so the hole mobility suitable for the device presented in the present invention is not realized.

[0283] Comparative Example 9 is a fused ring structure that is bent from the fourth ring compared to the skeleton of the present invention, and thus hole mobility suitable for the device presented in the present invention is not realized, resulting in relatively poor device characteristics.

[0284] Therefore, for the reasons presented above, it is believed that the compound of the present invention exhibits improved driving, efficiency, and / or lifespan characteristics.

[0285] Experimental Example 2

[0286] 1) Fabrication of organic light-emitting devices

[0287] A transparent electrode ITO thin film obtained from OLED glass (manufactured by Samsung Corning) was ultrasonically cleaned sequentially using trichloroethylene, acetone, ethanol, and distilled water for 5 minutes each, and then stored in isopropanol before use. Next, the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added to the cell in the vacuum deposition equipment.

[0288]

[0289] Then the vacuum level inside the chamber is 10 -6 After evacuating to reach 10 torr, a current was applied to the cell to evaporate 2-TNATA and deposit a 600 Å thick hole injection layer on an ITO substrate. N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was added to another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate it and deposit a 300 Å thick hole transport layer on the hole injection layer.

[0290]

[0291] After forming the hole injection layer and the hole transport layer in this way, a blue light-emitting material having the following structure was deposited as a light-emitting layer thereon. Specifically, a blue light-emitting host material, H1, was vacuum-deposited to a thickness of 200 Å in one cell within a vacuum deposition device, and a blue light-emitting dopant material, D1, was vacuum-deposited thereon at a thickness of 5% relative to the host material.

[0292]

[0293] Next, a compound of the following structural formula E1 was deposited as an electron transport layer to a thickness of 300 Å.

[0294]

[0295] An OLED device was fabricated by depositing lithium fluoride (LiF) as an electron injection layer with a thickness of 10 Å and using an Al cathode with a thickness of 1,000 Å. Meanwhile, all organic compounds required for fabricating an OLED device were each 10 Å thick. -8 ~10 -6 It was purified by vacuum sublimation under 10 torr and used in OLED production.

[0296] An organic light-emitting device was manufactured in the same manner as in Experimental Example 2, except that in Experimental Example 2, the hole transport layer NPB was formed to a thickness of 250 Å, and then an electron blocking layer of a compound shown in Table 7 below was formed to a thickness of 50 Å on top of the hole transport layer.

[0297] The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the blue organic light-emitting device manufactured according to the present invention were as shown in Table 7 below.

[0298] No. Compound (electron barrier material) Driving voltage (V) Luminous efficacy (cd / A) CIE (x, y) Lifespan (T 95) Example 350074.856.85(0.133, 0.100)84 Example 360264.886.83(0.134, 0.102)88 Example 370414.866.86(0.133, 0.102)86 Example 380754.856.88(0.133, 0.101)90 Example 390854.846.85(0.134, 0.100)89 Example 401064.816.81(0.134, 0.100)86 Example 411294.806.90(0.133, 0.101)88 Example 421474.846.83(0.133, 0.100)84 Example 431804.796.86(0.133, 0.100)88 Example 441874.806.90(0.133, 0.101)88 Example 452164.836.88(0.134, 0.101)90 Example 462264.856.87(0.133, 0.100)84 Example 472414.866.87(0.133, 0.100)81 Example 482714.816.87(0.133, 0.101)86 Example 492814.856.91(0.134, 0.100)90 Example 503034.866.83(0.133, 0.101)91 Example 513334.886.84(0.134, 0.100)88 Example 523504.846.86(0.133, 0.101)88 Example 533644.866.84(0.133, 0.100)86 Example 543694.796.84(0.133, 0.101)82 Example 553994.766.88(0.134, 0.101)86 Example 564124.816.90(0.133, 0.100)85 Example 574354.846.90(0.133, 0.101)86 Example 584454.866.90(0.134, 0.101)86 Example 594884.766.81(0.133, 0.100)89 Example 604904.716.88(0.134, 0.101)87 Example 614994.766.81(0.134, 0.100)87 Example 625004.776.83(0.133, 0.100)87 Example 635014.786.90(0.134, 0.101)91 Example 645024.786.92(0.133, 0.100)93 Example 655214.806.91(0.133, 0.101)92 Comparative Example 10NPB5.526.06(0.133, 0.100)53 Comparative Example 11 Comparative Compound A5.206.21(0.133, 0.101)53 Comparative Example 12 Comparative Compound B5.266.19(0.134, 0.100)56 Comparative Example 13 Comparative Compound C5.296.31(0.133, 0.100)60 Comparative Example 14 Comparative Compound D5.266.22(0.134, 0.100)59 Comparative Example 15 Comparative Compound E5.256.20(0.133, 0.100)61Comparative Example 16Comparative Compound F5.246.19(0.133, 0.101)58Comparative Example 17Comparative Compound G5.036.51(0.134, 0.101)66Comparative Example 18Comparative Compound H5.066.49(0.133, 0.100)68.

[0299]

[0300] As can be seen from the results in Table 7 above, the organic light-emitting device using the electron blocking layer material of the blue organic light-emitting device of the present invention has a lower driving voltage and significantly improved luminous efficiency and lifespan compared to Comparative Examples 10 to 18.

[0301] Specifically, the heterocyclic compounds used in Examples 35 to 65 corresponding to the present invention each have the advantage of being able to implement a higher T1 level and being able to control the LUMO level to a level more suitable as an electron blocking layer by the first substituent (arylamine group) and the second substituent (aryl group or heteroaryl group) used.

[0302] In contrast, Comparative Example 10 has a core structure that is not a 5-ring heterocycle, and Comparative Examples 11 and 12 have a monosubstituted structure, making it difficult to form structures of various shapes. Therefore, it is difficult to control all of them to have physicochemical properties suitable as electron blocking layers.

[0303] Comparative Example 10 does not have a core structure that corresponds to a 5-ring heterocycle, and Comparative Example 13 has an amine structure in which two 5-ring heterocycles are connected to triphenylene via a biphenylene linker, and corresponds to a 1-substituted structure centered on one 5-ring heterocycle. Both compounds of Comparative Examples 10 and 13 have a symmetrical structure, but this structure has a disadvantage in that the film-forming properties are poor when forming a film on a device, making it difficult to form a uniform film, which may significantly deteriorate the device properties.

[0304] Comparative Example 14 is a compound using a triazine substituent, and the device characteristics as an electron blocking layer are not excellent because it uses a substituent rich in electrons rather than holes.

[0305] Comparative Example 15 is a structure in which an arylamine substituent is positioned in the middle ring of a 5-ring heterocycle, and unlike the present invention, the arylamine substituent is not positioned in the linear structural direction in the terminal ring, so it cannot implement electron blocking characteristics suitable for the device presented in the present invention.

[0306] Comparative examples 16 and 17 are structures in which two arylamine groups are connected to both ends of a 5-ring heterocyclic structure. Due to the absence of the second substituent, the excellent electron donating group properties provided by the second substituent are excluded, and thus the electron blocking properties aimed at by the present invention cannot be realized.

[0307] Comparative Example 18 is a fused ring structure that is bent from the fourth ring compared to the skeleton of the present invention, and thus the electron blocking characteristics suitable for the device presented in the present invention are not implemented, resulting in relatively poor device characteristics.

[0308] Accordingly, for the reasons presented above, it is judged that the compound of the present invention shows improved driving, efficiency, and life characteristics compared to the compound used in the comparative example.

[0309] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A heterocyclic compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X1 and X2 are the same or different from each other, and are each independently O; or S, R1 to R3 are the same or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; -CN; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)RR'; and -SiRR'R", R, R' and R" are the same or different from each other, and each independently represents a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, L1 to L4 are the same or different from each other, and each independently represents a direct bond; or a substituted or unsubstituted C6 to C60 arylene group, Ar1 to Ar3 are the same or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, a is an integer from 0 to 3, b is 0 or 1, c is an integer from 0 to 4, m, n, j, and k are each integers from 0 to 4, p, q and r are integers from 1 to 4, respectively, When each of a, c, m, n, j, k, p, q and r is 2 or more, the substituents within the parentheses are the same or different.

2. In claim 1, The above chemical formula 1 is a heterocyclic compound 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 the above chemical formulas 1-1 to 1-4, X1, X2, R1 to R3, L1 to L4, Ar1 to Ar3, a, b, c, m, n, j, k, p, q and r are the same as defined in the above chemical formula 1.

3. In claim 1, The above chemical formula 1 is a heterocyclic compound represented by the following chemical formula 1-5 or 1-6: [Chemical Formula 1-5] [Chemical Formula 1-6] In the above chemical formulas 1-5 and 1-6, X1, X2, R1 to R3, L1 to L4, Ar1 to Ar3, a, c, m, n, j, k, p, q and r are the same as defined in the above chemical formula 1.

4. In claim 1, A heterocyclic compound wherein R1 to R3 are the same or different and each independently represent hydrogen or deuterium.

5. In claim 1, A heterocyclic compound wherein L1 to L4 are the same or different and each independently represent a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.

6. In claim 1, A heterocyclic compound wherein Ar1 to Ar3 are the same or different and each independently represent a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.

7. In claim 1, A heterocyclic compound having a deuterium content of 0% to 100% in the above chemical formula 1.

8. In claim 1, The above chemical formula 1 is a heterocyclic compound represented by any one of the following: .

9. An organic light-emitting device comprising a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, An organic light-emitting device, wherein at least one of the organic layers comprises at least one heterocyclic compound according to any one of claims 1 to 8.

10. In claim 9, An organic light-emitting device wherein the organic layer comprises at least one layer of a hole transport layer, a hole transport auxiliary layer, and an electron blocking layer, and at least one layer of the hole transport layer, the hole transport auxiliary layer, and the electron blocking layer comprises at least one type of the heterocyclic compound.

11. In claim 9, An organic light-emitting device further comprising one 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.

Images