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WO2022203403A1 - Nouveau composé hétérocyclique et dispositif électroluminescent organique le comprenant - Google Patents

Nouveau composé hétérocyclique et dispositif électroluminescent organique le comprenant Download PDF

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WO2022203403A1
WO2022203403A1 PCT/KR2022/004090 KR2022004090W WO2022203403A1 WO 2022203403 A1 WO2022203403 A1 WO 2022203403A1 KR 2022004090 W KR2022004090 W KR 2022004090W WO 2022203403 A1 WO2022203403 A1 WO 2022203403A1
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heterocyclic compound
light emitting
substituted
unsubstituted
formula
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Korean (ko)
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김윤희
권순기
천형진
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Gyeongsang National University GNU
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same, and more particularly, to a novel heterocyclic compound exhibiting thermally activated delayed fluorescence (TADF) and an organic light emitting device comprising the same it's about
  • TADF thermally activated delayed fluorescence
  • a typical organic light emitting device has a structure including an anode and a cathode and an organic material layer therebetween.
  • the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • excitons generated when driving an organic light emitting diode are stochastically generated in a singlet state of 25% and a triplet state of 75%. , the internal quantum efficiency remains at a maximum of 25%.
  • a phosphorescent light emitting material using an iridium or platinum complex capable of using triplet energy is used, and it is known that it has excellent quantum efficiency characteristics.
  • these materials are expensive, and in particular, due to the instability of the blue light-emitting material, there is a limit to their application.
  • thermally activated delayed fluorescence (TADF) materials are in the spotlight. Unlike phosphors that convert singlet excitons into triplets and convert them into light, thermally activated delayed fluorescent materials convert triplet excitons into singlets and convert them into light. In theory, both singlet and triplet excitons are converted into light. 100% internal quantum efficiency is possible. Accordingly, as phosphorescent materials are attracting attention as a material that can overcome the limitations of lifetime and efficiency, research on this is being actively conducted.
  • the TADF material uses an electron-donating substituent called a donor and an electron-accepting substituent called an acceptor to localize HOMO and LUMO in a molecule, thereby lowering the energy difference between S 1 and T 1 , ⁇ Est. Allows inverse interterm crossover (RISC) to occur.
  • RISC inverse interterm crossover
  • One aspect of the present invention aims to provide a novel heterocyclic compound. Specifically, one aspect is to provide a thermally activated delayed fluorescence (TADF) material having excellent luminous efficiency and improved lifespan characteristics.
  • TADF thermally activated delayed fluorescence
  • one aspect of the present invention aims to provide an organic light emitting device having improved color purity, quantum efficiency, thermal stability and lifespan characteristics by using the novel heterocyclic compound as a material for an organic material layer of an organic light emitting device.
  • one aspect of the present invention provides a heterocyclic compound represented by the following formula (1).
  • R 1 to R 3 are each independently (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted (C3-C30) ) cycloalkyl or substituted or unsubstituted (C2-C30)heterocycloalkyl;
  • R e to R f are each independently hydrogen, (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted (C3 -C30)cycloalkyl or substituted or unsubstituted (C2-C30)heterocycloalkyl, wherein R e to R f are adjacent to each other or may be linked to form a fusion ring;
  • X 1 and X 2 are each independently O, S or NR aa ;
  • L 1 and L 2 are each independently (C1-C30)alkylene or (C6-C30)arylene;
  • R aa is hydrogen or (C1-C30)alkyl
  • a to c are each independently an integer of 0 to 2.
  • one aspect of the present invention provides an organic light emitting device including the compound represented by Formula 1 above.
  • the heterocyclic compound according to an aspect of the present invention is an organic light-emitting material exhibiting thermally activated delayed fluorescence (TADF).
  • TADF thermally activated delayed fluorescence
  • the heterocyclic compound according to an embodiment of the present invention has high triplet energy and thermal stability, and may exhibit thermally activated delayed fluorescence through inverse cross-crossing.
  • heterocyclic compound according to an aspect of the present invention greatly reduces a Stokes shift value, exhibits a surprisingly small full-width at half maximum, and excellent color purity is possible.
  • the organic light emitting device employing the heterocyclic compound according to an embodiment of the present invention may have improved luminous efficiency and improved stability of the device to have a long lifespan.
  • the heterocyclic compound according to an aspect of the present invention as a light emitting material, particularly a thermally activated delayed fluorescent dopant material, in a light emitting device, an organic light emitting device having improved color purity, high quantum efficiency, low power consumption and long life can be provided. have.
  • Example 2 is a UV absorption spectrum and PL spectrum of heterocyclic compound 2 (Example 2).
  • thermogravimetric analysis (TGA) curve of heterocyclic compound 1 (Example 1).
  • DSC differential calorimetry
  • a hydrogen atom bonded to a carbon element is a halogen, a nitro group, a hydroxyl group, a cyano group, an amine group, a formyl group (-CHO), a carboxy group (-COOH), (C1-C7) alkyl, ( means substituted with one or more substituents selected from C1-C7) alkoxy, (C1-C7) alkylcarbonyl, (C1-C7) alkoxycarbonyl, (C6-C12) aryl and (C2-C12) heteroaryl do.
  • alkyl refers to a monovalent straight-chain or branched saturated hydrocarbon group composed only of carbon and hydrogen atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl , tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1- Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nony
  • alkylene as used herein means a divalent organic radical derived by the removal of one hydrogen from the alkyl, and follows the definition of alkyl.
  • cycloalkyl refers to a completely saturated or partially unsaturated non-aromatic monocyclic or multicyclic hydrocarbon ring of carbon atoms, wherein aryl or heteroaryl is fused. cases are included. Multicyclic ring systems include fused cyclics, bridged cyclics and spirocyclics.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, perhydronaphthyl, perhydroindenyl, decalin, cycle[3.1.1]heptane, bicyclo[2.2.1]heptane, cycle rho[2.2.2]octane, bicycle[3.2.2]nonane, spiro[2.5]octane, spiro[3.5]nonane, adamantyl, norbornyl, and the like.
  • Multicyclic ring systems include fused cyclics, bridged cyclics and spirocyclics.
  • aryl refers to a functional group derived from an aromatic hydrocarbon by removal of one hydrogen, and is preferably a single or It includes a fused ring system, and includes a form in which a plurality of aryls are connected by a single bond.
  • fusion and “condensation” described in the present invention may be interpreted the same.
  • Examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like, However, the present invention is not limited thereto.
  • arylene refers to a divalent organic radical derived by removal of one hydrogen from the aryl, and follows the definition of aryl.
  • the number of carbon atoms according to the definition of the substituent described in Formula 1 does not include the number of carbon atoms of the substituent that may be further substituted.
  • the heterocyclic compound according to an aspect of the present invention is a novel compound having a boron-centered condensed ring structure, and is contained in an organic material layer such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer of an organic light emitting device. It is an organic material exhibiting an effective effect.
  • the heterocyclic compound is an organic light emitting material that exhibits thermally activated delayed fluorescence (TADF), and exhibits surprisingly improved quantum efficiency and small Stokes shift value, and realizes blue light emission with high color purity. This is possible.
  • TADF thermally activated delayed fluorescence
  • the heterocyclic compound according to an embodiment has the advantage that it can be applied in various embodiments as an organic material of an organic light emitting device.
  • One aspect of the present invention provides a heterocyclic compound represented by the following formula (1).
  • R 1 to R 3 are each independently (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted (C3-C30) ) cycloalkyl or substituted or unsubstituted (C2-C30)heterocycloalkyl;
  • R a to R f are each independently hydrogen, (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted (C3 -C30)cycloalkyl or substituted or unsubstituted (C2-C30)heterocycloalkyl, wherein R a to R f are adjacent to each other or may be linked to form a fusion ring;
  • X 1 and X 2 are each independently O, S or NR aa ;
  • L 1 and L 2 are each independently (C1-C30)alkylene or (C6-C30)arylene;
  • R aa is hydrogen or (C1-C30)alkyl
  • a to c are each independently an integer of 0 to 2.
  • the heterocyclic compound according to an aspect has the structural characteristics as described above, for example, m-xylene is substituted for boron- and nitrogen-based condensed rings, so it can be utilized as a high-performance thermally activated delayed fluorescent material.
  • the heterocyclic compound since the heterocyclic compound has a small structural change before and after excitation, the Stokes shift value is greatly reduced, and it exhibits a surprisingly small full-width at half maximum, and it is possible to realize blue light emission with high color purity.
  • it has excellent thermal stability, which is one of the important factors for providing driving stability to the organic light emitting device, and the organic light emitting device including the same can implement high efficiency and long life characteristics.
  • heterocyclic compound according to an embodiment may be represented by the following Chemical Formula 1-1.
  • R 4 to R 8 are each independently hydrogen, (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted (C3 -C30) cycloalkyl or substituted or unsubstituted (C2-C30) heterocycloalkyl, wherein R 4 to R 9 are a substituent adjacent to each other or may be linked to form a fusion ring;
  • a to c are each independently an integer of 0 to 2;
  • R 1 to R 3 are the same as defined in Formula 1 above.]
  • the heterocyclic compound according to an embodiment of the present invention may be represented by the following Chemical Formula 2 in terms of having better color purity.
  • R 11 to R 13 are each independently hydrogen, (C1-C30)alkyl or (C6-C30)aryl;
  • R 4 to R 9 are each independently hydrogen or (C6-C30) aryl, wherein R 4 and R 5 , R 6 and R 7 and R 8 and R 9 are or may be linked to form a fusion ring;
  • Z a and Z b are each independently O, S or NR aa ;
  • R aa is hydrogen or (C1-C30)alkyl.
  • the heterocyclic compound according to an embodiment of the present invention may be represented by the following Chemical Formulas 3, 4, 5 or 6 in terms of having improved durability and excellent color purity along with improvement of luminous efficiency.
  • R 4 to R 9 are each independently hydrogen or (C6-C20)aryl
  • R 11 to R 13 are each independently hydrogen, (C1-C20)alkyl or (C6-C20)aryl;
  • Z 1 to Z 3 are each independently O or S.
  • Z 1 to Z 3 are the same as each other, and may be O or S.
  • R 4 , R 7 and R 9 are the same as each other, and may be hydrogen or (C6-C12)aryl, preferably hydrogen or phenyl.
  • R 5 , R 6 and R 8 are the same as each other, and may be hydrogen or (C6-C12)aryl, preferably hydrogen or phenyl.
  • R 11 to R 13 are the same as each other and may be hydrogen, (C1-C10)alkyl or (C6-C12)aryl, preferably hydrogen, (C1-C5)alkyl or It may be phenyl.
  • the heterocyclic compound according to an embodiment of the present invention may be included in the organic material layer of the organic light emitting device due to its structural specificity, and more specifically, may be included in the light emitting layer in the organic material layer.
  • heterocyclic compound according to an embodiment of the present invention may be more specifically selected from compounds having the following structure, but is not limited thereto.
  • the heterocyclic compound according to an embodiment may be prepared using materials and reaction conditions known in the art.
  • an aspect of the present invention provides an organic light emitting device including the heterocyclic compound according to an embodiment.
  • the organic light emitting device may include a first electrode; a second electrode; and one or more organic material layers interposed between the first electrode and the second electrode.
  • the organic material layer of the organic light emitting device may have a structure in which, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like are stacked.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.
  • the organic material layer may include the heterocyclic compound according to an embodiment. More specifically, the heterocyclic compound according to an embodiment may be included in the emission layer of the organic light emitting device.
  • organic light emitting diode may be manufactured in a possible manner within a range recognized by those skilled in the art.
  • the heterocyclic compound according to an embodiment is applicable to various organic light emitting devices, and the organic light emitting device is a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel lighting device, and a monochromatic or white flexible lighting device may be used, but is not limited thereto.
  • the organic light emitting device may include an anode, a cathode, and an organic material layer disposed therebetween.
  • the organic material layer of the above-described organic light emitting device may include one or more of an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, Except for including the hetorocyclic compound according to an embodiment in the organic material layer, it is a matter of course that it can be prepared in a structure known in the art using conventional manufacturing methods and materials in the art.
  • the heterocyclic compound according to an embodiment of the present invention may be included in one or more of the organic material layers, and more specifically, in the organic material layer, an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer , may be used instead of one or more of the electron transport layer and the electron injection layer, or may be used by forming a layer together with them.
  • an auxiliary layer buffer layer
  • a hole injection layer a hole transport layer
  • a light emitting layer a hole blocking layer
  • the organic light emitting diode according to an embodiment of the present invention is formed using a physical vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to form a metal or conductive metal oxide or These alloys are deposited to form an anode, and an organic material layer including at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. It can be manufactured by In addition, the auxiliary layer (buffer layer) may be formed between the hole transport layer and the light emitting layer or between the electron transport layer and the light emitting layer.
  • PVD physical vapor deposition
  • the organic material layer may have a multilayer structure including an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto, and may have a single layer structure.
  • auxiliary layer buffer layer
  • hole injection layer hole injection layer
  • hole transport layer hole transport layer
  • light emitting layer an electron transport layer
  • electron injection layer electron injection layer
  • the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.
  • the heterocyclic compound according to an embodiment of the present invention may be included in the light emitting layer preferably among the organic material layers, and the heterocyclic compound according to an embodiment is a blue light emitting material, and a light emitting material (phosphorescent host). ) or as a Thermally Activated Delayed Fluorescence (TADF) dopant material.
  • TADF Thermally Activated Delayed Fluorescence
  • the substrate is PET (polyethylene terephthalate), PEN (polyethylenenaphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS (polystylene), POM (polyoxyethlene), in addition to glass and quartz plates.
  • AS resin acrylonitrile styrene copolymer
  • ABS resin acrylonitrile butadiene styrene copolymer
  • TAC Triacetyl cellulose
  • An anode is positioned on the substrate.
  • This anode is an electrode for injecting holes into the hole injection layer positioned thereon.
  • As the anode material a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer.
  • metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof
  • metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO)
  • combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb
  • conductive polymers such as poly(3-methylthiophene
  • a hole injection layer is positioned on the anode.
  • a condition required for the material of the hole injection layer is that the hole injection efficiency from the anode is high, and the injected holes must be efficiently transported. For this, the ionization potential should be small, the transparency to visible light should be high, and the stability to the hole should be excellent.
  • the hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection material examples include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene (HATCN), quinacridone-based organic material, and perylene )-based organic materials, anthraquinone or polyaniline and polythiophene-based conductive polymers, but are not limited thereto, and specifically, CuPc (copper phthalocyanine), NPD (N,N'-dinaphthyl-N,N'-phenyl-(1,1'-biphenyl)-4,4'-diamine), m-MTDATA (4,4',4"-tris(3-Methylphenylphenylamino)triphenylamine), 1-TNATA (4,4', 4''-tris[1-naphthyl(phenyl)amino] triphenyl amine), 2-TNATA (4,4',4''-tris[2-napo
  • a hole transport layer is positioned on the hole injection layer.
  • the hole transport layer receives the holes from the hole injection layer and transports them to the light emitting layer positioned thereon, and serves to prevent high hole mobility, stability of holes, and electrons.
  • Tg glass transition temperature
  • NPB NPB
  • NPD spiro- It may be an arylamine-based compound, a perylene-arylamine-based compound, an azacycloheptatriene compound, a bis(diphenylvinylphenyl)anthracene, a silicon germanium oxide compound, or a silicon-based arylamine compound.
  • NPB N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine
  • NPD N,N'-bis(naphthalen-1-yl)-N, N'-bis(phenyl)-2,2'-dimethylbenzidine
  • TPD N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine
  • TTB N,N,N',N'- tetrakis(4-methylphenyl)-(1,1'biphenyl)-4,4-diamine
  • TTP N1,N4-diphenyl-N1,N4-dim-tolylbenzene-1,4-diamine
  • ETPD N,N '-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-d
  • a light emitting layer is positioned on the hole transport layer.
  • the light emitting layer is a layer that emits light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material with high quantum efficiency.
  • a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence, and more preferably the present invention It may include a heterocyclic compound according to an embodiment of the.
  • the above-described light emitting layer includes the heterocyclic compound according to an embodiment of the present invention in the light emitting layer, so that superior luminous efficiency and high color purity can be realized.
  • An electron transport layer is positioned on the emission layer.
  • Such an electron transport layer requires a material that has high electron injection efficiency and can efficiently transport injected electrons from a cathode positioned thereon. To this end, it must be made of a material having high electron affinity and electron movement speed and excellent stability to electrons.
  • the electron transport material satisfying the above conditions include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; and a hydroxyflavone-metal complex, preferably TSPO1 (diphenyl-4-triphenylsilylphenylphosphine oxide), TPBI (1,3,5-tris(N-phenylbenzimiazole-2-yl)benzene); Alq3 (Tris(8-hydroxyquinolinato)aluminum); Bphen (Bathophenanthroline), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2-(4-biphenyl)-5-(4-tert-butyl)-1,3,4-oxadizole), TAZ (3-(4-biphenyl)-4-phenyl-5-(4-tert- azole compounds such as butyl)-1,2,4-triazole), OXD-7 (1,3-bis[
  • an electron injection layer may be stacked on the electron transport layer.
  • the electron injection layer may include a metal complex compound such as Balq, Alq 3 , Be(bq) 2 , Zn(BTZ) 2 , Zn(phq) 2 , PBD, spiro-PBD, TPBI, Tf-6P, and the like; aromatic compounds having an imidazole ring; boron compounds; It can be produced using a low molecular weight material including
  • a cathode is positioned on the electron injection layer.
  • a cathode serves to inject electrons
  • the material used as the cathode is not limited as long as the material used for the cathode in the art is used, and for efficient electron injection, a metal having a low work function is more preferable.
  • suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver; or a suitable alloy thereof; this can be used
  • an electrode having a two-layer structure such as lithium fluoride and aluminum (LiF/Al), lithium oxide and aluminum (LiO 2 /Al), strontium oxide and aluminum having a thickness of 100 ⁇ m or less may be used.
  • the heterocyclic compound according to an embodiment of the present invention may be used as an auxiliary layer (buffer layer) material, a hole injection material, a hole transport material, a light emitting material, an electron transport material or an electron injection material, preferably light emitting It may be used as a material (phosphorescent host) or a dopant material for thermally activated delayed fluorescence, and more preferably used as a dopant material for TADF.
  • the organic light-emitting device including the heterocyclic compound according to an embodiment of the present invention may be a top emission type, a back emission type, or a double-sided emission type.
  • compound 1-a (7.8 g, 28.58 mmol) and 1,3,5-tribromobenzene (3.0 g, 9.5 mmol) were dissolved in 100.0 mL of toluene and sodium terbutoxide (8.2 g, 85.6 mmol) , 1.0 M Tri-tert buthylphosphin in toluene (1.71 mL, 1.71 mmol) and tris (dibenzylideneacetone) dipalladium (0) (0.39 g, 0.428 mmol) were added, and then nitrogen The mixture was stirred for 12 hours under reflux atmosphere. Upon completion of the reaction, the mixture was cooled to room temperature and filtered using a silica filter. The solvent was concentrated and the sample was purified by silica gel column chromatography to obtain compound 1-b (5.8 g, 68%).
  • compound 1-b (5.0 g, 5.60 mmol) was dissolved in 1,2-dichlorobenzene, boron tribromide (1.06 mL, 11.2 mmol) was added, and then stirred at 180 o C in a nitrogen atmosphere for 20 hours. . After completion of the reaction, after cooling to room temperature, N,N-diisopropylethylamine (3.9 mL, 22.4 mmol) was added thereto, followed by filtering using a silica filter. The solvent was concentrated and the sample was purified by silica gel column chromatography to obtain heterocyclic compound 1 (2.0 g, 40%).
  • step 1 of Example 1 using the same method except that 4-bromo-1,1'-biphenyl was used instead of 3-bromo-1,1'-biphenyl, Compound 2- a (8.4 g, 72%) was obtained.
  • step 2 of Example 1 compound 2-b (6.1 g, 70%) was obtained in the same manner except that compound 2-a was used instead of compound 1-a.
  • step 3 of Example 1 a heterocyclic compound 2 (2.0 g, 40%) was obtained in the same manner except that compound 2-b was used instead of compound 1-b.
  • step 1 of Example 1 using the same method except that 1-bromobenzene was used instead of 3-bromo-1,1'-biphenyl, compound 3-a (6.2 g, 74% ) was obtained.
  • step 2 of Example 1 compound 3-b (3.92 g, 62%) was obtained in the same manner except that compound 3-a was used instead of compound 1-a.
  • step 3 of Example 1 a heterocyclic compound 3 (0.58 g, 58%) was obtained in the same manner except that compound 3-b was used instead of compound 1-b.
  • step 1 of Example 1 1-bromobenzene was used instead of 3-bromo-1,1'-biphenyl, and 2,4,6-trimethylaniline was used instead of 2,6-dimethylaniline.
  • Compound 4-a (4.84 g, 72%) was obtained in the same manner except that it was used.
  • step 2 of Example 1 compound 4-b (1.5 g, 66%) was obtained in the same manner except that compound 4-a was used instead of compound 1-a.
  • step 3 of Example 1 a heterocyclic compound 4 (0.38 g, 38%) was obtained in the same manner except that compound 4-b was used instead of compound 1-b.
  • Each of the heterocyclic compounds 1 to 5 prepared in Examples 1 to 5 was diluted to a concentration of 0.2 mM in tetrahydrofuran (THF), and using a Shimadzu UV-350 Spectrometer, UV The absorption spectrum was measured. The results are shown in FIGS. 1 to 5 .
  • Each of the heterocyclic compounds 1 to 5 prepared in Examples 1 to 5 was diluted to a concentration of 10 mM in toluene (Tol), and an ISC PC1 spectrofluorometer equipped with a Xenon lamp was used. , the photoluminescence (RTPL, RT Photoluminecscence) spectrum was measured at room temperature. The results are shown in FIGS. 1 to 5 .
  • Each of the heterocyclic compounds 1 to 5 prepared in Examples 1 to 5 was diluted to a concentration of 10 mM in tetrahydrofuran (THF), and an ISC PC1 spectrofluorometer equipped with a Xenon lamp was used.
  • PL (LTPL) spectrum was measured at low temperature (100K) using The results are shown in FIGS. 1 to 5 .
  • thermogravimetric analysis TGA was performed by heating at 10 °C per minute (min) from 40 °C to 800 °C under nitrogen atmosphere using TA instrument TGA Q50. was carried out, and the results are shown in FIG. 6 .
  • TGA thermogravimetric analysis
  • FIG. 6 thermogravimetric analysis
  • Example 1 Example 2 Example 3 Example 4 Example 5 UV-Sol. THF (nm) 444 444 429 430 481 PL-Sol. Tol (nm) 460 458 445 445 495 Stokes shift (nm) 16 14 16 15 14 FWHM (nm) 20 15 18 18 20 E g (eV) (optical) 2.66 2.69 2.79 2.78 2.47 S 1 (eV) 2.79 2.78 2.88 2.89 2.58 T 1 (eV) 2.67 2.67 2.72 2.78 2.44 ⁇ E st (eV) 0.12 0.11 0.16 0.11 0.14
  • heterocyclic compounds 1 to 5 of the present invention are all thermally activated delayed fluorescence (TADF) materials having ⁇ E st of 0.2 eV or less and excellent luminous efficiency.
  • TADF thermally activated delayed fluorescence
  • the heterocyclic compounds 1 to 5 of the present invention have a molecular structure fixed by a condensed ring, the difference in the maximum absorption (UV) wavelength and the maximum emission (PL) wavelength is the Stoke shift ( Stokes shift) value is greatly reduced. That is, the heterocyclic compound according to the present invention not only exhibits improved quantum efficiency, but also exhibits a surprisingly small full-width at half maximum, enabling the implementation of high-purity blue (Compounds 1 to 4) or green (Compound 5) light emission. In addition, it can be seen that the organic light emitting diode has excellent thermal stability, which is one of the important factors providing driving stability.
  • the heterocyclic compound according to the present invention is a TADF material exhibiting excellent color purity, thermal stability and lifespan characteristics.
  • An organic light emitting device was manufactured through a vacuum deposition process using the heterocyclic compound according to the present invention.
  • the structure of the fabricated organic light emitting device is ITO (70 nm) / HATCN (1 nm) / TAPC (25 nm) / TCTA (10 nm) / mCP (10 nm) / heterocyclic compound 1 of the present invention (Example 1) (25 nm) / DPEPO (5 nm)/TmPyPB (40 nm)/LiF (0.9 nm)/Al (100 nm).
  • the transparent electrode ITO thin film cell obtained from the glass for OLED was ultrasonically washed using trichloroethylene, acetone, ethanol, and distilled water sequentially, and then placed in isopropanol and stored for use.
  • HATCN was deposited on the ITO thin film to form a 1 nm hole injection layer, and then a hole transport layer was formed on the hole injection layer.
  • the hole transport layer is TAPC (1,1-bis((di-4-tolylamino)phenyl)cyclohexane) (25nm)/TCTA (tris(4-carbazoyl-9-ylphenyl)amine) (10nm)/mCP (N,N' -dicarbazolyl-3,5-benzene) (10 nm) was formed in a sequentially stacked structure. A light emitting layer was formed on the hole transport layer.
  • the light emitting layer was formed to a thickness of 25 nm by doping 20 wt% of the heterocyclic compound 1 (Example 1) of the present invention as a dopant to DPEPO (bis-(2-(diphenylphosphino)phenyl)ether oxide) as a host.
  • DPEPO bis-(2-(diphenylphosphino)phenyl)ether oxide
  • EBL exciton blocking layer
  • TmPyPB was deposited on the exciton blocking layer to form an electron transport layer of 30 nm.
  • An organic light-emitting device was manufactured by depositing LiF (0.9 nm)/Al (100 nm) on the electron transport layer to form a cathode.
  • Each structure has a stacked structure in turn and was manufactured by a general vacuum deposition process.
  • a light emission test was performed by applying a voltage of 0 to 15V to the organic light emitting device manufactured as described above, and the driving voltage (V on ), External Quantum Efficiency (EQE), and current efficiency (CE, Current efficiency) of the device were performed. ), power efficiency (PE), the maximum wavelength of the EL spectrum, and color purity were evaluated and described in Table 2 below.
  • the organic light-emitting device including the heterocyclic compound according to an embodiment of the present invention as a dopant material of the light-emitting layer exhibited excellent EQE and excellent color purity, thereby exhibiting a high-purity deep blue color. That is, when the heterocyclic compound of the present invention is applied to a light emitting device, thermally activated delayed fluorescence is expressed, thereby providing a high efficiency, high color purity blue organic light emitting device that achieves an excellent EQE value.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un nouveau composé hétérocyclique et un dispositif électroluminescent organique le comprenant, et plus particulièrement, un nouveau composé hétérocyclique présentant une fluorescence retardée activée thermiquement (TADF), et un dispositif électroluminescent organique comprenant le composé hétérocyclique.
PCT/KR2022/004090 2021-03-24 2022-03-23 Nouveau composé hétérocyclique et dispositif électroluminescent organique le comprenant Ceased WO2022203403A1 (fr)

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KR10-2021-0037855 2021-03-24
KR1020220035516A KR102696222B1 (ko) 2021-03-24 2022-03-22 신규한 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
KR10-2022-0035516 2022-03-22

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EP4567088A1 (fr) 2023-12-06 2025-06-11 Idemitsu Kosan Co.,Ltd. Composé et dispositif électroluminescent organique comprenant le composé
WO2025120516A1 (fr) 2023-12-06 2025-06-12 Idemitsu Kosan Co., Ltd. Composé et dispositif électroluminescent organique comprenant le composé

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KR20190037176A (ko) * 2017-09-28 2019-04-05 주식회사 엘지화학 화합물 및 이를 포함하는 유기 발광 소자
JP6641069B1 (ja) * 2019-03-29 2020-02-05 住友化学株式会社 発光素子及びその製造方法並びに発光素子用組成物及びその製造方法
KR20200081302A (ko) * 2018-12-27 2020-07-07 주식회사 엘지화학 화합물 및 이를 포함하는 유기발광소자
KR20200119453A (ko) * 2019-04-09 2020-10-20 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
WO2020251049A1 (fr) * 2019-06-14 2020-12-17 学校法人関西学院 Composé aromatique polycyclique

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KR20190037176A (ko) * 2017-09-28 2019-04-05 주식회사 엘지화학 화합물 및 이를 포함하는 유기 발광 소자
KR20200081302A (ko) * 2018-12-27 2020-07-07 주식회사 엘지화학 화합물 및 이를 포함하는 유기발광소자
JP6641069B1 (ja) * 2019-03-29 2020-02-05 住友化学株式会社 発光素子及びその製造方法並びに発光素子用組成物及びその製造方法
KR20200119453A (ko) * 2019-04-09 2020-10-20 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
WO2020251049A1 (fr) * 2019-06-14 2020-12-17 学校法人関西学院 Composé aromatique polycyclique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4567088A1 (fr) 2023-12-06 2025-06-11 Idemitsu Kosan Co.,Ltd. Composé et dispositif électroluminescent organique comprenant le composé
WO2025120516A1 (fr) 2023-12-06 2025-06-12 Idemitsu Kosan Co., Ltd. Composé et dispositif électroluminescent organique comprenant le composé

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