Organic electroluminescent device and heterocyclic compound for the same

Abstract

The invention relates to an organic electroluminescent device and a heterocyclic compound. The device comprises a first electrode; a hole transport region on the first electrode; an emission layer on the hole transport region; an electron transport region on the emission layer; and a second electrode on the electron transport region wherein the emission layer comprises a heterocyclic compound comprising a nitrogen-containing monoring, at least one linker, and two or more carbazole moieties, the at least one linker is a substituted or unsubstituted dibenzofuran group or a substituted or unsubstituted dibenzothiophene group, and at least one of the carbazole moieties and the nitrogen-containing monoring are bonded to the at least one linker in an ortho relationship.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is a divisional application of Chinese Patent Application No. 201910553461.4, and Korean Patent Application No. 10-2018-0073189 filed with the Korean Intellectual Property Office on June 26, 2018 and entitled “Organic electroluminescent device and heterocyclic compound for organic electroluminescent device” is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments relate to an organic electroluminescent device and a heterocyclic compound for an organic electroluminescent device. Background Art

[0004] The development of organic electroluminescent displays as image display devices is actively underway. Unlike liquid crystal display devices, organic electroluminescent displays are self-luminescent displays in which holes and electrons injected from the first electrode and the second electrode are recombined in the emission layer, and the luminescent material of the organic compound contained in the emission layer emits light to achieve display.

[0005] The organic electroluminescent device may include, for example, an organic device including a first electrode, a hole transport layer on the first electrode, an emission layer on the hole transport layer, an electron transport layer on the emission layer, and a second electrode on the electron transport layer. Holes are injected from the first electrode, and the injected holes move via the hole transport layer and are injected into the emission layer. At the same time, electrons are injected from the second electrode, and the injected electrons move via the electron transport layer and are injected into the emission layer. The holes and electrons injected into the emission layer recombine to generate excitons in the emission layer. The organic electroluminescent device emits light using light generated by the transition of the excitons to the ground state. Summary of the invention

[0006] The embodiment may be achieved by providing a heterocyclic compound represented by the following Formula 1,

[0007] [Formula 1]

[0008]

[0009] Among them, in formula 1,

[0010] Z 1 To Z 3 Each independently is CR 1 or N,

[0011] Z 1 To Z 3 At least one of them is N,

[0012] R 1is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms,

[0013] Ar 1 To Ar 3 are each independently a group represented by the following Formula 2, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, and

[0014] Ar 1 To Ar 3 At least one of them is a group represented by Formula 2:

[0015] [Formula 2]

[0016]

[0017] In formula 2,

[0018] X 1 is O or S,

[0019] "n" is an integer from 1 to 3,

[0020] "a" to "c" are each independently an integer from 0 to 4,

[0021] "d" is an integer from 0 to 2, and

[0022] R 2 To R 5 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms,

[0023] When Ar 1 To Ar 3 When only one of is a group represented by the above formula 2, "n" is 2 or 3, and

[0024] At least one of the carbazole moieties in Formula 2 is relative to the carbazole moiety in Formula 1 comprising Z 1 To Z 3 The nitrogen-containing monocyclic rings are bonded in an ortho relationship.

[0025] The embodiment may be implemented by providing an organic electroluminescent device, the organic electroluminescent device comprising:

[0026] a first electrode;

[0027] a hole transport region on the first electrode;

[0028] an emitting layer on the hole transport region;

[0029] an electron transport region on the emissive layer; and

[0030] a second electrode on the electron transport region,

[0031] wherein the emissive layer comprises a heterocyclic compound as defined herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Features will become apparent to those skilled in the art by describing exemplary embodiments in detail with reference to the accompanying drawings, in which:

[0033] Figure 1 shows a cross-sectional view of an organic electroluminescent device according to an embodiment;

[0034] Figure 2 A cross-sectional view showing an organic electroluminescent device according to an embodiment; and

[0035] Figure 3 A cross-sectional view of an organic electroluminescent device according to an embodiment is shown. DETAILED DESCRIPTION

[0036] Now the exemplary embodiments will be described more fully below with reference to the accompanying drawings; however, they may be implemented in different forms and should not be construed as limited to the embodiments set forth herein. On the contrary, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the exemplary embodiments to those skilled in the art.

[0037] In the drawings, the dimensions of layers and regions may be exaggerated for clarity. Like reference numerals refer to like elements throughout.

[0038] It should be understood that although the terms first, second, etc. can be used to describe different elements in this article, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. For example, the first element discussed below can be referred to as the second element, and similarly, the second element can be referred to as the first element. As used herein, the singular form is intended to also include the plural form, unless the context clearly indicates otherwise.

[0039] It should also be understood that the terms “includes,” “including,” “comprises,” or “comprising,” when used in this specification, specify the presence of the features, numbers, steps, operations, elements, components, or combinations thereof, but do not exclude the presence or addition of one or more other features, numbers, steps, operations, elements, components, or combinations thereof. It should also be understood that when a layer, film, region, plate, etc. is referred to as being “on” another component, it can be “directly” “on” the other component, or there may be intervening layers.

[0040] First, refer to Figures 1 to 3 An organic electroluminescent device according to an exemplary embodiment is explained.

[0041] Figure 1 A cross-sectional view of an organic electroluminescent device according to an embodiment is shown. Figure 2 A cross-sectional view of an organic electroluminescent device according to an embodiment is shown. Figure 3 A cross-sectional view of an organic electroluminescent device according to an embodiment is shown.

[0042] refer to Figures 1 to 3 , the organic electroluminescent device 10 according to the embodiment may include a first electrode EL1 , a hole transport region HTR, an emission layer EML, an electron transport region ETR, and a second electrode EL2 .

[0043] The first electrode EL1 has conductivity. The first electrode EL1 may be a pixel electrode or an anode. The first electrode EL1 may be a transmissive electrode, a semi-transmissive reflective electrode or a reflective electrode. If the first electrode EL1 is a transmissive electrode, the first electrode EL1 may include a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) or indium tin zinc oxide (ITZO). If the first electrode EL1 is a semi-transmissive reflective electrode or a reflective electrode, the first electrode EL1 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, a compound thereof, or a mixture thereof (e.g., a mixture of Ag and Mg). In addition, the first electrode EL1 may include a plurality of layers, the plurality of layers including a reflective layer or a semi-transmissive reflective layer formed using the above materials, or a transparent layer formed using ITO, IZO, ZnO or ITZO. For example, the first electrode EL1 may have a three-layer structure of ITO / Ag / ITO.

[0044] The thickness of the first electrode EL1 may be about to about For example, about to about

[0045] A hole transport region HTR is provided on the first electrode EL1. The hole transport region HTR may include at least one of a hole injection layer HIL, a hole transport layer HTL, a hole buffer layer, or an electron blocking layer EBL. The thickness of the hole transport region HTR may be, for example, about 100 Å. to about

[0046] The hole transport region HTR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multi-layer structure including a plurality of layers formed using a plurality of different materials.

[0047] For example, the hole transport region HTR may have a single-layer structure (e.g., a hole injection layer HIL and a hole transport layer HTL), and may have a single-layer structure formed using a hole injection material and a hole transport material. In an embodiment, the hole transport region HTR may have a single-layer structure formed using a plurality of different materials, or a structure of a hole injection layer HIL / hole transport layer HTL, a hole injection layer HIL / hole transport layer HTL / hole buffer layer, a hole injection layer HIL / hole buffer layer, a hole transport layer HTL / hole buffer layer, or a hole injection layer HIL / hole transport layer HTL / electron blocking layer EBL laminated from the first electrode EL1.

[0048] The hole transport region HTR may be formed using various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), inkjet printing, laser printing, and laser induced thermal imaging (LITI).

[0049] The hole injection layer HIL may include, for example, a phthalocyanine compound (e.g., copper phthalocyanine); N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (DNTPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4',4"-tris{N-(2-naphthyl)-N-phenylamino}-triphenylamine (2-TNATA), poly(3,4-ethylenedioxythiophene) / poly(4-phenylethylenedioxythiophene) / triphenylamine (TDATA), and poly(4-phenylethylenedioxythiophene) / triphenylamine (TDATA). The products include poly(4-styrene sulfonate) (PANI / PSS), polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), polyaniline / camphorsulfonic acid (PANI / CSA), polyaniline / poly(4-styrenesulfonate) (PANI / PSS), N,N'-dinaphth-1-yl)-N,N'-diphenyl-benzidine (NPB), triphenylamine-containing polyether ketone (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN), etc.

[0050] The hole transport layer HTL may include, for example, carbazole derivatives (e.g., N-phenylcarbazole and polyvinylcarbazole), fluorine-based derivatives, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), triphenylamine-based derivatives (e.g., 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA)), N,N'-di(1-naphth-1-yl)-N,N'-diphenyl-benzidine (NPB), 4,4'-cyclohexylenebis[N,N-bis(4-methylphenyl)aniline] (TAPC), 4,4'-bis[N,N'-(3-tolyl)amino]-3,3'-dimethylbiphenyl (HMTPD), 1,3-bis(N-carbazolyl)benzene (mCP), and the like.

[0051] The thickness of the hole transport region HTR may be about to about For example, about to about If the hole transport region HTR includes both the hole injection layer HIL and the hole transport layer HTL, the thickness of the hole injection layer HIL may be about 500 Å. to about For example, about to about And the thickness of the hole transport layer HTL can be about to about If the thicknesses of the hole transport region HTR, the hole injection layer HIL, and the hole transport layer HTL satisfy the above ranges, satisfactory hole transport properties may be obtained without a significant increase in driving voltage.

[0052] In addition to the above materials, the hole transport region HTR may further include a charge generating material to increase conductivity. The charge generating material may be uniformly or non-uniformly dispersed in the hole transport region HTR. The charge generating material may be, for example, a p-dopant. In an embodiment, the p-dopant may be one of a quinone derivative, a metal oxide, or a compound containing a cyano group. Examples of p-dopants may include quinone derivatives (e.g., tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyanoquinodimethane (F4-TCNQ)), metal oxides (e.g., tungsten oxide and molybdenum oxide).

[0053] As described above, in addition to the hole injection layer HIL and the hole transport layer HTL, the hole transport region HTR may further include at least one of a hole buffer layer or an electron blocking layer. The hole buffer layer may compensate for the resonance distance according to the wavelength of light emitted from the emission layer EML and increase the luminous efficiency. The material contained in the hole transport region HTR may be used as the material contained in the hole buffer layer. The electron blocking layer is a layer that prevents electron injection from the electron transport region ETR to the hole transport region HTR.

[0054] An emission layer EML may be provided on the hole transport region HTR. In an embodiment, the emission layer EML may have a thickness of about 100 Å. to about The thickness, for example, is about to about In an embodiment, the emission layer EML may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multi-layer structure having a plurality of layers formed using a plurality of different materials.

[0055] The emission layer EML may include, for example, a heterocyclic compound including a nitrogen-containing monocyclic ring, (eg, at least one) linker, and two or more carbazole moieties. In an embodiment, the linker may be, for example, a substituted or unsubstituted dibenzofuran group or a substituted or unsubstituted dibenzothiophene group.

[0056] At least one of the carbazole moieties and the nitrogen-containing monocyclic ring can be bonded to the linker in an ortho relationship. For example, the nitrogen-containing monocyclic ring and the carbazole moiety can be connected via a linker, and at least one of the carbazole moieties and the nitrogen-containing monocyclic ring can be bonded to the linker in an ortho relationship. For example, the nitrogen-containing monocyclic ring can be bonded to one ring atom of the linker, and one of the carbazole moieties can be bonded to another ring atom of the linker, wherein the other ring atom of the linker is directly adjacent to one ring atom of the linker on the ring (e.g., one ring atom of the linker can be located at the 3-position of the linker, and the other ring atom of the linker can be located at the 4-position of the linker).

[0057] In an embodiment, if two carbazole moieties are included, only one of the two may be bonded in an ortho relationship relative to the nitrogen-containing monocyclic ring, and the other carbazole moiety may be bonded in a meta or para relationship relative to the nitrogen-containing monocyclic ring. In an embodiment, each of the two carbazole moieties (e.g., both) may be bonded to a linker in an ortho relationship relative to the nitrogen-containing monocyclic ring. In an embodiment, the heterocyclic compound may include two linkers.

[0058] In an embodiment, the heterocyclic compound may include one or two linkers. If the heterocyclic compound includes one linker, each of the two or more carbazole moieties may be bonded to the linker. If the heterocyclic compound includes two linkers, at least one carbazole moiety may be bonded to each of the linkers.

[0059] In an embodiment, the nitrogen-containing monocyclic ring may be, for example, a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrimidine group, or a substituted or unsubstituted triazine group. In an embodiment, the nitrogen-containing monocyclic ring may be, for example, a substituted or unsubstituted triazine group.

[0060] In an embodiment, the nitrogen-containing monocycle may be substituted by at least one substituted or unsubstituted phenyl group. In an embodiment, if the heterocyclic compound includes a linker, the nitrogen-containing monocycle may be unsubstituted, or may be disubstituted by two substituted or unsubstituted phenyl groups. In an embodiment, if the heterocyclic compound includes two linkers, the nitrogen-containing monocycle may be substituted by a substituted or unsubstituted phenyl group. In an embodiment, the nitrogen-containing monocycle may, for example, be substituted by one or two unsubstituted phenyl groups.

[0061] In an embodiment, the heterocyclic compound may be represented, for example, by Formula 1 below.

[0062] [Formula 1]

[0063]

[0064] In formula 1, Z 1 To Z 3 can be independently CR1 or N, Z 1 To Z 3 At least one of them is N. 1 For example, it may be a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 1 To Ar 3 Each may be independently, for example, a group represented by the following Formula 2, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 1 To Ar 3 At least one of them may be a group represented by Formula 2. It is understood that the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and the substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms are different from the group represented by Formula 2.

[0065] [Formula 2]

[0066]

[0067] In formula 2, X 1 It may be, for example, O or S. "n" may be, for example, an integer of 1 to 3, "a" to "c" may each independently be, for example, an integer of 0 to 4, and "d" may be, for example, an integer of 0 to 2. 2 To R 5 Each of them may be independently, for example, a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 2 To R 5 Each independently may be, for example, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. In an embodiment, when n of Formula 2 is 1, the compound represented by Formula 1 may include another carbazole moiety thereon.

[0068] In the description, means the part to be connected or the bonding position (for example, in Ar of Formula 1 1 To Ar 3 ).

[0069] In the description, "substituted or unsubstituted" may mean substituted by at least one substituent selected from deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, boron groups, phosphine groups, alkyl groups, alkenyl groups, aryl groups and heterocycles, or unsubstituted. In addition, each substituent illustrated above may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group, or a phenyl group substituted by a phenyl group.

[0070] In the description, the halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0071] In the description, the alkyl group may be a linear, branched or cyclic type. The carbon number of the alkyl group may be 1 to 30, 1 to 20, 1 to 10 or 1 to 4. The alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl decyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like.

[0072] In the description, an aryl group means a functional group or a substituent derived from an aromatic hydrocarbon ring. The aryl group can be a monocyclic aryl group or a heterocyclic aryl group. The number of carbon atoms used to form the ring in the aryl group can be 6 to 30, 6 to 20, or 6 to 15. Examples of aryl groups can include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, quaterphenyl, pentaphenyl, hexaphenyl, biphenylene, triphenylenyl, pyrenyl, benzofluoranthenyl, Ji et al.

[0073] In the description, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. If the fluorenyl group is substituted, examples are shown below.

[0074]

[0075] In the description, the heteroaryl group can be a heteroaryl group comprising at least one of O, N, P, Si or S as a heteroatom. If the heteroaryl group comprises two heteroatoms, the two heteroatoms can be identical or different. The carbon number of the ring for forming the heteroaryl group can be 2 to 30 or 2 to 20. The heteroatom number of the ring for forming the heteroaryl group can be 1 to 10, 1 to 6 or 1 to 3, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. The heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group can have, for example, a two-ring or three-ring structure. Examples of heteroaryl groups can include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothiphenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazole, phenothiazinyl, dibenzosilyl, dibenzofuranyl, and the like.

[0076] In the description, the silyl group includes an alkylsilyl group and an arylsilyl group. Examples of the silyl group may include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.

[0077] In the description, the boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group may include trimethyl boron, triethyl boron, tert-butyl dimethyl boron, triphenyl boron, diphenyl boron, phenyl boron, and the like.

[0078] In the description, the alkenyl group may be straight chain or branched. The carbon number is not particularly limited, but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkenyl group may include vinyl, 1-butenyl, 1-pentenyl, 1,3-butadienylaryl, styryl, styrylvinyl, and the like.

[0079] In the description, the carbon number of the amino group is not particularly limited, but can be 1 to 30. The amino group can include an alkylamino group and an arylamino group. Examples of the amino group include a methylamino group, a dimethylamino group, a phenylamino group, a diphenylamino group, a naphthylamino group, a 9-methyl-anthrylamino group, a triphenylamino group, and the like.

[0080] In an embodiment, R 1 It can be, for example, a hydrogen atom. 1 To Z 3 They may each independently be CH or N.

[0081] In an embodiment, Z 1 To Z 3 Each (eg, all) of can be N.

[0082] In an embodiment, Ar other than that represented by Formula 2 1 To Ar 3 At least one of may be, for example, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms. 1 To Ar 3 At least one of the may be, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group.

[0083] In an embodiment, if Ar 1 To Ar 3 If only one of is represented by Formula 2, then “n” in Formula 2 is 2 or 3.

[0084] In an embodiment, at least one of the carbazole moieties in Formula 2 may be bonded in an ortho relationship with respect to the nitrogen-containing monocyclic ring of Formula 1.

[0085] In an embodiment, X 1 Can be 0. In an embodiment, X 1 It can be S.

[0086] If "a" is 2, 3, or 4, then 2, 3, or 4 R 2 The groups may be the same or different. If "b" is 2, 3 or 4, then 2, 3 or 4 R 3 The groups may be the same or different. If "c" is 2, 3 or 4, then 2, 3 or 4 R 4 The groups may be the same or different, and if "d" is 2, then the two R 5 The groups may be the same or different.

[0087] In an embodiment, if "a" is 1, then R 2 It may not be a hydrogen atom. If "b" is 1, then R 3 It may not be a hydrogen atom. If "c" is 1, then R 4 may not be a hydrogen atom, and / or if "d" is 1, then R 5 It may not be a hydrogen atom.

[0088] In an embodiment, if "a" is 1, 2, 3 or 4, then R 2 It may be, for example, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group having 2 to 15 ring carbon atoms.

[0089] In an embodiment, if "b" is 1, 2, 3 or 4, then R 3 It may be a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group having 2 to 15 ring carbon atoms.

[0090] In an embodiment, if "c" is 1, 2, 3 or 4, then R 4 It may be a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group having 2 to 15 ring carbon atoms.

[0091] In an embodiment, if "d" is 1 or 2, then R 5 It may be a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group having 2 to 15 ring carbon atoms.

[0092] In an embodiment, each (eg, all) of "a" to "d" may be zero.

[0093] In an embodiment, the compound represented by Formula 1 may be represented by the following Formula 1-1.

[0094] [Formula 1-1]

[0095]

[0096] In formula 1-1, Z1 To Z 3 ,Ar 1 ,Ar 2 , R 2 To R 5 , "a" to "d" and X 1 May be defined the same as those of Formula 1 and Formula 2. In an embodiment, "d" may be 0 or 1.

[0097] In an embodiment, in Formula 1-1, Ar 1 and Ar 2 Each of them may be, for example, a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 15 ring carbon atoms. 1 and Ar 2 Each may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0098] At least one of the two carbazole moieties of Formula 1-1 may be relative to the nitrogen-containing monocyclic ring (e.g., containing Z 1 To Z 3 ) are bonded in an ortho relationship.

[0099] In an embodiment, the compound represented by Formula 1 may be represented by the following Formula 1-2.

[0100] [Formula 1-2]

[0101]

[0102] In formula 1-2, Z 1 To Z 3 , R 2 To R 5 , "a" to "d" and X 1 May be defined the same as those of Formula 1 and Formula 2. In an embodiment, "d" may be 0 or 1.

[0103] In an embodiment, in Formula 1-2, each of “a” to “d” may be 0.

[0104] At least one of the two carbazole moieties in Formula 1-2 may be relative to the nitrogen-containing monocyclic ring (e.g., containing Z 1 To Z 3 ) are bonded in an ortho relationship.

[0105] In an embodiment, the compound represented by Formula 1 may be represented by the following Formulas 1-3.

[0106] [Formula 1-3]

[0107]

[0108] In formula 1-3, X 2 and X 3 R may be independently, for example, O or S. 2 To R 9 "a" to "c" and "e" to "g" may each independently be an integer of, for example, 0 to 4, and "d" and "h" may each independently be an integer of, for example, 0 to 2. Z 1 To Z 3 and Ar 1 can be defined as the same as those of Formula 1.

[0109] In an embodiment, in Formula 1-3, X 2 and X 3 Can be the same.

[0110] In an embodiment, in Formula 1-3, Ar 1 It may be, for example, a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms. 1 For example, it may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group.

[0111] At least one of the two carbazole moieties in Formula 1-3 may be relative to the nitrogen-containing monocyclic ring (e.g., containing Z 1 To Z 3 ) are bonded in an ortho relationship.

[0112] In an embodiment, the compound represented by Formula 1-3 may be represented by the following Formula 1-4.

[0113] [Formula 1-4]

[0114]

[0115] In formula 1-4, X 2 and X 3 R may be independently, for example, O or S. 2 To R9 "a" to "c" and "e" to "g" may each independently represent, for example, an integer of 0 to 4, and "d" and "h" may each independently represent, for example, an integer of 0 to 2. Z may each independently represent, for example, a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. "a" to "c" and "e" to "g" may each independently represent, for example, an integer of 0 to 4, and "d" and "h" may each independently represent, for example, an integer of 0 to 2. 1 To Z 3 can be defined as the same as those of Formula 1.

[0116] In an embodiment, in Formula 1-4, X 2 and X 3 Can be the same.

[0117] At least one of the two carbazole moieties in Formula 1-4 is relative to the Z 1 To Z 3 The ring is substituted in an ortho relationship.

[0118] In an embodiment, the compound represented by Formula 1 may be represented by the following Formula 1-5 or Formula 1-6.

[0119] [Formula 1-5]

[0120]

[0121] [Formula 1-6]

[0122]

[0123] In formula 1-5 and formula 1-6, Z 1 To Z 3 ,Ar 1 ,Ar 2 , R 2 , R 5 , "a", "d", and X 1 May be defined the same as those of Formula 1 and Formula 2. In an embodiment, "d" may be 0 or 1.

[0124] In an embodiment, the compound represented by Formula 1 may be represented by one of the following Formulas 1-7 to 1-9.

[0125] [Formula 1-7]

[0126]

[0127] [Formula 1-8]

[0128]

[0129] [Formula 1-9]

[0130]

[0131] In Formula 1-7 to Formula 1-9, Z 1 To Z 3 ,Ar 1 ,Ar 2 , R 2 , R 5 , "a", "d", and X 1 can be defined as the same as those of Formula 1 and Formula 2.

[0132] In an embodiment, the compound represented by Formula 1 may be represented by one of the following Formulas 1-10 to 1-12.

[0133] [Formula 1-10]

[0134]

[0135] [Formula 1-11]

[0136]

[0137] [Formula 1-12]

[0138]

[0139] In Formulas 1-10 to 1-12, Z 1 To Z 3 ,Ar 1 ,Ar 2 , R 2 , R 5 , "a", "d", and X 1 can be defined as the same as those of Formula 1 and Formula 2.

[0140] In an embodiment, the compound represented by Formula 1 may be represented by the following Formula 1-13 or Formula 1-14.

[0141] [Formula 1-13]

[0142]

[0143] [Formula 1-14]

[0144]

[0145] In formula 1-13 and formula 1-14, Z 1 To Z 3 ,Ar 1 ,Ar 2 , R 2 , R 5, "a", "d", and X 1 can be defined as the same as those of Formula 1 and Formula 2.

[0146] In an embodiment, the compound represented by Formula 1 may be represented by one of the following Formulas 1-15 to 1-17.

[0147] [Formula 1-15]

[0148]

[0149] [Formula 1-16]

[0150]

[0151] [Formula 1-17]

[0152]

[0153] In Formulas 1-15 to 1-17, Z 1 To Z 3 ,Ar 1 ,Ar 2 , R 2 , R 5 , "a" and "d" may be defined as the same as those of Formula 1, and X 2 and X 3 Can be O or S.

[0154] In an embodiment, the heterocyclic compound may be, for example, a compound of the following Compound Group 1.

[0155] [Compound Group 1]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164] In an embodiment, the emission layer EML may include one type or two or more types of heterocyclic compounds. In an embodiment, the emission layer EML may further include other suitable materials in addition to the heterocyclic compounds.

[0165] In an embodiment, the emission layer EML may include a host and a dopant, and the dopant may include a heterocyclic compound. In an embodiment, the heterocyclic compound represented by Formula 1 may be included in the emission layer EML as a dopant. In an embodiment, the heterocyclic compound represented by Formula 1 may be included in the emission layer EML as a dopant for thermally activated delayed fluorescence. The emission layer EML includes a heterocyclic compound and may be a blue emission layer that emits blue light having a wavelength region of less than about 470nm. For example, a heterocyclic compound may be included in the emission layer EML as a dopant, emitting deep blue light having a wavelength region of about 440nm to about 470nm, or about 450nm to about 470nm.

[0166] In an embodiment, the host material may include a suitable material. For example, it may include at least one of bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 1,3-bis(carbazole-9-yl)benzene (mCP), 2,8-bis(diphenylphosphino)dibenzo[b,d]furan (PPF), 4,4',4"-tri(carbazole-9-yl)-triphenylamine (TCTA), or 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBi). For example, tris(8-hydroxyquinolinyl)aluminum (Alq 3 )、4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tri(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBi), 3-tert-butyl-9,10-di(naphthalene-2-yl)anthracene (TBADN ), distyrylarylene (DSA), 4,4'-bis(9-carbazolyl)-2,2'-dimethyl-biphenyl (CDBP), 2-methyl-9,10-bis(naphthalene-2-yl)anthracene (MADN), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), hexaphenylcyclotriphosphazene (CP1), 1,4-bis(triphenylsilyl)benzene (UGH2), hexaphenylcyclotrisiloxane (DPSiO 3 ), octaphenylcyclotetrasiloxane (DPSiO 4 ), 2,8-bis(diphenylphosphoryl)dibenzofuran (PPF), etc. can be used as the host material.

[0167] In an embodiment, the emission layer EML may further include N,N,N',N'-tetraphenyl-pyrene-1,6-diamine (TPD), 4,4'-bis(2-(9-ethyl-9H-carbazole-3-yl)vinyl)-1,1'-biphenyl (BCzVBi), 4,4'-bis(9-ethyl-3-carbazole vinylidene)-1,1'-biphenyl, 10-phenyl-10H,10 'H-spiro[acridine-9,9'-anthracen]-10'-one (ACRSA), 3,4,5,6-tetra-9H-carbazole-9-yl-1,2-phthalonitrile (4CzPN), 2,4,5,6-tetra-9H-carbazole-9-yl-isophthalonitrile (4CzIPN), bis[4-(9,9-dimethyl-9,10-dihydroacridine]phenyl]sulfone (DMAC-DPS) and 2-phenoxazine-4, At least one of 6-diphenyl-1,3,5-triazine (PSZ-TRZ) as a dopant. In addition, the emission layer EML may further include styryl derivatives (e.g., 1,4-bis[2-(3-N-ethylcarbazolyl)vinyl]benzene (BCzVB), 4-(di-p-tolylamino)-4'-[(di-p-tolylamino)styryl]styrene (DPAVB) and N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalene-2-yl)vinyl)phenyl)-N-phenylaniline (N-BDAVBi)), perylene and its derivatives (e.g., 2,5,8,11-tetra-tert-butylperylene (TBP)), pyrene and its derivatives (e.g., 1,1-dipyrene, 1,4-dipyrenylbenzene, 1,4-bis(N,N-diphenylamino)pyrene), etc. as known dopant materials.

[0168] The emission layer EML may be a blue emission layer that emits blue light. The emission layer EML may be a fluorescent emission layer that radiates fluorescent light. The emission layer EML may be a delayed fluorescent emission layer that radiates delayed fluorescent light.

[0169] An electron transport region ETR may be provided on the emission layer EML. The electron transport region ETR may include at least one of a hole blocking layer HBL, an electron transport layer ETL, or an electron injection layer EIL.

[0170] The electron transport region ETR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multilayer structure having a plurality of layers formed using a plurality of different materials.

[0171] For example, the electron transport region ETR may have a single-layer structure of an electron injection layer EIL or an electron transport layer ETL, or a single-layer structure formed using an electron injection material and an electron transport material. In addition, the electron transport region ETR may have a single-layer structure containing a plurality of different materials, or a structure of an electron transport layer ETL / electron injection layer EIL laminated from an emission layer EML, or a structure of a hole blocking layer HBL / electron transport layer ETL / electron injection layer EIL. The thickness of the electron transport region ETR may be, for example, about to about

[0172] The electron transport region ETR may be formed using various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), inkjet printing, laser printing, and laser induced thermal imaging (LITI).

[0173] If the electron transport region ETR includes an electron transport layer ETL, the electron transport region ETR may include tris(8-hydroxyquinolinolato)aluminum (Alq 3 ), 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene, 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, 2-(4-(N-phenylbenzimidazol-1-ylphenyl)-9,10-dinaphthylanthracene, 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (TPBi), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bp hen), 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalene-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD), bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-biphenyl-4-ato)aluminum (BAlq), bis(benzoquinolinolato-10-ato)beryllium (Bebq 2 ), 9,10-di(naphthalene-2-yl)anthracene (ADN), and mixtures thereof. The thickness of the electron transport layer ETL may be about to about For example, about to about If the thickness of the electron transport layer ETL satisfies the above range, satisfactory electron transport properties may be obtained without a significant increase in driving voltage.

[0174] If the electron transport region ETR includes an electron injection layer EIL, the electron transport region ETR may be formed using LiF, lithium quinolate (LiQ), Li2 O, BaO, NaCl, CsF, lanthanide metals (e.g., Yb) or metal halides (e.g., RbCl and RbI). The electron injection layer EIL can also be formed using a mixture material of an electron transport material and an insulating organic metal salt. The organic metal salt can be a material having an energy band gap of about 4 eV or greater than 4 eV. In particular, the organic metal salt can include, for example, metal acetates, metal benzoates, metal acetoacetates, metal acetylacetonates or metal stearates. The thickness of the electron injection layer EIL can be about 1000 Å. to about For example, about to about If the thickness of the electron injection layer EIL satisfies the above range, satisfactory electron injection properties can be obtained without a significant increase in driving voltage.

[0175] The electron transport region ETR may include a hole blocking layer as described above. The hole blocking layer may include, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), or bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO).

[0176] A second electrode EL2 is provided on the electron transport region ETR. The second electrode EL2 may be a common electrode or a cathode. The second electrode EL2 may be a transmissive electrode, a semi-transmissive reflective electrode or a reflective electrode. If the second electrode EL2 is a transmissive electrode, the second electrode EL2 may include a transparent metal oxide, for example, ITO, IZO, ZnO, ITZO, etc.

[0177] If the second electrode EL2 is a semi-transmissive reflective electrode or a reflective electrode, the second electrode EL2 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound thereof, or a mixture thereof (e.g., a mixture of Ag and Mg). The second electrode EL2 may have a multilayer structure including a reflective layer or a semi-transmissive reflective layer formed using the above materials and a transparent conductive layer formed using ITO, IZO, ZnO, ITZO, etc.

[0178] In an implementation, the second electrode EL2 may be connected to the auxiliary electrode. If the second electrode EL2 is connected to the auxiliary electrode, the resistance of the second electrode EL2 may be reduced.

[0179] In the organic electroluminescent device 10, holes injected from the first electrode EL1 may move to the emission layer EML via the hole transport region HTR, and electrons injected from the second electrode EL2 may move to the emission layer EML via the electron transport region ETR, according to a voltage applied to each of the first electrode EL1 and the second electrode EL2. The electrons and holes are recombined in the emission layer EML to generate excitons, and the excitons may emit light via transition from an excited state to a ground state.

[0180] If the organic electroluminescent device 10 is a top emission type, the first electrode EL1 may be a reflective electrode, and the second electrode EL2 may be a transmissive electrode or a semi-transmissive reflective electrode. If the organic electroluminescent device 10 is a bottom emission type, the first electrode EL1 may be a transmissive electrode or a semi-transmissive reflective electrode, and the second electrode EL2 may be a reflective electrode.

[0181] The organic electroluminescent device 10 according to the embodiment may include the heterocyclic compound represented by Formula 1, and thus, high efficiency and blue emission (eg, deep blue emission) may be simultaneously achieved.

[0182] The embodiment provides a heterocyclic compound represented by Formula 1. Unless otherwise explained, the above-described explanation of Formula 1 will apply. For example, the heterocyclic compound according to the embodiment may be represented by the following Formula 1.

[0183] [Formula 1]

[0184]

[0185] In formula 1, Z 1 To Z 3 can be independently CR 1 or N. In an embodiment, Z 1 To Z 3 At least one of may be N. In an embodiment, R 1 It may be, for example, a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 1 To Ar 3 Each may be independently, for example, a group represented by Formula 2, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 1 To Ar 3 At least one of them may be a group represented by Formula 2.

[0186] [Formula 2]

[0187]

[0188] In formula 2, X 1 It may be, for example, O or S, "n" may be, for example, an integer from 1 to 3, "a" to "c" may each independently be, for example, an integer from 0 to 4, and "d" may be, for example, an integer from 0 to 2. 2 To R 5 Each of them can be independently, for example, a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms. 1 To Ar 3 If only one of the groups is a group represented by Formula 2, "n" may be 2 or 3. In an embodiment, at least one of the carbazole moieties in Formula 2 may be bonded in an ortho relationship with respect to the nitrogen-containing monocyclic ring of Formula 1.

[0189] In an embodiment, the heterocyclic compound according to the embodiment may be a compound of the above compound group 1.

[0190] The heterocyclic compound according to the embodiment may have a difference between a singlet energy level and a triplet energy level of about 0.2 eV or less, and thus, may be used as a material for thermally activated delayed fluorescence. The heterocyclic compound according to the embodiment may be applied as a material for an organic electroluminescent device and may contribute to an increase in efficiency.

[0191] The following examples and comparative examples are provided to highlight the characteristics of one or more than one embodiment, but it should be understood that the examples and comparative examples are not interpreted as limiting the scope of the embodiments, and the comparative examples are not interpreted as being outside the scope of the embodiments. In addition, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

[0192] (synthesis example)

[0193] The heterocyclic compound according to the embodiment can be synthesized, for example, as follows.

[0194] 1. Synthesis of Compound 1

[0195]

[0196] (Synthesis of Intermediate A)

[0197] In a 500 ml three-necked flask under an argon (Ar) atmosphere, 2,4-dibromo-1,3,5-trifluorobenzene (10.00 g), (2-hydroxyphenyl)boric acid (4.76 g), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3 ) 4 , 1.99 g) and potassium carbonate (K 2 CO 3 , 9.54 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 180 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 8.57 g (yield 82%) of Intermediate A. The molecular weight of Intermediate A measured by FAB-MS was 303.

[0198] (Synthesis of Intermediate B)

[0199] In an argon (Ar) atmosphere, in a 300 ml three-necked flask, intermediate A (8.50 g) and K 2 CO 3 (7.75 g) was dissolved in anhydrous DMSO (100 ml), and then stirred at about 110° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 1,000 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (300 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography and recrystallization to obtain 3.57 g (yield 45%) of Intermediate B. The molecular weight of Intermediate B measured by FAB-MS was 283.

[0200] (Synthesis of Intermediate C)

[0201] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate B (3.50 g), bis(pinacolato)diboron (3.14 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (PdCl 2 (dppf, 1.01 g) and potassium acetate (KOAc, 2.43 g) were dissolved in anhydrous 1,4-dioxane (70 ml) and then stirred at about 90° C. for about 8 hours. After cooling in air, water was added and the mixture was collected with CH 2 Cl 2The organic layer was extracted and treated with MgSO 4 The solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 3.18 g (yield 78%) of Intermediate C. The molecular weight of Intermediate C measured by FAB-MS was 330.

[0202] (Synthesis of Intermediate D)

[0203] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate C (3.00 g), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.43 g), Pd(PPh 3 ) 4 (0.53 g) and potassium phosphate (K 3 PO 4 , 3.86 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 60 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 2.85 g (yield 72%) of Intermediate D. The molecular weight of Intermediate D measured by FAB-MS was 435.

[0204] (Synthesis of Compound 1)

[0205] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate D (2.80 g), carbazole (2.15 g) and K 2 CO 3 (4.45 g) was dissolved in anhydrous DMSO (30 ml) and then stirred at about 150° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (150 ml) and MgSO 4 It was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 3.75 g (yield 80%) of Compound 1. The molecular weight of Compound 1 measured by FAB-MS was 729.

[0206] 2. Synthesis of Compound 24

[0207]

[0208] (Synthesis of Intermediate E)

[0209] In an argon (Ar) atmosphere, 1,4-difluoro-2-iododibenzo[b,d]thiophene (5.00 g), bis(pinacolato)diboron (3.66 g), PdCl 2 (dppf) (1.18 g) and KOAc (2.84 g) were dissolved in anhydrous 1,4-dioxane (80 ml) and then stirred at about 90° C. for about 8 hours. After cooling in air, water was added and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was then removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 3.10 g (yield 62%) of Intermediate E. The molecular weight of Intermediate E measured by FAB-MS was 346.

[0210] (Synthesis of Intermediate F)

[0211] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate E (3.00 g), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.32 g), Pd(PPh 3 ) 4 (0.50g) and K 3 PO 4 (3.68 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 50 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 2.74 g (yield 70%) of Intermediate F. The molecular weight of Intermediate F measured by FAB-MS was 451.

[0212] (Synthesis of Compound 24)

[0213] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate F (2.70 g), carbazole (2.61 g) and K 2 CO 3 (5.39 g) was dissolved in anhydrous DMSO (30 ml) and then stirred at about 150° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (150 ml) and MgSO 4The reaction mixture was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.94 g (yield 85%) of Compound 24. The molecular weight of Compound 24 measured by FAB-MS was 745.

[0214] 3. Synthesis of Compound 107

[0215]

[0216] (Synthesis of Intermediate G)

[0217] In a 500 ml three-necked flask under argon (Ar) atmosphere, 1-bromo-2,4-difluoro-3-iodobenzene (10.00 g), (2-hydroxyphenyl)boric acid (4.33 g), Pd(PPh 3 ) 4 (1.81 g) and K 2 CO 3 (8.69 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 160 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 7.69 g (yield 86%) of Intermediate G. The molecular weight of Intermediate G measured by FAB-MS was 285.

[0218] (Synthesis of Intermediate H)

[0219] In a 300 ml three-necked flask under argon (Ar) atmosphere, intermediate G (7.60 g) and K 2 CO 3 (7.37 g) was dissolved in anhydrous DMSO (100 ml), and then stirred at about 110° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 1,000 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (300 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography and recrystallization to obtain 2.69 g (yield 38%) of Intermediate H. The molecular weight of Intermediate H measured by FAB-MS was 265.

[0220] (Synthesis of Intermediate I)

[0221] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate H (2.60 g), bis(pinacolato)diboron (2.49 g), PdCl 2 (dppf) (0.80 g) and KOAc (1.93 g) were dissolved in anhydrous 1,4-dioxane (50 ml) and then stirred at about 90° C. for about 8 hours. After cooling in air, water was added and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 1.84 g (yield 60%) of Intermediate I. The molecular weight of Intermediate I measured by FAB-MS was 312.

[0222] (Synthesis of Intermediate J)

[0223] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate I (3.00 g), 2,4-dichloro-6-phenyl-1,3,5-triazine (0.65 g), Pd(PPh 3 ) 4 (0.33 g) and K 3 PO 4 (2.45 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 50 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 2.27 g (yield 75%) of Intermediate J. The molecular weight of Intermediate J measured by FAB-MS was 525.

[0224] (Synthesis of Compound 107)

[0225] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate J (2.20 g), carbazole (1.40 g) and K 2 CO 3 (2.89 g) was dissolved in anhydrous DMSO (30 ml) and then stirred at about 150° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (150 ml) and MgSO 4The reaction mixture was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 2.75 g (yield 80%) of Compound 107. The molecular weight of Compound 107 measured by FAB-MS was 819.

[0226] 4. Synthesis of Compound 109

[0227]

[0228] (Synthesis of Intermediate K)

[0229] In a 500 ml three-necked flask under argon (Ar) atmosphere, 1,5-dibromo-2,4-difluorobenzene (10.00 g), (2-hydroxyphenyl)boronic acid (5.07 g), Pd(PPh 3 ) 4 (2.13 g) and K 2 CO 3 (10.17 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 180 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 8.91 g (yield 85%) of Intermediate K. The molecular weight of Intermediate K measured by FAB-MS was 285.

[0230] (Synthesis of Intermediate L)

[0231] In an argon (Ar) atmosphere, in a 300 ml three-necked flask, intermediate K (8.90 g) and K 2 CO 3 (8.63 g) was dissolved in anhydrous DMSO (100 ml), and then stirred at about 110° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 1,000 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (300 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography and recrystallization to obtain 7.20 g (yield 87%) of Intermediate L. The molecular weight of Intermediate L measured by FAB-MS was 265.

[0232] (Synthesis of Intermediate M)

[0233] In a 500 ml three-necked flask under argon (Ar) atmosphere, intermediate L (7.20 g), bis(pinacolato)diboron (6.89 g), PdCl 2 (dppf) (2.22 g) and KOAc (5.33 g) were dissolved in anhydrous 1,4-dioxane (140 ml) and then stirred at about 90° C. for about 8 hours. After cooling in air, water was added and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 4.41 g (yield 52%) of Intermediate M. The molecular weight of Intermediate M measured by FAB-MS was 312.

[0234] (Synthesis of Intermediate N)

[0235] In a 300 ml three-necked flask under argon (Ar) atmosphere, intermediate M (4.40 g), 2,4-dichloro-6-phenyl-1,3,5-triazine (1.59 g), Pd(PPh 3 ) 4 (0.81 g) and K 3 PO 4 (5.98 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 70 ml), and then stirred at about 80° C. for about 10 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by silica gel column chromatography to obtain 5.04 g (yield 68%) of Intermediate N. The molecular weight of Intermediate N measured by FAB-MS was 525.

[0236] (Synthesis of Compound 109)

[0237] In a 200 ml three-necked flask under argon (Ar) atmosphere, intermediate N (2.50 g), carbazole (1.59 g) and K 2 CO 3 (3.28 g) was dissolved in anhydrous DMSO (30 ml) and then stirred at about 150° C. for about 6 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (150 ml) and MgSO 4The reaction mixture was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 3.08 g (yield 79%) of Compound 109. The molecular weight of Compound 109 measured by FAB-MS was 819.

[0238] 5. Synthesis of Compound 133

[0239]

[0240] (Synthesis of Intermediate O)

[0241] In a 500 ml three-necked flask under argon (Ar) atmosphere, 2,4-dichloro-6-phenyl-1,3,5-triazine (5.00 g), 2,3,4-trifluorophenylboric acid (7.78 g), Pd(PPh 3 ) 4 (2.55 g) and K 2 CO 3 (12.2 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 200 ml), and then stirred at about 80° C. for about 8 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.24 g (yield 46%) of Intermediate O. The molecular weight of Intermediate O measured by FAB-MS was 417.

[0242] (Synthesis of Intermediate P)

[0243] In a 500 ml three-necked flask under argon (Ar) atmosphere, intermediate O (4.00 g), 2-bromophenol (3.32 g) and K 2 CO 3 (5.30 g) was dissolved in anhydrous DMSO (150 ml), and then stirred at about 60° C. for about 3 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 1,000 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (300 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.15 g (yield 60%) of Intermediate P. The molecular weight of Intermediate P measured by FAB-MS was 723.

[0244] (Synthesis of Intermediate Q)

[0245] In a 300 ml three-necked flask under Ar atmosphere, intermediate P (4.00 g), carbazole (1.85 g) and K 2 CO 3 (3.06 g) was dissolved in anhydrous DMSO (50 ml) and then stirred at about 100°C for about 3 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 5.34 g (yield 95%) of Intermediate Q. The molecular weight of Intermediate Q measured by FAB-MS was 1,017.

[0246] (Synthesis of Compound 133)

[0247] In a 500 ml three-necked flask under Ar atmosphere, intermediate Q (5.00 g), Pd(OAc) 2 (0.11g), K 2 CO 3 (2.04 g) and PPh 3 (0.26 g) was dissolved in anhydrous dimethylacetamide (50 ml) and then stirred at about 140°C for about 1 hour. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 The reaction mixture was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 3.36 g (yield 80%) of Compound 133. The molecular weight of Compound 133 measured by FAB-MS was 855.

[0248] 6. Synthesis of Compound 131

[0249]

[0250] (Synthesis of Intermediate R)

[0251] In a 500 ml three-necked flask under Ar atmosphere, 2,4-dichloro-6-phenyl-1,3,5-triazine (5.00 g), 2,4,5-trifluorophenylboric acid (7.78 g), Pd(PPh 3 ) 4 (2.55 g) and K 2 CO 3(12.2 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 200 ml), and then stirred at about 80° C. for about 8 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.80 g (yield 52%) of Intermediate R. The molecular weight of Intermediate R measured by FAB-MS was 417.

[0252] (Synthesis of Intermediate S)

[0253] In a 500 ml three-necked flask under Ar atmosphere, intermediate R (4.00 g), 2-bromophenol (3.32 g) and K 2 CO 3 (5.30 g) was dissolved in anhydrous DMSO (150 ml), and then stirred at about 60° C. for about 3 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 1,000 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (300 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.51 g (yield 65%) of Intermediate S. The molecular weight of Intermediate S measured by FAB-MS was 723.

[0254] (Synthesis of Intermediate T)

[0255] In a 300 ml three-necked flask under Ar atmosphere, intermediate S (4.00 g), carbazole (1.85 g) and K 2 CO 3 (3.06 g) was dissolved in anhydrous DMSO (50 ml) and then stirred at about 100°C for about 3 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 Dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 5.06 g (yield 90%) of Intermediate T. The molecular weight of Intermediate T measured by FAB-MS was 1,017.

[0256] (Synthesis of Compound 131)

[0257] In a 500 ml three-necked flask under Ar atmosphere, intermediate T (5.00 g), Pd(OAc) 2 (0.11g), K 2 CO 3 (2.04 g) and PPh 3 (0.26 g) was dissolved in anhydrous dimethylacetamide (50 ml) and then stirred at about 140° C. for about 1 hour. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was separated by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 The reaction mixture was dried, and the solvent was removed by distillation under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 3.45 g (yield 82%) of Compound 131. The molecular weight of Compound 131 measured by FAB-MS was 855.

[0258] 7. Synthesis of Compound 23

[0259]

[0260] (Synthesis of Intermediate U)

[0261] In a 300 ml three-necked flask under Ar atmosphere, 2-chloro-4,6-diphenyl-1,3,5-triazine (5.00 g), 2,3,4-trifluorophenylboric acid (3.29 g), Pd(PPh 3 ) 4 (1.08 g) and K 2 CO 3 (5.16 g) was dissolved in a degassed mixed solvent of toluene / ethanol / water (10:1:2, 100 ml), and then stirred at about 80° C. for about 8 hours. After the reaction was completed, water was added, and CH 2 Cl 2 The organic layer was extracted and treated with MgSO 4 The solvent was distilled off under reduced pressure. The crude product thus obtained was separated by recrystallization to obtain 4.07 g (yield 60%) of Intermediate U. The molecular weight of Intermediate U measured by FAB-MS was 363.

[0262] (Synthesis of Intermediate V)

[0263] Under Ar atmosphere, in a 500 ml three-necked flask, intermediate U (4.00 g), 2-bromophenol (1.90 g) and K 2 CO 3(3.80 g) was dissolved in anhydrous DMSO (50 ml) and then stirred at about 60° C. for about 3 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 The crude product thus obtained was separated by recrystallization to obtain 4.09 g (yield 72%) of Intermediate V. The molecular weight of Intermediate V measured by FAB-MS was 516.

[0264] (Synthesis of Intermediate W)

[0265] In a 500 ml three-necked flask under Ar atmosphere, intermediate V (4.00 g), Pd(OAc) 2 (0.08g), K 2 CO 3 (1.61 g) and PPh 3 (0.20 g) was dissolved in anhydrous dimethylacetamide (40 ml) and then stirred at about 140° C. for about 1 hour. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 The crude product thus obtained was separated by recrystallization to obtain 2.36 g (yield 70%) of Intermediate W. The molecular weight of Intermediate W measured by FAB-MS was 435.

[0266] (Synthesis of Compound 23)

[0267] In a 300 ml three-necked flask under Ar atmosphere, intermediate W (2.00 g), carbazole (1.54 g) and K 2 CO 3 (3.17 g) was dissolved in anhydrous DMSO (30 ml) and then stirred at about 180°C for about 8 hours. After the temperature was lowered to ambient temperature, the reaction solution was poured into 300 ml of water and stirred. The resulting precipitate was recovered by suction filtration and dissolved in CH 2 Cl 2 (200 ml) and MgSO 4 The crude product thus obtained was separated by recrystallization to obtain 1.94 g (yield 58%) of Compound 23. The molecular weight of Compound 23 measured by FAB-MS was 729.

[0268] 8. Synthesis of Compound 29

[0269]

[0270] Compound 29 was synthesized by following the same procedure used to synthesize compound 23, but using 2-chloro-4,6-diphenylpyrimidine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine.

[0271] (Device Manufacturing Example)

[0272] The organic electroluminescent devices of Examples 1 to 8 were manufactured using Compounds 1, 23, 24, 29, 107, 109, 131, and 133 as dopant materials for an emission layer.

[0273] [Exemplary compounds]

[0274]

[0275] Organic electroluminescent devices of Comparative Examples 1 to 3 were manufactured using the following Compounds X-1 to X-3 as dopant materials for the emission layer.

[0276] [Comparative Compounds]

[0277]

[0278] The singlet energy level (S1) and triplet energy level (T1) of the exemplary compound and the comparative compound were calculated by the non-empirical molecular orbital method. In particular, the calculation was performed by using Gaussian 09 of Gaussian Co., using B3LYP as a functional function and using 6-31G (d) as a basis function. The results are shown in the following Table 1. ΔE ST Represents the difference between the singlet energy level and the triplet energy level.

[0279] [Table 1]

[0280] S1 energy level (eV) T1 energy level (eV) <![CDATA[ΔE ST ]]> Exemplary Compound 1 2.84 2.75 0.11 Exemplary Compound 24 2.97 2.87 0.10 Exemplary Compound 107 2.97 2.90 0.07 Exemplary Compound 109 2.96 2.87 0.09 Exemplary Compound 23 2.91 2.81 0.10 Exemplary Compound 29 3.01 2.90 0.11 Exemplary Compound 131 2.92 2.85 0.07 Exemplary Compound 133 2.89 2.81 0.08 Comparative Compound X-1 2.76 2.58 0.18 Comparative Compound X-2 2.75 2.56 0.19 Comparative Compound X-3 2.89 2.74 0.15

[0281] Referring to the results in Table 1, all exemplary compounds showed low ΔE ST The comparative compounds showed relatively high ΔE ST value, and is considered unsuitable for use as a material for thermally activated delayed fluorescence.

[0282] Each of the organic electroluminescent devices of Examples 1 to 8 and Comparative Examples 1 to 3 was manufactured by forming a first electrode to a thickness of about 150 nm using ITO, a hole injection layer to a thickness of about 10 nm using HAT-CN, a hole transport layer to a thickness of about 80 nm using NPB, an electron blocking layer to a thickness of about 5 nm using mCP, an emission layer to a thickness of about 20 nm using DPEPO doped with 18% of the exemplary compound or the comparative compound, a hole blocking layer to a thickness of about 10 nm using DPEPO, an electron transport layer to a thickness of about 30 nm using TPBi, an electron injection layer to a thickness of about 0.5 nm using LiF, and a second electrode to a thickness of about 100 nm using Al. Each layer was formed by a vacuum deposition method.

[0283] The maximum emission wavelength (e.g., wavelength of maximum emission) and external quantum efficiency of each of the organic electroluminescent devices according to Examples 1 to 8 and Comparative Examples 1 to 3 were measured and are shown in the following Table 2. EQE in Table 2 means the maximum emission wavelength at about 10 mA / cm 2 In order to evaluate the emission properties of the organic electroluminescent device thus manufactured, a light emission brightness measurement apparatus C9920-11 of HAMAMATSU Photonics Co. was used.

[0284] [Table 2]

[0285] Emitting layer dopant materials <![CDATA[λ 最大 (nm)]]> EQE(%) Example 1 Exemplary Compound 1 470 9 Example 2 Exemplary Compound 24 463 11 Example 3 Exemplary Compound 107 459 14 Example 4 Exemplary Compound 109 461 13 Example 5 Exemplary Compound 23 460 13 Example 6 Exemplary Compound 29 452 10 Example 7 Exemplary Compound 131 464 15 Example 8 Exemplary Compound 133 462 14 Comparative Example 1 Comparative Compound X-1 474 5 Comparative Example 2 Comparative Compound X-2 472 2 Comparative Example 3 Comparative Compound X-3 466 3

[0286] Referring to the results of Table 2, Examples 1 to 8 showed improved efficiency when compared with Comparative Examples 1 to 3. These results are considered to be obtained because the azine group functions as an electron acceptor and the carbazole group functions as an electron donor in the exemplary compounds, and the exemplary compounds exhibit properties of materials for thermally activated delayed fluorescence. In addition, the azine group and the carbazole group are bonded in an ortho relationship, and the electron acceptor and the electron donor are twisted, HOMO and LUMO are effectively spaced apart, and the properties of materials for thermally activated delayed fluorescence are exhibited.

[0287] Meanwhile, in Comparative Example 1, since the azine group and the carbazole group are not bonded in an ortho relationship, the donor and the acceptor are not sufficiently twisted and TADF is not exhibited. In Comparative Examples 2 and 3, ΔE ST The value is relatively large, and only one carbazole group is included. Therefore, the function of the electron donor is weak, reverse intersystem crossing does not occur sufficiently, and the properties as a material for thermally activated delayed fluorescence are not shown at present.

[0288] The heterocyclic compound according to the embodiment may be used as a dopant of thermally activated delayed fluorescence for emitting deep blue color.

[0289] The organic electroluminescent device including the heterocyclic compound according to the embodiment may promote deep blue emission and may have excellent efficiency at the same time.

[0290] The organic electroluminescent device according to the embodiment may have excellent efficiency.

[0291] The heterocyclic compound according to the embodiment may be applied to an organic electroluminescent device and may contribute to high efficiency.

[0292] Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and interpreted in a general and descriptive sense only, and not for limiting purposes. In some cases, as will be apparent to one of ordinary skill in the art from the time this application is filed, features, characteristics, and / or elements described in conjunction with a particular embodiment may be used alone or in combination with features, characteristics, and / or elements described in conjunction with other embodiments, unless otherwise expressly indicated. Therefore, it should be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the claims.

Claims

1. A heterocyclic compound represented by the following formula 1: [Formula 1] in, In formula 1, Z 1 To Z 3 Each independently is CR 1 or N, Z 1 To Z 3 At least one of them is N, R 1 is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, Ar 1 To Ar 3 are each independently a group represented by the following Formula 2, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, and Ar 1 To Ar 3 At least two of them are groups represented by Formula 2: [Formula 2] In formula 2, X 1 is O or S, "n" is an integer from 1 to 3, "a" to "c" are each independently an integer from 0 to 4, "d" is an integer from 0 to 2, and R 2 To R 5 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, and At least one of the carbazole moieties in Formula 2 is relative to the carbazole moiety in Formula 1 comprising Z 1 To Z 3 The nitrogen-containing monocyclic rings are bonded in an ortho relationship.

2. The heterocyclic compound as claimed in claim 1, wherein Z 1 To Z 3 Each of them is N.

3. The heterocyclic compound according to claim 1, wherein the compound represented by Formula 1 is represented by the following Formula 1-3: [Formula 1-3] In formula 1-3, X 2 and X 3 are each independently O or S, R 2 To R 9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, "a" to "c" and "e" to "g" are each independently an integer from 0 to 4, "d" and "h" are each independently an integer from 0 to 2, and Z 1 To Z 3 and Ar 1 are defined as the same as those of Formula 1.

4. The heterocyclic compound according to claim 1, wherein the compound represented by Formula 1 is represented by the following Formula 1-4: [Formula 1-4] In formula 1-4, X 2 and X 3 are each independently O or S, R 2 To R 9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 ring carbon atoms, "a" to "c" and "e" to "g" are each independently an integer from 0 to 4, "d" and "h" are each independently an integer from 0 to 2, and Z 1 To Z 3 are defined as the same as those of Formula 1.

5. The heterocyclic compound according to claim 1, wherein the heterocyclic compound is a compound of the following compound group 1: [Compound Group 1] 6. Organic electroluminescent device, include: a first electrode; a hole transport region on the first electrode; an emitting layer on the hole transport region; an electron transport region on the emissive layer; as well as a second electrode on the electron transport region, The first electrode and the second electrode each independently comprise: Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, a compound thereof or a mixture thereof; or a transparent metal oxide, The emission layer comprises the heterocyclic compound according to any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, wherein the emission layer comprises a host and a dopant, and The dopant comprises the heterocyclic compound according to any one of claims 1 to 5. The organic electroluminescent device as claimed in claim 7 , wherein the dopant is a thermally activated delayed fluorescence dopant.

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