Heterocyclic compound, organic light-emitting device, and composition for organic material layer of organic light-emitting device

Abstract

The present specification relates to a heterocyclic compound of chemical formula 1, an organic light-emitting device including the heterocyclic compound, and a composition for an organic material layer of the organic light-emitting device.

Description

[0001] Cross-references This application claims priority and benefit to Korean Patent Application No. 10-2023-0130400, filed on September 27, 2023, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This disclosure relates to compositions of heterocyclic compounds, organic light-emitting devices, and organic material layers for use in organic light-emitting devices. Background Technology

[0003] An electroluminescent device is a self-emissive display device that has the advantages of wide viewing angle, high response speed and excellent contrast.

[0004] Organic light-emitting devices have a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to an organic light-emitting device with this structure, electrons and holes injected from the two electrodes combine and pair in the organic thin film, and light is emitted as these annihilate. The organic thin film can be formed as a single layer or multiple layers, depending on the requirements.

[0005] Depending on the requirements, the materials of organic thin films can possess light-emitting properties. For example, as materials for organic thin films, compounds capable of forming the light-emitting layer itself can be used alone, or compounds capable of functioning as the host or dopant in a host-dopant type light-emitting layer can be used. Furthermore, compounds capable of functioning as hole injection, hole transport, electron blocking, and electron transport / injection can also be used as materials for organic thin films.

[0006] To improve the performance, lifespan, or efficiency of organic light-emitting devices, there is an ongoing need to develop organic thin film materials.

[0007] <Prior art documents> (Patent Document 1) U.S. Patent No. 4,356,429 Summary of the Invention [Technical Objectives] This disclosure relates to compositions of heterocyclic compounds, organic light-emitting devices, and organic material layers for use in organic light-emitting devices.

[0008] [Technical Solution] Embodiments of this disclosure provide a heterocyclic compound represented by the following chemical formula 1: [Chemical Formula 1]

[0009] In chemical formula 1, X is O or S; Ar1 is a C6 to C60 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl; Ar2 is a substituted or unsubstituted C6 to C60 aryl group; R1 to R4 are each independently: hydrogen; deuterium; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; or substituted or unsubstituted C2 to C60 heteroaryl. D is deuterium, d1 is an integer from 1 to 4, and d2 is an integer from 1 to 8; r1 and r2 are each an independent integer from 1 to 3. r3 is an integer from 0 to 3, and the sum of d1 and r3 is 4; r4 is an integer from 0 to 7, and the sum of d2 and r4 is 8; and When each of r1 to r4 is 2 or greater, the substituents in parentheses are either the same or different from each other.

[0010] Furthermore, another embodiment of this disclosure provides an organic light-emitting device, which includes: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the one or more organic material layers includes the above-mentioned heterocyclic compound.

[0011] Furthermore, another embodiment of this disclosure provides a composition for an organic material layer, the composition comprising the above-mentioned heterocyclic compounds.

[0012] [Beneficial Effects] When used in organic light-emitting devices, the compounds of Formula 1 described herein can exhibit low driving voltage characteristics, high luminous efficiency characteristics, and / or long lifetime characteristics.

[0013] Specifically, as represented by Formula 1, the heterocyclic compounds of this disclosure are characterized by a phenylene group in which the nitrogen atoms of the triazine and carbazole moieties are bonded at ortho positions. The compounds also include aryl groups and dibenzofuran or dibenzothiophene groups substituted at specific positions as other substituents for the triazine, while deuterium must be included in the carbazole and phenylene groups. The structural deformation is enhanced by the substitution of the triazine and carbazole groups at ortho positions, thereby facilitating charge transport. Furthermore, a high first excited triplet (T1) energy level can be achieved by including a large and rigid structure due to the substituents at specific positions of the dibenzofuran or dibenzothiophene groups. In addition, the inclusion of deuterium at specific positions enhances thermal stability, thereby improving the lifetime characteristics of the device. Attached Figure Description

[0014] Figures 1 to 3 Each diagram is a schematic illustration of the stacked structure of an organic light-emitting device according to an embodiment of the present disclosure.

[0015] <Figure Labels> 100: Base 200: Anode 300: Organic material layer 301: Hole Injection Layer 302: Hole transport layer 303: Emissive layer 304: Cavity Blocking Layer 305: Electron Transport Layer 306: Electron Injection Layer 400: Cathode Detailed Implementation [Best Implementation] This disclosure will be described in more detail below.

[0016] As used herein, unless otherwise specifically stated otherwise, if a specified part “includes” a specified element, it means that another element may be included rather than excluded.

[0017] As used in this article, “N to N’” means N or more and N’ or less.

[0018] As used in this article, in chemical formulas It refers to the bonding position.

[0019] The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent, and the position to be substituted is not restricted, as long as the position is where the hydrogen atom is substituted (i.e., the substituent is a substituted position), and when two or more substituents are substituted, the two or more substituents can be the same as or different from each other.

[0020] As used herein, the term “substituted or unsubstituted” means substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen groups; -CN; C1 to C60 alkyl; C2 to C60 alkenyl; C2 to C60 alkynyl; C1 to C60 haloalkyl; C1 to C60 alkoxy; C6 to C60 aryloxy; C1 to C60 alkylthio; C6 to C60 arylthio; C1 to C60 alkylsulfonyl; C6 to C60 arylsulfonyl; C3 to C60 cycloalkyl; C2 to C60 heterocycloalkyl; C6 to C60 aryl; C2 to C60 heteroaryl; silyl; phosphine oxide; and amino groups, or substituted by substituents linked by two or more substituents selected from the substituents shown above, or unsubstituted.

[0021] As used in this article, the phrase "substituents not indicating their presence in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, due to deuterium ( 2 H is an isotope of hydrogen, therefore some hydrogen atoms can be deuterium.

[0022] In one embodiment of this application, the phrase "substituents not indicated in the chemical formula or compound structure" may mean that the positions where substituents may appear can be entirely hydrogen or deuterium. In other words, since deuterium is an isotope of hydrogen, some hydrogen atoms may be deuterium as an isotope, and in this document, the deuterium content may be 0% to 100%.

[0023] In one embodiment of this application, in the case where "the substituents are not indicated in the chemical formula or compound structure", hydrogen and deuterium can be mixed in the compound unless deuterium is explicitly excluded, such as when the deuterium content is 0%, the hydrogen content is 100%, or all substituents are hydrogen.

[0024] In one embodiment of this application, deuterium is an isotope of hydrogen, an element having a deuterium nucleus with one proton and one neutron as its nucleus, and can be represented as hydrogen-2, and its element symbol can also be written as D or 2 H.

[0025] In one embodiment of this application, an isotope means an atom having the same number of atoms (Z) but different mass numbers (A), and can also be interpreted as an element having the same number of protons but different numbers of neutrons.

[0026] In one embodiment of this application, the substitution rate (T%) of a specific substituent can be defined as T2 / T1×100%=T%, where T1 is defined as the total number of substituents that the basic compound can have, and T2 is defined as the number of specific substituents in the basic compound.

[0027] That is to say, in one example, by The 20% deuterium substitution rate in a phenyl group means that the total number of substituents a phenyl group can have is 5 (T1 in the formula), and the number of deuteriums in the phenyl group is 1 (T2 in the formula). In other words, a 20% deuterium substitution rate in a phenyl group can be represented by the following structural formula.

[0028]

[0029] Furthermore, in one embodiment of this application, "phenyl with 0% deuterium content" may mean a phenyl that does not contain deuterium atoms (i.e., a phenyl with 5 hydrogen atoms).

[0030] As used in this article, halogens can be fluorine, chlorine, bromine, or iodine.

[0031] As used herein, alkyl groups include straight-chain or branched groups and may be substituted with other substituents. The number of carbon atoms in an alkyl group can be from 1 to 60, specifically from 1 to 40, and more specifically from 1 to 20. Specific examples of alkyl groups may include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

[0032] As used herein, alkenyl groups include straight-chain or branched groups and may be substituted with other substituents. The number of carbon atoms in an alkenyl group can be from 2 to 60, specifically from 2 to 40, and more specifically from 2 to 20. Specific examples of alkenyl groups may include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, bis(diphenyl-1-yl)vinyl-1-yl, styreneyl, and styreneyl.

[0033] As used herein, an alkynyl group comprises a straight or branched chain having 2 to 60 carbon atoms and may be substituted with other substituents. The number of carbon atoms in an alkynyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

[0034] As used herein, haloalkyl means an alkyl group substituted with a halogen group, and specific examples of haloalkyl include, but are not limited to, -CF3 and -CF2CF3.

[0035] As used herein, alkoxy groups are represented by -O (R101), and examples of the alkyl groups described above can be applied to R101.

[0036] As used herein, aryl groups are represented by -O (R102), and the above examples of aryl groups can be applied to R102.

[0037] As used herein, alkylthio groups are represented by -S(R103), and the examples of the above alkyl groups can be applied to R103.

[0038] As used herein, arylthio groups are represented by -S(R104), and the above examples of aryl groups can be applied to R104.

[0039] As used herein, alkyl sulfonyl groups are represented by -S(=O)2(R105), and examples of the above alkyl groups can be applied to R105.

[0040] As used herein, arylsulfonyl groups are represented by -S(=O)2(R106), and the above examples of aryl groups can be applied to R106.

[0041] As used herein, cycloalkyl groups include monocyclic or polycyclic groups having 3 to 60 carbon atoms and may be substituted with other substituents. In this document, polycyclic means a group in which the cycloalkyl group is directly attached to or fused with another cyclic group. The other cyclic group may be cycloalkyl, but may also be different types of cyclic groups, such as heterocycloalkyl, aryl, and heteroaryl. The number of carbon atoms in a cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples of cycloalkyl groups may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

[0042] As used herein, heterocyclic alkyl groups include O, S, Se, N, or Si as heteroatoms, and include monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may be substituted with other substituents. In this document, polycyclic means a group in which the heterocyclic alkyl group is directly attached to or fused with other cyclic groups. In this document, the other cyclic groups may be heterocyclic alkyl groups, but may also be different types of cyclic groups, such as cycloalkyl, aryl, and heteroaryl. The number of carbon atoms in a heterocyclic alkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

[0043] As used herein, aryl groups include monocyclic or polycyclic groups having 6 to 60 carbon atoms and may be substituted with other substituents. In this document, polycyclic means a group in which the aryl group is directly attached to or fused with another cyclic group. The other cyclic group may be aryl, but may also be of different types, such as cycloalkyl, heterocycloalkyl, and heteroaryl. Aryl groups include spirocyclic groups. The number of carbon atoms in an aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of aryl groups may include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, perylene, fluoranyl, phenoxide, pyrene, tetraphenyl, pentaphenyl, fluorenyl, indole, acenaphthene, benzo[a]fluorenyl, spirodifluorenyl, 2,3-dihydro-1H-indole and their fused-ring groups.

[0044] As used in this article, the triphenyl group can be selected from the following structures.

[0045]

[0046] As used herein, the fluorene group can be substituted, and adjacent substituents can combine with each other to form a ring.

[0047] When the fluorene group is substituted, the structure can include the following structures, however, the structure is not limited to these.

[0048]

[0049] As used herein, heteroaryl groups include O, S, Se, N, or Si as heteroatoms, and include monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may also be substituted with other substituents. In this document, polycyclic means a group in which the heteroaryl group is directly attached to or fused with other cyclic groups. In this document, the other cyclic groups may be heteroaryl groups, but may also be different types of cyclic groups, such as cycloalkyl, heterocycloalkyl, and aryl groups. The number of carbon atoms in a heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl groups may include pyridyl, pyrroloyl, pyrimidinyl, pyridazinyl, furanyl, thiopheneyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazonyl, oxadiazolyl, thiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiaranyl, diazinyl, oxazinyl, thiazolyl, dioxinyl, triazinyl, tetraazinyl, quinolinyl, isoquinolinyl, and quinazolinyl. Isoquinazolinyl, quinoxalinyl, naphridinyl, acridineyl, phenanthridineyl, imidazopyridyl, diazanaphthyl, triazaindenyl, indoleyl, indoleazinyl, benzothiazolyl, benzooxazolyl, benzoimidazolyl, benzothiopheneyl, benzofuranyl, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, phenazinyl, dibenzothiopheneyl, spirobis(dibenzothiophene), di Hydrophenazinyl, phenoxazinyl, phenanthridineyl, thiopheninyl, indolo[2,3-a]carbazoleyl, indolo[2,3-b]carbazoleyl, indololinyl, 10,11-dihydrodibenzo[b,f]azapyridineyl, 9,10-dihydroacridinyl, phenanthridineyl, phenothiazinyl, phthalazinyl, naphthidyl, phenanthrolinyl, naphthobenzofuranyl, naphthobenzothiopheninyl, benzo[c][1,2,5]thiadi Azolyl, 2,3-dihydrobenzo[b]thiophenyl, 2,3-dihydrobenzofuranyl, 5,10-dihydrodibenzo[b,e][1,4]azasilyl, pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]inzolyl, pyrido[1,2-a]imidazo[1,2-e]indolyl, and 5,11-dihydroindo[1,2-b]carbazoleyl, etc., but not limited to these.

[0050] As used in this article, the benzo[carbazole] group can be any of the following structures.

[0051]

[0052] As used in this article, the dibenzocarbazoyl group can be any of the following structures.

[0053]

[0054] As used herein, when the substituent is carbazolyl, benzocarbazolyl, or dibenzocarbazolyl, it means a nitrogen or carbon bond with the carbazolyl, benzocarbazolyl, or dibenzocarbazolyl.

[0055] As used herein, when carbazolyl, benzocarbazolyl, or dibenzocarbazolyl is substituted, the additional substituent may be substituted on the nitrogen or carbon of carbazolyl, benzocarbazolyl, or dibenzocarbazolyl.

[0056] As used in this article, the naphthobenzofuranyl group can be any of the following structures.

[0057]

[0058] As used in this article, the naphthobenzothiophene group can be any of the following structures.

[0059]

[0060] As used herein, silyl groups are substituents comprising Si and having a Si atom directly attached as a free radical, and are represented by -Si(R107)(R108)(R109). R107 to R109 may be the same as or different from each other, and may each be a substituent formed independently of at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl.

[0061] Depending on the substituents bonded to the Si element, silyl groups can include alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, and arylheteroarylsilyl groups. Alkylsilyl, arylsilyl, or heteroarylsilyl groups refer to silyl groups where the Si element is substituted with an alkyl, aryl, or heteroaryl group, respectively. Alkylarylsilyl groups refer to silyl groups where the Si element is substituted with both an alkyl and aryl group. Furthermore, arylheteroarylsilyl groups refer to silyl groups where the Si element is substituted with both an aryl and heteroaryl group.

[0062] Specific examples of silanes include, but are not limited to, the following structures.

[0063] (trimethylsilyl) (triethylsilyl) (tert-butyldimethylsilyl) (Vinyl dimethylsilyl) (propyl dimethylsilyl) (Triphenylsilyl) (diphenylsilyl) and (Phenylsilyl group).

[0064] As used herein, the phosphine oxide group is represented by -P(=O)(R110)(R111). R110 and R111 may be the same as or different from each other, and may each be independently a substituent formed by at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl. Specifically, the phosphine oxide group may be substituted with an alkyl or aryl group, and the examples described above may be used as alkyl and aryl groups. Examples of phosphine oxide groups may include, but are not limited to, dimethylphosphine oxide groups, diphenylphosphine oxide groups, and dinaphthylphosphine oxide groups.

[0065] As used herein, the amino group is represented by -N(R112)(R113). R112 and R113 may be the same as or different from each other, and may each be a substituent formed independently of at least one of the following groups: hydrogen; deuterium; halogen group; alkyl; alkenyl; alkoxy; cycloalkyl; heterocycloalkyl; aryl; and heteroaryl. The amino group may be selected from the group consisting of: -NH2; monoalkylamino; monoarylamino; monoheteroarylamino; dialkylamino; diarylamino; diheteroarylamino; alkylarylamino; alkylheteroarylamino; and arylheteroarylamino, and although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 30. Specific examples of amino groups may include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamino, anthraceneamino, 9-methylanthraylamino, diphenylamino, phenylnaphthylamino, xylylamino, phenyltolylamino, triphenylamino, biphenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenyltriphenylamine, and biphenyltriphenylamine.

[0066] As used in this article, the above description of aryl groups can be applied to arylene groups, except that arylene groups are divalent groups.

[0067] As used in this article, the above description of heteroaryl groups can be applied to heteroaryl groups, except that heteroaryl groups are divalent groups.

[0068] One embodiment of this disclosure provides a heterocyclic compound represented by chemical formula 1.

[0069] [Chemical Formula 1]

[0070] In chemical formula 1, X is O or S; Ar1 is a C6 to C60 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl; Ar2 is a substituted or unsubstituted C6 to C60 aryl group; R1 to R4 are each independently: hydrogen; deuterium; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; or substituted or unsubstituted C2 to C60 heteroaryl. D is deuterium, d1 is an integer from 1 to 4, and d2 is an integer from 1 to 8; r1 and r2 are each an independent integer from 1 to 3. r3 is an integer from 0 to 3, and the sum of d1 and r3 is 4; r4 is an integer from 0 to 7, and the sum of d2 and r4 is 8; and When each of r1 to r4 is 2 or greater, the substituents in parentheses are either the same or different from each other.

[0071] In embodiments of this disclosure, X can be O.

[0072] In embodiments of this disclosure, X can be S.

[0073] In embodiments of this disclosure, chemical formula 1 may be represented by any of the following chemical formulas 1-1 to 1-4.

[0074] [Chemical Formula 1-1]

[0075] [Chemical Formula 1-2]

[0076] [Chemical Formulas 1-3]

[0077] [Chemical Formulas 1-4]

[0078] In chemical formulas 1-1 to 1-4 Each substituent is as defined in Formula 1 above.

[0079] In embodiments of this disclosure, chemical formula 1 may be represented by chemical formula 1-O or chemical formula 1-S.

[0080] [Chemical formula 1-O]

[0081] [Chemical Formula 1-S]

[0082] In chemical formula 1-O and chemical formula 1-S, Each substituent is as defined in Formula 1 above.

[0083] In the embodiments of this disclosure, R1 to R4 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C30 alkyl; substituted or unsubstituted C3 to C30 cycloalkyl; substituted or unsubstituted C2 to C30 heterocycloalkyl; or substituted or unsubstituted C2 to C30 heteroaryl.

[0084] In the embodiments of this disclosure, R1 to R4 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C3 to C20 cycloalkyl; substituted or unsubstituted C2 to C20 heterocycloalkyl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0085] In the embodiments of this disclosure, R1 to R4 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C30 alkyl; or substituted or unsubstituted C3 to C30 cycloalkyl.

[0086] In embodiments of this disclosure, R1 to R4 can each be independently: hydrogen; or deuterium.

[0087] In embodiments of this disclosure, R1 to R4 can each be hydrogen independently.

[0088] In the embodiments of this disclosure, R1 and R2 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C30 alkyl; substituted or unsubstituted C3 to C30 cycloalkyl; substituted or unsubstituted C2 to C30 heterocycloalkyl; or substituted or unsubstituted C2 to C30 heteroaryl.

[0089] In the embodiments of this disclosure, R1 and R2 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C3 to C20 cycloalkyl; substituted or unsubstituted C2 to C20 heterocycloalkyl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0090] In the embodiments of this disclosure, R1 and R2 may each be independently: hydrogen; deuterium; substituted or unsubstituted C1 to C30 alkyl; or substituted or unsubstituted C3 to C30 cycloalkyl.

[0091] In embodiments of this disclosure, R1 and R2 may each be independently: hydrogen; or deuterium.

[0092] In embodiments of this disclosure, R1 and R2 may each be hydrogen independently.

[0093] In the embodiments of this disclosure, R3 and R4 may each be independently: hydrogen; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0094] In the embodiments of this disclosure, R3 and R4 may each be independently: hydrogen; substituted or unsubstituted C1 to C30 alkyl; substituted or unsubstituted C3 to C30 cycloalkyl; substituted or unsubstituted C2 to C30 heterocycloalkyl; or substituted or unsubstituted C2 to C30 heteroaryl.

[0095] In the embodiments of this disclosure, R3 and R4 may each be independently: hydrogen; substituted or unsubstituted C1 to C10 alkyl; substituted or unsubstituted C3 to C20 cycloalkyl; substituted or unsubstituted C2 to C20 heterocycloalkyl; or substituted or unsubstituted C2 to C20 heteroaryl.

[0096] In the embodiments of this disclosure, R3 and R4 may each be independently: hydrogen; substituted or unsubstituted C1 to C30 alkyl; or substituted or unsubstituted C3 to C30 cycloalkyl.

[0097] In embodiments of this disclosure, R3 and R4 may each be hydrogen independently.

[0098] In embodiments of this disclosure, D is deuterium, d1 is an integer from 1 to 4, and d2 is an integer from 1 to 8.

[0099] In other words, chemical formula 1 must include one or more deuterium groups in each of the phenylene and carbazole groups.

[0100] Typically, compounds substituted only with hydrogen and compounds substituted with deuterium exhibit different thermodynamic behaviors due to differences in atomic mass and van der Waals radius, among other things. In the case of deuterium, deuterium has a lower vibrational energy than hydrogen, and the bond between carbon and deuterium is shorter in length and has a stronger dissociation energy compared to the bond between carbon and hydrogen. Therefore, compared to compounds substituted only with hydrogen, compounds substituted with deuterium possess a lower ground state energy, and their polarizability can be reduced by decreasing the volume of the molecular hard core. Furthermore, compounds substituted with deuterium have the effect of increasing the volume of the device thin film by weakening intermolecular interactions and reducing crystallinity by bringing the thin film into an amorphous state. Therefore, when the heterocyclic compounds of the present invention are used as materials for organic light-emitting diode (OLED) devices, device efficiency and lifetime characteristics can be improved.

[0101] In embodiments of this disclosure, r3 and r4 can be 0.

[0102] In embodiments of this disclosure, chemical formula 1 may be represented by the following chemical formula 1-1-1.

[0103] [Chemical Formula 1-1-1]

[0104] In chemical formula 1-1-1, Each substituent is as defined in Formula 1 above.

[0105] In embodiments of this disclosure, chemical formula 1 may be represented by the following chemical formula 1-D.

[0106] [Chemical Formula 1-D]

[0107] In chemical formula 1-D, Each substituent is as defined in Formula 1 above.

[0108] In embodiments of this disclosure, the deuterium substitution rate of Formula 1 can be greater than 0% and at most 100%.

[0109] In embodiments of this disclosure, the deuterium substitution rate of Formula 1 can be from 10% to 90%.

[0110] In embodiments of this disclosure, the deuterium substitution rate of Formula 1 can be from 20% to 80%.

[0111] In embodiments of this disclosure, the deuterium substitution rate of Formula 1 can be from 30% to 60%.

[0112] As used herein, the deuterium substitution rate of Formula 1 refers to the rate of substitution of deuterium relative to the total number of hydrogens and deuteriums included in Formula 1. For example, when Formula 1 contains 20 hydrogens and 20 deuteriums, the deuterium substitution rate is 50%, which corresponds to 20 deuteriums out of a total of 40 hydrogens and deuteriums.

[0113] In the embodiments of this disclosure, the heterocyclic compounds of Formula 1 satisfy the above-mentioned range of deuterium substitution rates. The photochemical properties of the deuterium-free and deuterium-containing compounds are substantially similar. However, when deposited as thin films, the deuterium-containing materials tend to pack with narrower intermolecular distances.

[0114] Therefore, when manufacturing EOD (electronic devices only) and HOD (hole devices only) and checking the current density based on voltage, it can be confirmed that the heterocyclic compound of chemical formula 1 of this disclosure exhibits balanced charge transport characteristics compared to the deuterium-free compound.

[0115] Furthermore, when the surface of the film was observed using an atomic force microscope (AFM), it was confirmed that the film deposited with deuterium-containing compounds had a more uniform surface without aggregated areas.

[0116] Furthermore, since the bond dissociation energy of the carbon-deuterium (CD) single bond is higher than that of the carbon-hydrogen (CH) single bond, the heterocyclic compound according to Formula 1 of this disclosure exhibits increased overall molecular stability, thereby improving the lifespan of the device.

[0117] In embodiments of this disclosure, chemical formula 1 includes the structures of chemical formula A and chemical formula B, wherein chemical formula A has a deuterium substitution rate greater than 0% and 100% or less, and chemical formula B has a deuterium substitution rate of 0% to 100%.

[0118] [Chemical Formula A]

[0119] [Chemical Formula B]

[0120] In chemical formula A and chemical formula B, It is the position where chemical formula A and chemical formula B are bonded, and Each substituent is as defined in Formula 1 above.

[0121] In embodiments of this disclosure, the deuterium substitution rate of chemical formula A or chemical formula B means the substitution rate of deuterium relative to the total number of hydrogen and deuterium included in chemical formula A or chemical formula B.

[0122] In embodiments of this disclosure, the deuterium substitution rate of chemical formula A can be from 10% to 100%, and the deuterium substitution rate of chemical formula B can be from 0% to 80%.

[0123] In embodiments of this disclosure, the deuterium substitution rate of chemical formula A can be from 30% to 100%, and the deuterium substitution rate of chemical formula B can be from 0% to 50%.

[0124] In embodiments of this disclosure, the deuterium substitution rate of chemical formula A may be 100%, and the deuterium substitution rate of chemical formula B may be 0%.

[0125] In embodiments of this disclosure, Ar1 can be a C6 to C30 aryl group substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl.

[0126] In embodiments of this disclosure, Ar1 can be a C6 to C20 aryl group substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl.

[0127] In embodiments of this disclosure, Ar1 can be a phenyl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; aryl; and heteroaryl; a biphenyl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; aryl; and heteroaryl; or a terphenyl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; Aryl; and heteroaryl, naphthyl substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; aryl; and heteroaryl; phenanthrene substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; aryl; and heteroaryl; or triphenylene substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen group; alkyl; cycloalkyl; aryl; and heteroaryl.

[0128] In embodiments of this disclosure, Ar1 may be a C6 to C60 aryl group.

[0129] In embodiments of this disclosure, Ar1 may be a C6 to C30 aryl group.

[0130] In embodiments of this disclosure, Ar1 may be a C6 to C20 aryl group.

[0131] In embodiments of this disclosure, Ar2 may be a substituted or unsubstituted C6 to C30 aryl group.

[0132] In embodiments of this disclosure, Ar2 may be a substituted or unsubstituted C6 to C20 aryl group.

[0133] In embodiments of this disclosure, Ar2 may be a substituted or unsubstituted C6 to C15 aryl group.

[0134] In embodiments of this disclosure, Ar2 may be: a substituted or unsubstituted phenyl; or a substituted or unsubstituted biphenyl.

[0135] In embodiments of this disclosure, Ar2 may be a C6 to C60 aryl group.

[0136] In embodiments of this disclosure, Ar2 may be a C6 to C30 aryl group.

[0137] In embodiments of this disclosure, Ar2 may be a C6 to C20 aryl group.

[0138] In embodiments of this disclosure, Ar2 may be a C6 to C15 aryl group.

[0139] In embodiments of this disclosure, Ar1 may be a C6 to C20 aryl group substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl; and Ar2 may be a substituted or unsubstituted C6 to C15 aryl group.

[0140] In embodiments of this disclosure, Ar1 and Ar2 may not contain deuterium.

[0141] In embodiments of this disclosure, Ar1 and Ar2 may each be independently C6 to C60 aryl.

[0142] In embodiments of this disclosure, Ar1 and Ar2 may each be independently C6 to C30 aryl.

[0143] In embodiments of this disclosure, Ar1 and Ar2 may each be independently C6 to C20 aryl groups.

[0144] In embodiments of this disclosure, Ar1 and Ar2 may each be independently C6 to C15 aryl.

[0145] In embodiments of this disclosure, chemical formula 1 may be represented by any of the following compounds.

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] Furthermore, by introducing various substituents into the structure of Formula 1, compounds possessing the unique properties of the introduced substituents can be synthesized. For example, substituents commonly used in materials used to manufacture organic light-emitting devices (such as hole injection layer materials, hole transport layer materials, light-emitting layer materials, electron transport layer materials, and charge generation layer materials) can be introduced into the core structure. Therefore, materials capable of meeting the requirements of the corresponding organic material layers can be synthesized.

[0155] Furthermore, by introducing various substituents into the structure of Formula 1, the band gap can be precisely controlled, the properties at the interface between organic materials can be enhanced, and the application of the materials can be modified in different ways.

[0156] Another embodiment of this disclosure provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the one or more organic material layers comprises one or more heterocyclic compounds represented by chemical formula 1.

[0157] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, and the light-emitting layer may include one or more heterocyclic compounds of Formula 1.

[0158] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, and the light-emitting layer may include a heterocyclic compound of Formula 1.

[0159] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may include one or more heterocyclic compounds of Formula 1.

[0160] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may include a heterocyclic compound of Formula 1.

[0161] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a green host, and the green host may include one or more heterocyclic compounds of Formula 1.

[0162] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a red host, and the red host may include one or more heterocyclic compounds of Formula 1.

[0163] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a blue host, and the blue host may include one or more heterocyclic compounds of Formula 1.

[0164] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, and the light-emitting layer may include a heterocyclic compound of Formula 1 as an N-type host.

[0165] In embodiments of this disclosure, the organic material layer comprising heterocyclic compounds may further comprise compounds represented by the following chemical formula 2 or chemical formula 3.

[0166] [Chemical Formula 2]

[0167] [Chemical Formula 3]

[0168] Among them, in chemical formulas 2 and 3, R11, R12, R21, and R22 are each independently selected from the group consisting of: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C2 to C60 alkenyl; substituted or unsubstituted C2 to C60 alkoxy; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; substituted or unsubstituted silyl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amino group. L11, L12, L21, and L22 are each independently: a direct bond (single bond); a substituted or unsubstituted C6 to C60 arylene; or a substituted or unsubstituted C2 to C60 heteroarylene. Ar11, Ar12, Ar21, and Ar22 are each independently: cyano; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; or substituted or unsubstituted silyl. r11 and r12 are each an integer in the range of 1 to 7. r21 is an integer in the range of 1 to 6. r22 is an integer in the range of 1 to 4. l11, l12, l21, and l22 are each independently an integer in the range of 1 to 3. When r11, r12, r21, r22, l11, l12, l21, and l22 are each 2 or higher, the substituents in parentheses are the same or different from each other.

[0169] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, and the light-emitting layer may further include a compound of chemical formula 2 or chemical formula 3.

[0170] In embodiments of this disclosure, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may also include a compound of chemical formula 2 or chemical formula 3.

[0171] In embodiments of this disclosure, the light-emitting layer may further include a compound of formula 2 as a P-type host.

[0172] In embodiments of this disclosure, R11 and R12 may each be independently selected from the group consisting of: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; and substituted or unsubstituted C2 to C60 heteroaryl.

[0173] In embodiments of this disclosure, R11 and R12 may each be independently selected from the group consisting of: hydrogen; deuterium; substituted or unsubstituted C6 to C60 aryl groups; and substituted or unsubstituted C2 to C60 heteroaryl groups.

[0174] In embodiments of this disclosure, R11 and R12 may each be independently: hydrogen; or deuterium.

[0175] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a substituted or unsubstituted C6 to C60 arylene group.

[0176] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.

[0177] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a substituted or unsubstituted C6 to C15 arylene group.

[0178] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; a substituted or unsubstituted phenylene; or a substituted or unsubstituted biphenylene.

[0179] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a substituted or unsubstituted phenylene oxide.

[0180] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a deuterium-substituted or unsubstituted C6 to C60 arylene group.

[0181] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a C6 to C30 arylene group substituted with or unsubstituted with deuterium.

[0182] In embodiments of this disclosure, L11 and L12 may each be independently: a direct bond; or a C6 to C15 arylene group substituted with or unsubstituted with deuterium.

[0183] In embodiments of this disclosure, Ar11 and Ar12 may each be independently: cyano; substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C2 to C30 heteroaryl; or substituted or unsubstituted C1 to C30 silyl.

[0184] In embodiments of this disclosure, Ar11 and Ar12 may each be independently: substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C2 to C30 heteroaryl; or substituted or unsubstituted C1 to C30 silyl.

[0185] In embodiments of this disclosure, Ar11 and Ar12 may each be independently: cyano; substituted or unsubstituted C6 to C30 aryl; or substituted or unsubstituted C6 to C30 arylsilyl.

[0186] In embodiments of this disclosure, Ar11 and Ar12 may each be independently: cyano; substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl; substituted or unsubstituted naphthyl; substituted or unsubstituted triphenylene; substituted or unsubstituted fluorenyl; or substituted or unsubstituted triphenylsilyl.

[0187] In embodiments of this disclosure, Ar11 and Ar12 may each be independently: substituted or unsubstituted C6 to C30 aryl; or substituted or unsubstituted C6 to C30 arylsilyl.

[0188] In the embodiments of this disclosure, Ar11 and Ar12 may each be independently: substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl; substituted or unsubstituted naphthyl; substituted or unsubstituted triphenylene; substituted or unsubstituted fluorenyl; or substituted or unsubstituted triphenylsilyl.

[0189] In embodiments of this disclosure, Ar11 and Ar12 may each be independently a C6 to C30 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; cyano; alkyl; and aryl, or a C6 to C30 arylsilyl group substituted or unsubstituted with deuterium.

[0190] In embodiments of this disclosure, chemical formula 2 may be represented by any of the following compounds.

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197] In embodiments of this disclosure, the light-emitting layer may further include a compound of formula 3 as a P-type host.

[0198] In embodiments of this disclosure, R21 and R22 may each be independently selected from the group consisting of: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; and substituted or unsubstituted C2 to C60 heteroaryl.

[0199] In embodiments of this disclosure, R21 and R22 may each be independently selected from the group consisting of: hydrogen; deuterium; substituted or unsubstituted C6 to C60 aryl groups; and substituted or unsubstituted C2 to C60 heteroaryl groups.

[0200] In embodiments of this disclosure, R21 and R22 may each be independently: hydrogen; or deuterium.

[0201] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a substituted or unsubstituted C6 to C30 arylene; or a substituted or unsubstituted C2 to C30 heteroarylene.

[0202] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a substituted or unsubstituted C6 to C15 arylene; or a substituted or unsubstituted C2 to C15 heteroarylene.

[0203] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a substituted or unsubstituted phenylene; a substituted or unsubstituted biphenylene; or a substituted or unsubstituted divalent dibenzofuranyl.

[0204] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a substituted or unsubstituted phenylene group; or a substituted or unsubstituted divalent dibenzofuranyl group.

[0205] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a deuterated or unsubstituted C6 to C30 arylene; or a deuterated or unsubstituted C2 to C30 heteroarylene.

[0206] In embodiments of this disclosure, L21 and L22 may each be independently: a direct bond; a deuterated or unsubstituted C6 to C15 arylene; or a deuterated or unsubstituted C2 to C15 heteroarylene.

[0207] In embodiments of this disclosure, Ar21 and Ar22 may each be independently: substituted or unsubstituted C6 to C30 aryl; or substituted or unsubstituted C2 to C30 heteroaryl.

[0208] In the embodiments of this disclosure, Ar21 and Ar22 may each be independently: substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; substituted or unsubstituted terphenyl; substituted or unsubstituted triphenylene; substituted or unsubstituted dibenzofuranyl; or substituted or unsubstituted dibenzothiophene.

[0209] In embodiments of this disclosure, Ar21 and Ar22 may each be independently: a deuterated or unsubstituted C6 to C30 aryl group; or a deuterated or unsubstituted C2 to C30 heteroaryl group.

[0210] In embodiments of this disclosure, chemical formula 3 may be represented by any of the following compounds.

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217] The organic material layer of the organic light-emitting device disclosed herein can be formed as a single-layer structure, but it can also be formed as a multilayer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of this disclosure can have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer as organic material layers. However, the structure of the organic light-emitting device is not limited to this, and it can include fewer organic material layers.

[0218] In embodiments of this disclosure, the first electrode may be an anode, and the second electrode may be a cathode.

[0219] In embodiments of this disclosure, the first electrode may be a cathode, and the second electrode may be an anode.

[0220] The organic light-emitting device according to the embodiments of this disclosure can be manufactured using conventional manufacturing methods and materials for organic light-emitting devices, except that one or more organic material layers are formed using a heterocyclic compound represented by the above-described chemical formula 1.

[0221] When manufacturing organic light-emitting devices, heterocyclic compounds represented by chemical formula 1 can be formed into organic material layers using solution coating and vacuum deposition methods. In this document, solution coating methods refer to, but are not limited to, spin coating, dip coating, inkjet printing, screen printing, spray coating, and roll coating.

[0222] In embodiments of this disclosure, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the blue organic light-emitting device. For example, the heterocyclic compound represented by Formula 1 may be included in the light-emitting layer of the blue organic light-emitting device.

[0223] In another embodiment of this disclosure, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the green organic light-emitting device. For example, the heterocyclic compound represented by Formula 1 may be included in the light-emitting layer of the green organic light-emitting device.

[0224] In another embodiment of this disclosure, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the red organic light-emitting device. For example, the heterocyclic compound represented by Formula 1 may be included in the light-emitting layer of the red organic light-emitting device.

[0225] The organic light-emitting device disclosed herein may further include one or more layers selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

[0226] Figures 1 to 3 The stacking order of electrodes and organic material layers in an organic light-emitting device according to an embodiment of this disclosure is illustrated by way of example. However, the scope of this application is not limited to these figures, and structures of organic light-emitting devices known in the art may also be used in this application.

[0227] Figure 1 An organic light-emitting device is shown in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100. However, the structure is not limited to this, and as shown... Figure 2 As shown, an organic light-emitting device in which the cathode, organic material layer and anode are sequentially stacked on a substrate can also be realized.

[0228] Figure 3 An example is shown in which the organic material layers have a multilayer structure. According to... Figure 3 The organic light-emitting device includes a hole injection layer 301, a hole transport layer 302, a light-emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of this application is not limited to this stacked structure, and if necessary, layers other than the light-emitting layer can be omitted, or other required functional layers can be added.

[0229] The organic material layer, including heterocyclic compounds of formula 1, may also include other materials as needed.

[0230] In the organic light-emitting devices according to embodiments of this disclosure, materials other than heterocyclic compounds of Formula 1 are illustrated below. However, these are for illustrative purposes only and are not intended to limit the scope of this application, and other materials known in the art may be substituted.

[0231] As anode materials, materials with relatively large work functions can be used, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of anode materials include: metals such as vanadium, chromium, copper, zinc, and gold or their alloys; 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, but are not limited thereto.

[0232] Materials with relatively small work functions can be used as cathode materials, and metals, metal oxides, or conductive polymers can be used. Specific examples of cathode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; multilayer materials such as LiF / Al or LiO2 / Al, but are not limited to these.

[0233] As hole injection materials, known hole injection materials can 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 literature [Advanced Material, 6, p. 677 (1994)], such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), and 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB). Alternatively, soluble conductive polymers, such as polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid, or polyaniline / poly(4-styrenesulfonate), can also be used.

[0234] As hole transport materials, pyrazoline derivatives, aromatic amine derivatives, stilbene derivatives, and triphenyldiamine derivatives can be used, as well as low molecular weight materials or high molecular weight materials.

[0235] Metal complexes of oxadiazole derivatives, anthraquinone dimethyl ether and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethyl ether and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, biphenylquinone derivatives and 8-hydroxyquinoline and its derivatives can be used as electron transport materials, as well as low molecular weight materials and high molecular weight materials.

[0236] LiF is commonly used in the art as an example of an electron-injection material; however, this application is not limited thereto.

[0237] Red, green, or blue luminescent materials can be used, and two or more luminescent materials can be mixed and used as needed. In this paper, two or more luminescent materials can be deposited with separate supply sources, or premixed and deposited with a single supply source upon use. Furthermore, fluorescent materials can also be used as luminescent materials; however, phosphorescent materials can also be used. As luminescent materials, materials that emit light by combining holes and electrons injected separately from the anode and cathode can be used alone; however, materials having a host material and a dopant material that participate together in light emission can also be used.

[0238] When using substrates for luminescent materials in combination, substrates from the same series or different series can be mixed and used. For example, any two or more types of materials selected from N-type and P-type substrate materials can be chosen and used as the substrate material for the luminescent layer.

[0239] Depending on the materials used, the organic light-emitting device according to embodiments of this disclosure may be a top-emitting type, a bottom-emitting type, or a dual-emitting type.

[0240] The heterocyclic compounds according to embodiments of this disclosure can also be used in organic electronic devices, including organic solar cells, organic photoconductors, and organic transistors, based on similar principles used in organic light-emitting devices.

[0241] Furthermore, by introducing various substituents into the structure of compounds represented by Formula 1, the band gap can be finely tuned. In addition, it can enhance the interfacial properties between organic materials and expand the range of applications for these materials.

[0242] Another embodiment of this disclosure provides a composition for an organic material layer comprising a heterocyclic compound represented by chemical formula 1.

[0243] In embodiments of this disclosure, the composition for the organic material layer may further include compounds of formula 2 or formula 3.

[0244] In embodiments of this disclosure, the composition for the organic material layer may include a heterocyclic compound and a compound of formula 2 or formula 3 in a weight ratio of 1:10 to 10:1.

[0245] In embodiments of this disclosure, the composition for the organic material layer may include a heterocyclic compound and a compound of formula 2 or formula 3 in a weight ratio of 1:8 to 8:1, 1:5 to 5:1 or 1:3 to 3:1.

[0246] In embodiments of this disclosure, the composition for the organic material layer may include a heterocyclic compound and a compound of formula 2 or formula 3 in a weight ratio of 1:1 to 5:1 or 1:1 to 3:1.

[0247] Another embodiment of this disclosure provides a method for manufacturing an organic light-emitting device, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the one or more organic material layers, wherein the formation of the one or more organic material layers comprises forming the one or more organic material layers using the composition described above for the organic material layers.

[0248] In embodiments of this disclosure, the formation of one or more organic material layers may include premixing a composition for the organic material layers and depositing the composition for the organic material layers as a single source.

[0249] As used herein, "premixed" means that a heterocyclic compound of Formula 1 and a compound of Formula 2 or Formula 3 are mixed together and placed in a single crucible (single source container) before being deposited onto an organic material layer. In the case of premixing, a single deposition source is used instead of two or more deposition sources, which has the advantage of simplifying the process.

[0250] When premixing compositions for use in organic material layers, the inherent thermal properties of each material to be premixed must be verified. This is because these properties can significantly affect deposition conditions (such as deposition rate) during the deposition of the premixed materials. If the thermal properties of the materials are not similar, repeatability and reproducibility in the deposition process cannot be maintained, making it impossible to manufacture uniform OLED devices.

[0251] To overcome these challenges, the electrical properties of materials can be tuned by utilizing appropriate combinations of core structures and substituents, while the thermal properties can be adjusted based on the molecular structure. By controlling the thermal properties of each material, the versatility of various premixed deposition processes for host-host combinations can be ensured. Therefore, this ensures the flexibility of premixed deposition processes that utilize not only two types of compounds as hosts but also three or more types of host materials.

[0252] In embodiments of this disclosure, the composition for the organic material layer may include another host, in addition to compounds of formula 2 or formula 3.

[0253] In embodiments of this disclosure, the composition for the organic material layer may include a compound of formula 2 or formula 3, and may also include another entity.

[0254] The present disclosure will be described in detail below with reference to the following examples. However, the following examples are merely illustrative of the present disclosure, and the scope of the disclosure is not limited thereto.

[0255] <Preparation Example> <Preparation Example 1> Preparation of Compound 1-1

[0256] 1) Preparation of compound 1-1-1-a 9-(2-bromophenyl)-9H-carbazole (10 g, 31.0 mM), D6-benzene (100 ml), and trifluoromethanesulfonic acid (CF3SO3H, 14.7 ml, 155 mM) were placed in a reactor and refluxed at 50 °C for 2 hours. After the reaction was complete, the mixture was neutralized with a supersaturated aqueous solution of K3PO4. Distilled water and dichloromethane (DCM) were added to the mixture at room temperature to extract the organic layer. The separated organic layer was dried over MgSO4 and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:4) to obtain 9.8 g of compound 1-1-1-a (yield: 95%).

[0257] 2) Preparation of compound 1-1-1-b Compound 1-1-1-a (9.8 g, 29.3 mM), Pd(dppf)Cl2 ([1,1′-bis(diphenylphosphine)ferrocene]palladium(II) chloride) (1.07 g, 1.47 mM), and KOAc (potassium acetate) (5.75 g, 58.6 mM) were placed in a reactor, dissolved in 100 mL of 1,4-dioxane, and then refluxed at 101 °C for 4 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4, and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:1) to obtain 8 g of compound 1-1-1-b (yield: 72%).

[0258] 3) Preparation of compound 1-1-1-c Compound [A] (1-bromo-6-chlorodibenzo[b,d]furan) (10 g, 35.5 mM), compound [B] (phenylboronic acid) (4.42 g, 35.5 mM), Pd(PPh3)4 (tetra(triphenylphosphine)palladium(0)) (2.05 g, 1.8 mM), and K2CO3 (9.82 g, 71 mM) were placed in a reactor, dissolved in 1,4-dioxane / H2O (100 mL / 20 mL), and then refluxed at 101 °C for 5 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4, and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:2) to obtain 9.5 g of compound 1-1-1-c (yield: 96%).

[0259] 4) Preparation of compound 1-1-1-d Compound 1-1-1-c (9.5 g, 34.1 mM), bis(pinacol)diboron (13.0 g, 51.2 mM), Pd2(dba)3 (3.12 g, 3.41 mM), and KOAc (8.37 g, 85.3 mM) were placed in a reactor, dissolved in 100 mL of 1,4-dioxane, and then refluxed at 101 °C for 4 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4, and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:1) to obtain 11 g of compound 1-1-1-d (yield: 87%).

[0260] 5) Preparation of compound 1-1-1-e Compound 1-1-1-d (11 g, 29.7 mM), compound [C](2,4-dichloro-6-phenyl-1,3,5-triazine) (6.7 g, 29.7 mM), Pd(PPh3)4 (1.7 g, 1.49 mM), and K2CO3 (10.3 g, 74.3 mM) were placed in a reactor, dissolved in 1,4-dioxane / H2O (110 mL / 22 mL), and then refluxed at 101 °C for 5 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4, and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:3) to obtain 10.1 g of compound 1-1-1-e (yield: 78%).

[0261] 6) Preparation of compound 1-1-1 Compounds 1-1-1-b (8 g, 21.0 mM), 1-1-1-e (9.1 g, 21.0 mM), Pd(PPh3)4 (1.8 g, 1.55 mM), and K2CO3 (7.3 g, 52.5 mM) were placed in a reactor, dissolved in 1,4-dioxane / H2O (100 mL / 20 mL), and then refluxed at 101 °C for 5 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4, and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:2) to obtain 9.0 g of compound 1-1-1 (yield: 66%).

[0262] The target compounds in Table 1 were synthesized in the same manner as described in Preparation Example 1, except that intermediate A in Table 1 was used instead of compound [A], intermediate B in Table 1 was used instead of compound [B], and intermediate C in Table 1 was used instead of compound [C].

[0263] [Table 1]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274] <Preparation Example 2> Preparation of Compounds 2-3

[0275] Compound [a] (3-bromo-1,1'-biphenyl) (3.7 g, 15.8 mM), compound [b] (9-phenyl-9H,9'H-3,3'-bicarbazole) (6.5 g, 15.8 mM), CuI (0.3 g, 1.58 mM), trans-1,2-diaminocyclohexane (0.19 mL, 1.58 mM), and K3PO4 (3.3 g, 31.6 mM) were dissolved in 1,4-dioxane (100 mL) and then refluxed at 110 °C for 12 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4 and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:3) and recrystallized from methanol to obtain 7.5 g of compounds 2-3 (yield: 85%).

[0276] The target compounds shown in Table 2 below were synthesized in the same manner as in Preparation Example 2, except that intermediate a from Table 2 was used instead of compound [a], and intermediate b from Table 2 was used instead of compound [b].

[0277] [Table 2]

[0278] <Preparation Example 3> Preparation of Compound 2-98

[0279] 1) Preparation of compound 2-98-1 In a single-necked round-bottom flask (rbf), 9H,9'H-3,3'-bicarbazole (10 g, 0.030 mol), compound [c] (4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D9) (7.26 g, 0.030 mol), CuI (0.57 g, 0.003 mol), trans-1,2-diaminocyclohexane (0.34 g, 0.003 mol), and K3PO4 (12.7 g, 0.060 mol) were dissolved in 100 mL of 1,4-dioxane and refluxed at 110 °C for 8 hours. After the reaction was complete, the mixture was cooled, extracted with DCM, and dried over MgSO4. The filtered organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 13.92 g of compound 2-98-1 (yield: 94%).

[0280] 2) Preparation of compound 2-98 In a single-necked round-bottom flask (RBF), compound 2-98-1 (13.92 g, 0.028 mol), compound [d](4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D9) (6.83 g, 0.028 mol), CuI (0.53 g, 0.0028 mol), trans-1,2-diaminocyclohexane (0.32 g, 0.0028 mol), and K3PO4 (11.89 g, 0.056 mol) were dissolved in 140 mL of 1,4-dioxane and then refluxed at 110 °C for 8 hours. After the reaction was complete, the mixture was cooled, extracted with DCM, and dried over MgSO4. The filtered organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 16.14 g of compound 2-98 (yield: 88%).

[0281] The target compounds shown in Table 3 below were synthesized in the same manner as in Preparation Example 3, except that intermediate c in Table 3 was used instead of compound [c], and intermediate d in Table 3 was used instead of compound [d].

[0282] When intermediate c and intermediate d are the same, the target compound can be directly synthesized by adding 2 equivalents of intermediate c during the preparation of compound 2-98-1 in Example 3.

[0283] [Table 3]

[0284] <Preparation Example 4> Preparation of Compound 2-106

[0285] 1) Preparation of compound 2-106-1 In a single-necked round-bottom flask (rbf), a mixture of 9H,9'H-3,3'-bicarbazole (10 g, 0.030 mol), trifluoromethanesulfonic acid (34 g, 0.023 mol), and D6-benzene (100 mL) was refluxed at 50 °C for 2 h. After cooling, the mixture was extracted with DCM and dried over MgSO4. The product was purified by column chromatography to give 7.07 g of compound 2-106-1 (yield: 68%).

[0286] 2) Preparation of compound 2-106-2 In a single-necked round-bottom flask (RBF), compound 2-106-1 (7.07 g, 0.02 mol), CuI (0.38 g, 0.002 mol), compound [e](4-bromo-1,1'-biphenyl) (4.66 g, 0.02 mol), trans-1,4-diaminocyclohexane (0.23 g, 0.002 mol), and K3PO4 (8.49 g, 0.04 mol) were dissolved in 70 mL of 1,4-dioxane and then refluxed at 110 °C for 8 hours. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4 and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:3) and recrystallized from methanol to give 8.28 g of compound 2-106-2 (yield: 83%).

[0287] 3) Preparation of compound 2-106 In a single-necked round-bottom flask (RBF), compound 2-106-2 (8.28 g, 0.017 mol), CuI (0.32 g, 0.0017 mol), compound [f] (4-bromo-1,1'-biphenyl) (3.96 g, 0.017 mol), trans-1,4-diaminocyclohexane (0.19 g, 0.0017 mol), and K3PO4 (7.22 g, 0.034 mol) were dissolved in 80 mL of 1,4-dioxane and then refluxed at 110 °C for 8 h. After the reaction was complete, distilled water and DCM were added at room temperature for extraction. The organic layer was dried over MgSO4 and then the solvent was removed using a rotary evaporator. The product was purified by column chromatography (DCM:hexane = 1:3) and recrystallized from methanol to obtain 8.63 g of compound 2-106 (yield: 78%).

[0288] The target compounds shown in Table 4 below were synthesized in the same manner as in Preparation Example 4, except that intermediate e from Table 4 was used instead of compound [e], and intermediate f from Table 4 was used instead of compound [f].

[0289] When intermediate e and intermediate f are the same, the target compound can be directly synthesized by adding 2 equivalents of intermediate e during the preparation of compound 2-106-1 in Example 4.

[0290] [Table 4]

[0291] <Preparation Example 5> Preparation of Compound 2-110

[0292] In a single-necked round-bottom flask (rbf), a mixture of compound [g] (compound 2-42) (12.17 g, 0.017 mol), trifluoromethanesulfonic acid (40.8 g, 0.27 mol), and D6-benzene (120 mL) was refluxed at 50 °C for 2 h. The mixture was extracted with DCM and water, and the organic layer was dried over MgSO4, concentrated, and then passed through a silica gel filter. After further concentration, the resulting product was recrystallized from methanol to obtain 8.87 g of compound 2-110 (yield: 78%).

[0293] The target compounds shown in Table 5 below were synthesized in the same manner as in Preparation Example 5, except that intermediate g from Table 5 was used instead of compound [g].

[0294] [Table 5]

[0295] <Preparation Example 6> Preparation of Compounds 3-5

[0296] 1) Preparation of compound 3-5-1 5,8-Dihydroindolo[2,3-c]carbazole (20 g, 78.03 mmol) and compound [h] (4-bromo-1,1'-biphenyl) (18.18 g, 78.03 mmol) were dissolved in 200 mL of toluene. Then, Pd2(dba)3 (tris(dibenzylacetone)dipalladium(0)) (3.57 g, 3.90 mmol), sodium tert-butoxide (18.75 g, 195.08 mmol), and Xphos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl) (3.72 g, 7.8 mmol) were added, and the mixture was refluxed and stirred at 101 °C for 6 hours. After the reaction was complete, the reaction solution was dissolved by adding ethyl acetate and then extracted with distilled water. The organic layer was dried over anhydrous MgSO4, and the solvent was removed using a rotary evaporator. The product was then purified by column chromatography using DCM and hexane as eluents to obtain 21.7 g of compound 3-5-1 (yield: 68%).

[0297] 2) Preparation of compounds 3-5 Compound 3-5-1 (21.7 g, 53.12 mmol) and compound [i] (3-bromo-1,1'-biphenyl) (12.38 g, 53.12 mmol) were dissolved in 220 mL of toluene. Then, Pd2(dba)3 (2.43 g, 2.66 mmol), sodium tert-butoxide (12.76 g, 132.80 mmol), and Xphos (2.53 g, 5.31 mmol) were added, and the mixture was refluxed at 101 °C with stirring for 6 hours. After the reaction was complete, the reaction solution was dissolved by adding ethyl acetate and then extracted with distilled water. The organic layer was dried over anhydrous MgSO4, and the solvent was removed using a rotary evaporator. Subsequently, the product was purified by column chromatography using DCM and hexane as eluents to obtain 20.9 g of compound 3-5 (yield: 70%).

[0298] The target compounds shown in Table 6 below were synthesized in the same manner as in Preparation Example 6, except that intermediate h from Table 6 was used instead of compound [h], and intermediate i from Table 6 was used instead of compound [i].

[0299] [Table 6]

[0300] <Preparation Example 7> Preparation of Compounds 3-78

[0301] In a single-necked round-bottom flask (rbf), a mixture of compound [j] (compound 3-5) (10 g, 17.83 mmol), trifluoromethanesulfonic acid (50 g), and D6-benzene (500 mL) was stirred at 50 °C for 1 hour. After the reaction was complete, the mixture was neutralized with a supersaturated aqueous solution of Na2CO3 dissolved in distilled water. After quenching, DCM was added to the mixture for dissolution, and the organic layer was then separated, dried over anhydrous MgSO4, and the solvent was removed using a rotary evaporator. Subsequently, the product was purified by column chromatography using DCM and hexane as eluents to obtain 7.4 g of compound 3-78 (yield: 70%).

[0302] The target compounds shown in Table 7 below were synthesized in the same manner as in Preparation Example 7, except that compound J in Table 7 was used instead of compound [j].

[0303] [Table 7]

[0304] It has been confirmed that for the compounds synthesized in Preparation Examples 1 to 7, the results were obtained by FD-mass spectrometry and proton nuclear magnetic resonance (NMR). 1 The target compound was synthesized by ¹H-NMR. The measurements by FD-MS (field desorption mass spectrometry) are shown in Table 8 below. 1 The H-NMR (CDCl3, 400MHz) measurements are shown in Table 9 below.

[0305] [Table 8]

[0306] [Table 9]

[0307] <Experimental Example> <Experimental Example 1> (1) Manufacturing of organic light-emitting devices A glass substrate coated with an indium tin oxide (ITO) film up to 1500 Å thick was ultrasonically washed with distilled water. After cleaning with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropanol, followed by drying. Then, UVO (ultraviolet ozone) treatment was performed using a UV (ultraviolet) cleaner for 5 minutes. Subsequently, the substrate was transferred to a plasma cleaner (PT) and plasma treatment was performed under vacuum to adjust the ITO work function and remove residual film, after which the substrate was transferred to a thermal evaporation apparatus for organic deposition.

[0308] On the ITO transparent electrode (anode), 2-TNATA (4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine) is formed as a hole injection layer and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) is formed as a hole transport layer; these are common layers.

[0309] The light-emitting layer is formed on a common layer by thermal vacuum deposition as follows. As the host for the light-emitting layer, a compound shown in Table 10 below is deposited to a thickness of 400 Å, and a green phosphorescent dopant Ir(ppy)3 is deposited with a doping concentration of 7%. Subsequently, BCP is deposited to a thickness of 60 Å as a hole-blocking layer, and Alq3 is deposited to a thickness of 200 Å on the hole-blocking layer as an electron transport layer. Finally, lithium fluoride (LiF) is deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer, and aluminum (Al) is deposited to a thickness of 1200 Å on the electron injection layer to form a cathode, thereby fabricating an organic light-emitting device.

[0310] Meanwhile, all organic compounds required for manufacturing OLED devices are purified before being used in OLED manufacturing. -8 Up to 10 -6 Each material was then subjected to vacuum sublimation and purification.

[0311] The compounds used in Comparative Examples 1 to 14, as shown in Table 10 below, are as follows.

[0312]

[0313] (2) Measurement of driving voltage, luminous efficiency and lifetime of organic light-emitting devices For each of the organic light-emitting devices manufactured as described above, electroluminescence (EL) characteristics were measured using an M7000 device (McScience, Inc.). Based on the measurement results, lifetime measurement was performed at 6,000 cd / m² using a lifetime measurement system (M6000) manufactured by McScience, Inc. 2 Lifetime measured at reference brightness (T) 90 The measurement results are shown in Table 10 below.

[0314] [Table 10]

[0315] According to Table 10, in Examples 1 to 45 corresponding to Chemical Formula 1 of this disclosure, the compounds have the structural characteristics in which carbazole and triazine groups are bonded to the ortho position of the phenyl linker and are deuterated. Furthermore, they possess a more robust structure by introducing a heteroaryl group in combination with an additional aryl substituent. The structural deformation is enhanced when the triazine group is substituted at the ortho position of the carbazole in the phenyl linker, which can promote charge transfer. Moreover, the introduction of an additional aryl group at the 1 position of the heteroaryl group provides an expanded and broad π-conjugated region, which can be used as an auxiliary means to tune the band gap. Due to the effect of the additional aryl group, the compounds possess a more robust and rigid structure, providing the advantage of maintaining a high T1 energy level.

[0316] When comparative compounds A to D were used in Comparative Examples 1 to 4, although the compounds were structurally similar to those of the present disclosure, they exhibited high driving voltage, low efficiency, and low lifetime. The difference between comparative compounds A to D and the present disclosure lies in the meta- or para-substitution of the triazine and carbazole groups on the phenyl linker. This increases bond rotation and molecular vibrational energy, which reduces the stability of the molecular structure, resulting in poor device performance in terms of lifetime and driving characteristics. Furthermore, based on the device results of Comparative Examples 1 to 4, it was confirmed that the effect of deuterium substitution on the carbazole substituents was insignificant at the meta- and para-positions of the phenyl linker.

[0317] In the cases where comparative compounds E and F are used in Comparative Examples 5 and 6, these compounds differ from the present disclosure in that no aryl substituent is introduced at the end of the heteroaryl group. It is confirmed that bond rotation becomes more favorable due to the exclusion of the aryl group in the molecular structure, which reduces the stability of the molecular structure, resulting in an increase in driving voltage and a decrease in lifetime.

[0318] In the case of using Comparative Compound G in Comparative Example 7, although the compound is structurally similar to the compound of this disclosure, the difference lies in that the phenyl linking group and the carbazole substituent are composed of light hydrogen (protium) instead of deuterium. Comparing the device results of Comparative Example 7 and Example 11 confirms that the structure of this disclosure exhibits superior drive voltage characteristics, efficiency characteristics, and lifetime characteristics due to the deuterium substitution effect. The deuterated materials of this disclosure exhibit improved drive characteristics and lifetime characteristics compared to Comparative Compound G due to enhanced molecular stability and amorphous properties. Furthermore, they are able to improve efficiency by minimizing energy loss via low vibrational energy, thereby facilitating energy transfer to the dopant.

[0319] The comparative compounds H and I used in Comparative Examples 8 and 9 differ from this disclosure in that the triazine group has a structure with two heteroaryl substituents. While materials with high electronegativity (such as oxygen or sulfur (S) atoms in dibenzofuran or dibenzothiophene) are advantageous for increasing charge mobility, they also have the disadvantage of promoting decreased molecular stability as electron mobility increases. It has been confirmed that when the triazine group is over-substituted with heteroaryl groups, this decrease in stability is exacerbated, leading to a reduction in device lifetime and efficiency.

[0320] In the cases where comparative compounds J and K are used in Comparative Examples 10 and 11, the difference between comparative compounds J and K and this disclosure is that the aryl group is substituted at the 2 and 4 positions of dibenzofuran and dibenzothiophene instead of the 1 position, and the carbazole group is substituted at the meta position of the phenyl linker. It is confirmed that in comparative compounds J and K, the reduction of steric hindrance between substituents leads to increased bond rotation and higher vibrational energy. This reduces the stability of the molecular structure, resulting in poorer device performance in terms of lifetime and drive characteristics.

[0321] In the case of using Comparative Compound L in Comparative Example 12, Comparative Compound L differs from the present disclosure in that the nitrile (-CN) substituent is bonded to the end of the aryl group. Since the nitrile group is a characteristic electron-withdrawing group (EWG), it weakens the electron-donating ability of the triazine, which is also an EWG. This hinders intramolecular electron flow and requires a higher driving voltage, leading to a decrease in luminescence efficiency. Furthermore, the high voltage causes charge accumulation within the emitter layer, resulting in nonradiative recombination and a shorter lifetime.

[0322] In the cases where comparative compounds M and N are used in Comparative Examples 13 and 14, these compounds differ from the present disclosure in that they have a structure substituted with carbazole fused to an additional heterocycle. It is confirmed that the carbazole-fused derivative-type substituent is larger than the simple carbazole substituent and expands the highest occupied molecular orbital (HOMO) region of the molecule, leading to an increase in driving voltage and a decrease in efficiency.

[0323] Typically, hydrogen-bonded compounds and deuterium-substituted compounds exhibit different thermodynamic behaviors. This is because the mass of a deuterium atom is twice that of a hydrogen atom, and this difference in atomic mass results in a lower vibrational energy for deuterium. Furthermore, the bond length between carbon and deuterium is shorter than that between carbon and hydrogen, and the dissociation energy required to break the bond is also higher. This is attributed to the fact that the van der Waals radius of deuterium is smaller than that of hydrogen, which leads to a narrower stretching range of the carbon-deuterium bond.

[0324] Compounds substituted with deuterium exhibit lower ground-state energies compared to those substituted with only hydrogen. As the carbon-deuterium bond length decreases, the volume of the molecular hard core diminishes. This reduces polarizability and weakens intermolecular interactions, thereby increasing the volume of the thin film in the device. These properties induce an amorphous state in the film, thus reducing crystallinity. Therefore, deuterium substitution can effectively enhance the thermal resistance of OLED devices, thereby improving their lifetime characteristics.

[0325] <Experimental Example 2> (1) Manufacturing of organic light-emitting devices A glass substrate coated with an indium tin oxide (ITO) film up to 1500 Å thick was ultrasonically washed with distilled water. After cleaning with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropanol, followed by drying. Then, UVO (ultraviolet ozone) treatment was performed using a UV (ultraviolet) cleaner for 5 minutes. Subsequently, the substrate was transferred to a plasma cleaner (PT) and plasma treatment was performed under vacuum to adjust the ITO work function and remove residual film, after which the substrate was transferred to a thermal evaporation apparatus for organic deposition.

[0326] On the ITO transparent electrode (anode), 2-TNATA (4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine) is formed as a hole injection layer and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) is formed as a hole transport layer; these are common layers.

[0327] The light-emitting layer is formed on a common layer via thermal vacuum deposition as follows. The light-emitting layer is formed by premixing the two types of compounds listed in Table 11 as the host material using the weight ratios described in Table 11; depositing the premixed composition from a single source to a thickness of 400 Å; and doping with a 7% green phosphorescent dopant Ir(ppy)3 during deposition. Subsequently, BCP (bath copper spirit) is deposited to a thickness of 60 Å as a hole-blocking layer, followed by Alq3 deposition to a thickness of 200 Å on the hole-blocking layer as an electron transport layer. Finally, lithium fluoride (LiF) is deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1200 Å on the electron injection layer, thereby fabricating an organic light-emitting device (OLED).

[0328] Meanwhile, all organic compounds required for manufacturing OLED devices are purified before being used in OLED manufacturing. -8 Up to 10 -6 Each material was then subjected to vacuum sublimation and purification.

[0329] (2) Measurement of driving voltage, luminous efficiency and lifetime of organic light-emitting devices For each of the organic light-emitting devices manufactured as described above, electroluminescence (EL) characteristics were measured using an M7000 device (McScience, Inc.). Based on the measurement results, lifetime measurement was performed at 6,000 cd / m² using a lifetime measurement system (M6000) manufactured by McScience, Inc. 2 Lifetime measured at reference brightness (T) 90 The measurement results are shown in Table 11 below.

[0330] [Table 11]

[0331]

[0332]

[0333] Referring to the results of Examples 46 to 132 in Table 11, excellent efficiency and lifetime effects are observed when the compound represented by Chemical Formula 1 (n-type) according to this disclosure is used together with the compound represented by Chemical Formula 2 (p-type). This result is due to the excitocomplexation phenomenon that occurs when both compounds are included simultaneously.

[0334] Exciton complexation is a process in which intermolecular electron exchange emits energy equivalent to the energy difference between the HOMO level of the donor (p-host) and the lowest unoccupied molecular orbital (LUMO) level of the acceptor (n-host). When exciton complexation occurs between two molecules, reverse intersystem crossing (RISC) takes place, which can increase the internal quantum efficiency of fluorescence up to 100%.

[0335] When a donor (p-host) with excellent hole transport capability and an acceptor (n-host) with excellent electron transport capability are used as hosts in the emissive layer, holes are injected into the p-host and electrons are injected into the n-host. In this case, excitons are not quenched by intermolecular electron exchange, and the lifetime of excitons that can retain energy is increased. This leads to an improvement in overall current efficiency and helps to increase device lifetime. In this disclosure, it is confirmed that the compound of Formula 1 acts as the acceptor and the compound of Formula 2 acts as the donor, exhibiting excellent device characteristics when used together as hosts for the emissive layer.

[0336] When a heterocyclic compound of Formula 1 and a compound of Formula 2 are mixed and used as materials for the emissive layer, not only can the current efficiency of the emissive layer be partially improved, but devices with long lifetime characteristics can also be realized. In some cases, the driving voltage can be increased when exocomplexation occurs due to the charge imbalance between holes and electrons in the emissive layer of the device. This problem is caused by the deviation in hole mobility and electron mobility of each material in the mixed matrix. Therefore, optimal performance devices can be constructed only when the balance of carrier current within the device is properly maintained, and this problem can be solved by adjusting the ratio between acceptor and donor.

[0337] <Experiment Example 3> (1) Manufacturing of organic light-emitting devices A glass substrate coated with an indium tin oxide (ITO) film up to 1500 Å thick was ultrasonically washed with distilled water. After cleaning with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropanol, followed by drying. Then, UVO (ultraviolet ozone) treatment was performed using a UV (ultraviolet) cleaner for 5 minutes. Subsequently, the substrate was transferred to a plasma cleaner (PT) and plasma treatment was performed under vacuum to adjust the ITO work function and remove residual film, after which the substrate was transferred to a thermal evaporation apparatus for organic deposition.

[0338] On the ITO transparent electrode (anode), 2-TNATA (4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine) is formed as a hole injection layer and NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) is formed as a hole transport layer; these are common layers.

[0339] The light-emitting layer is formed on a common layer via thermal vacuum deposition as follows. The light-emitting layer is formed by premixing the two types of compounds listed in Table 12 as the host material using the weight ratios described in Table 12; depositing the premixed composition from a single source to a thickness of 400 Å; and doping with a 7% green phosphorescent dopant Ir(ppy)3 during deposition. Subsequently, BCP (bath copper spirit) is deposited to a thickness of 60 Å as a hole-blocking layer, followed by Alq3 deposition to a thickness of 200 Å on the hole-blocking layer as an electron transport layer. Finally, lithium fluoride (LiF) is deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1200 Å on the electron injection layer, thereby fabricating an organic light-emitting device (OLED).

[0340] Meanwhile, all organic compounds required for manufacturing OLED devices are purified before being used in OLED manufacturing. -8 Up to 10 -6 Each material was then subjected to vacuum sublimation and purification.

[0341] (2) Measurement of driving voltage, luminous efficiency and lifetime of organic light-emitting devices For each of the organic light-emitting devices manufactured as described above, electroluminescence (EL) characteristics were measured using an M7000 device (McScience, Inc.). Based on the measurement results, lifetime measurement was performed at 6,000 cd / m² using a lifetime measurement system (M6000) manufactured by McScience, Inc. 2 Lifetime measured at reference brightness (T) 90 The measurement results are shown in Table 12 below.

[0342] [Table 12]

[0343]

[0344]

[0345] Comparing the results in Table 12 with those in Table 10, it is confirmed that when both the heterocyclic compound of Formula 1 and the compound of Formula 3 of this disclosure are used as the host for the luminescent layer, the driving voltage, luminous efficiency, and lifetime are all improved. Therefore, it is expected that excitocomplexation occurs when both the compound of Formula 1 and the compound of Formula 3 are included. The description of the excitocomplexation phenomenon is the same as that illustrated in Examples 46 to 132 of Experimental Examples 2. However, in the cases of Examples 133 to 219, it is confirmed that when the compound of Formula 3 acts as the donor and the heterocyclic compound of Formula 1 acts as the acceptor, excellent device characteristics are exhibited when both types of compounds are used together as the host for the luminescent layer.

[0346] In other words, it can be confirmed that when the heterocyclic compound of Formula 1 and the compound of Formula 3 according to this disclosure are used simultaneously as the host for the light-emitting layer, the driving voltage, luminous efficiency and lifetime are significantly superior.

Claims

1. A heterocyclic compound, said heterocyclic compound being represented by the following chemical formula 1: [Chemical Formula 1] in, In chemical formula 1, X is O or S; Ar1 is a C6 to C60 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl; Ar2 is a substituted or unsubstituted C6 to C60 aryl group; R1 to R4 are each independently: hydrogen; deuterium; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; or substituted or unsubstituted C2 to C60 heteroaryl. D is deuterium, d1 is an integer from 1 to 4, and d2 is an integer from 1 to 8; r1 and r2 are each an independent integer from 1 to 3. r3 is an integer from 0 to 3, and the sum of d1 and r3 is 4; r4 is an integer from 0 to 7, and the sum of d2 and r4 is 8; and When each of r1 to r4 is 2 or greater, the substituents in parentheses are either the same or different from each other.

2. The heterocyclic compound according to claim 1, in, Chemical formula 1 includes the structures of chemical formulas A and B. Among them, chemical formula A has a deuterium substitution rate of 30% to 100%, and Among them, chemical formula B has a deuterium substitution rate of 0% to 50%: [Chemical Formula A] [Chemical Formula B] In chemical formula A and chemical formula B, It is the position where chemical formula A and chemical formula B are bonded, and Each substituent is as defined in claim 1.

3. The heterocyclic compound according to claim 1, in, Chemical formula 1 is represented by the following chemical formula 1-D: [Chemical Formula 1-D] In chemical formula 1-D, Each substituent is as defined in claim 1.

4. The heterocyclic compound according to claim 1, in, Ar1 is a C6 to C30 aryl group that is substituted or unsubstituted by one or more substituents selected from the group consisting of: deuterium; halogen groups; alkyl; cycloalkyl; aryl; and heteroaryl.

5. The heterocyclic compound according to claim 1, in, R1 to R4 are each independently either hydrogen or deuterium.

6. The heterocyclic compound according to claim 1, in, Chemical formula 1 is represented by any of the following compounds: 。 7. An organic light-emitting device, comprising: First electrode; Second electrode; as well as One or more organic material layers are disposed between the first electrode and the second electrode. Wherein, at least one of the one or more organic material layers comprises one or more heterocyclic compounds according to any one of claims 1 to 6.

8. The organic light-emitting device according to claim 7, in, The organic material layer includes a light-emitting layer, and The light-emitting layer includes one or more heterocyclic compounds.

9. The organic light-emitting device according to claim 8, in, The light-emitting layer includes a main body, and The main body includes one or more heterocyclic compounds.

10. The organic light-emitting device according to claim 7, in, The organic material layer including the heterocyclic compound also includes a heterocyclic compound represented by the following chemical formula 2 or chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] Among them, in chemical formulas 2 and 3, R11, R12, R21, and R22 are each independently selected from the group consisting of: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C2 to C60 alkenyl; substituted or unsubstituted C2 to C60 alkoxy; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; substituted or unsubstituted silyl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amino group. L11, L12, L21, and L22 are each independently: a direct bond; a substituted or unsubstituted C6 to C60 arylene; or a substituted or unsubstituted C2 to C60 heteroarylene. Ar11, Ar12, Ar21, and Ar22 are each independently: cyano; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; or substituted or unsubstituted silyl. r11 and r12 are each an integer in the range of 1 to 7. r21 is an integer in the range of 1 to 6. r22 is an integer in the range of 1 to 4. l11, l12, l21, and l22 are each independently an integer in the range of 1 to 3. When r11, r12, r21, r22, l11, l12, l21, and l22 are each 2 or higher, the substituents in parentheses are the same or different from each other.

11. The organic light-emitting device according to claim 10, in, Chemical formula 2 is selected from the following compounds: 。 12. The organic light-emitting device according to claim 10, in, Chemical formula 3 is selected from the following compounds: 。 13. A composition for an organic material layer, comprising a heterocyclic compound according to any one of claims 1 to 6; and a compound represented by chemical formula 2 or chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] in, In chemical formulas 2 and 3, R11, R12, R21, and R22 are each independently selected from the group consisting of: hydrogen; deuterium; halogen group; cyano; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C2 to C60 alkenyl; substituted or unsubstituted C2 to C60 alkoxy; substituted or unsubstituted C3 to C60 cycloalkyl; substituted or unsubstituted C2 to C60 heterocycloalkyl; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; substituted or unsubstituted silyl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amino group. L11, L12, L21, and L22 are each independently: a direct bond; a substituted or unsubstituted C6 to C60 arylene; or a substituted or unsubstituted C2 to C60 heteroarylene. Ar11, Ar12, Ar21, and Ar22 are each independently: cyano; substituted or unsubstituted C6 to C60 aryl; substituted or unsubstituted C2 to C60 heteroaryl; or substituted or unsubstituted silyl. r11 and r12 are each an integer in the range of 1 to 7. r21 is an integer in the range of 1 to 6. r22 is an integer in the range of 1 to 4. l11, l12, l21, and l22 are each independently an integer in the range of 1 to 3. When r11, r12, r21, r22, l11, l12, l21, and l22 are each 2 or higher, the substituents in parentheses are the same or different from each other.

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