WO2019172623A1 - Composé pour dispositif électrique organique, dispositif électrique organique l'utilisant, et dispositif électronique associé - Google Patents

Composé pour dispositif électrique organique, dispositif électrique organique l'utilisant, et dispositif électronique associé Download PDF

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WO2019172623A1
WO2019172623A1 PCT/KR2019/002548 KR2019002548W WO2019172623A1 WO 2019172623 A1 WO2019172623 A1 WO 2019172623A1 KR 2019002548 W KR2019002548 W KR 2019002548W WO 2019172623 A1 WO2019172623 A1 WO 2019172623A1
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group
formula
ring
mmol
sub3
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최연희
이형동
박종광
소기호
이윤석
김원삼
박정환
황선필
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덕산네오룩스 주식회사
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Publication of WO2019172623A1 publication Critical patent/WO2019172623A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like according to their functions.
  • the LUMO and HOMO levels of the host material have a great influence on the efficiency and lifespan of the organic EL device. As a result, it is possible to prevent efficiency degradation and lifespan reduction due to charge balance control, dopant quenching, and light emission at the hole transport layer interface in the light emitting layer.
  • the energy transfer in the light emitting layer for thermal activated delayed fluorescent (TADF) and exciplex can be identified by the PL lifetime (TRTP) method.
  • the time resolved transient PL (TRTP) method is a method of observing a decay time of a spectrum after a pulsed light source is irradiated to a host thin film. It is a measuring method.
  • TRTP measurement is a measurement method that can distinguish between fluorescence and phosphorescence, and energy transfer method, exciplex energy transfer method, and TADF energy transfer method within a mixed host material.
  • the present invention has been proposed to solve the problems of the phosphorescent host material as described above, the charge balance control, efficiency and lifetime in the light emitting layer by adjusting the HOMO level for the host material of the phosphorescent organic electroluminescent device comprising a phosphorescent dopant Compound which can improve It aims at providing the organic electric element using this and its electronic device.
  • the present invention combines a specific first host material with a specific second host material as a main component to control efficient hole injection in the light emitting layer of the phosphorescent organic electroluminescent device, thereby reducing the energy barrier between the light emitting layer and the adjacent layer. It is possible to maximize the charge balance in the light emitting layer to provide high efficiency and long life of the organic electric device.
  • the present invention provides an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer.
  • an organic electric device comprising a first host compound represented by 1 and a second host compound represented by Formula 2 below.
  • the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
  • the mixture according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electric element, and also to greatly improve the life of the element.
  • FIG. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
  • halo or halogen as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
  • alkyl or “alkyl group” has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
  • heteroalkyl group means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
  • alkenyl group As used herein, the terms “alkenyl group”, “alkenyl group” or “alkynyl group” have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is not limited to this.
  • cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
  • alkoxyl group means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
  • alkenoxyl group means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
  • aryloxyl group or “aryloxy group” means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
  • aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
  • an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
  • the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.
  • aryl or "ar” means a radical substituted with an aryl group.
  • an arylalkyl group is an alkyl group substituted with an aryl group
  • an arylalkenyl group is an alkenyl group substituted with an aryl group
  • the radical substituted with an aryl group has the carbon number described herein.
  • an arylalkoxy group means an alkoxy group substituted with an aryl group
  • an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group
  • an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group.
  • the arylcarbonyl group is a carbonyl group substituted with an aryl group.
  • heteroalkyl means an alkyl including one or more heteroatoms unless otherwise indicated.
  • heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
  • heterocyclic group includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of a single ring and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
  • heteroatom refers to N, O, S, P or Si unless otherwise stated.
  • Heterocyclic groups may also include rings comprising SO 2 instead of carbon forming the ring.
  • a “heterocyclic group” includes the following compounds.
  • aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
  • aliphatic ring means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
  • ring refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.
  • heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
  • carbonyl used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
  • ether as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
  • substituted in the term “substituted or unsubstituted” as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 1 ⁇ C 20 alkoxyl group, C 1 ⁇ C 20 alkylamine group, C 1 ⁇ C 20 alkylthiophene group, C 6 ⁇ C 20 arylthiophene group, C 2 ⁇ C 20 alkenyl group, C 2 ⁇ C 20 alkynyl, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 20 aryl group, of a C 6 ⁇ C 20 substituted by deuterium aryl group, a C 8 ⁇ C 20 aryl alkenyl group, a silane group, a boron Group, germanium group, and C 2 ⁇ C 20 It is meant to be substituted with one or more substituents selected from the group consist
  • the substituent R 1 when a is an integer of 0, the substituent R 1 is absent, that is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. Omitted formulas and compounds may be omitted.
  • a is an integer of 1
  • one substituent R 1 is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, each of them is bonded as follows, wherein R 1 may be the same or different
  • a is an integer of 4 to 6
  • is bonded to the carbon of the benzene ring in a similar manner while the indication of hydrogen bonded to the carbon forming the benzene ring is omitted.
  • the present invention provides an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer.
  • an organic electric device comprising a first host compound represented by 1 and a second host compound represented by Formula 2 below.
  • M is an arylene group of C 6 -C 60 or Formula 1-1
  • A, B, C and D are each independently an aryl group of C 6 -C 20 or a heterocyclic group of C 2 -C 20 , C is bonded to L 3 , D is bonded to L 4 ,
  • X 1 is S or O
  • X 2 is NL 6 -Ar 7 , O, S or CR'R ",
  • X 3 and X 4 are each independently a single bond, NL 7 -Ar 8 , O, S or CR'R ",
  • R 'and R are each independently hydrogen; C 6 ⁇ C 60 aryl group; Fluorenyl group; C 3 ⁇ C 60 Heterocyclic group; C 1 ⁇ C 50 Alkyl group; and -L'-N (R a ) (R b ), and
  • R 'and R may combine with each other to form a ring as a spy
  • L ' is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group; selected from the group consisting of R a and R b independently of each other an C 6 -C 60 aryl group; Fluorenyl groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 And Ar 8 are each independently of the other C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl groups; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And an aryloxy group of C 6 -C 30 , and also Ar 1 Ar 5 may combine with each other to form a ring,
  • L 1 , L 2 , L 3 , L 4 , L 5 , L 6 and L 7 are each independently a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And aliphatic hydrocarbon groups,
  • R 4 , R 5 and R 6 are each independently of the C 6 ⁇ C 60 aryl group; Fluorenyl groups; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; C 1 ⁇ C 50 Alkyl group; C 2 ⁇ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); Is selected from the group consisting of
  • aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl groups; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group and C 8 -C 20
  • the present invention provides an organic electroluminescent device comprising a compound represented by any one of the following formulas A-1 to A-7 in Formula 1 independently of each other.
  • Z 1 to Z 48 are independently of each other CR c or N,
  • Z 1 to Z 48 bonded to L 1 to L 3 are carbon (C),
  • R c is the same as defined above for R a ,
  • the present invention provides an organic electroluminescent device comprising a compound represented by any one of L 1 to L 7 in Formula 1 or Formula 2 below.
  • Y is NL 8 -Ar 9 , O, S or CR'R ",
  • L 8 is the same as defined above in L 1 ,
  • Ar 9 is the same as defined in Ar 1 above,
  • a, c, d and e are independently integers from 0 to 4
  • b is an integer from 0 to 6
  • f and g are independently integers from 0 to 3
  • h is an integer from 0 to 2 I is an integer of 0 or 1
  • R 1 , R 2 and R 3 are independently of each other hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C 6 -C 60 aryl group; Fluorenyl groups; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; When selected from the group consisting of C 6 -C 30 aryloxy group and -L a -N (R d ) (R e ), or wherein a, b, c, d, e, f and g are 2 or more, And when h is
  • L a is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And C 3 -C 60 aliphatic hydrocarbon group, wherein R d and R e are each independently of the C 6 -C 60 aryl group; Fluorenyl groups; C 2 -C 60 heterocyclic group including at least one hetero atom selected from the group consisting of O, N, S, Si and P; And a fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 .
  • Z 49 , Z 50 and Z 51 are independently of each other CR f or N, at least one of Z 49 , Z 50 and Z 51 is N,
  • R f is hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C 6 -C 60 aryl group; Fluorenyl groups; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And an aryloxy group of C 6 -C 30 , and adjacent R 1 and R f may combine with each other to form an aromatic ring or a heteroaromatic ring. ⁇
  • the present invention provides an organic electric device including at least one of Ar 1 to Ar 5 including a compound represented by the following Chemical Formula 1-2.
  • X 5 is NL 10 -Ar 10 , O, S or CR'R ",
  • L 9 and L 10 are the same as the above definition of L 1 ,
  • Ar 10 is the same as the definition of Ar 1 ,
  • the present invention provides an organic electric device, for example, the first host compound represented by Formula 1 includes a compound represented by the following Formula 3.
  • X 1 , X 2 , Ar 1 to Ar 5 are the same as defined above,
  • Z 1 to Z 4 are each independently CR c or N,
  • R c is as defined above.
  • the present invention provides an organic electroluminescent device comprising a compound in which X 1 , X 2 of Formula 1 are independently O or S.
  • the present invention provides an organic electroluminescent device comprising a compound represented by any one of the following formula 4 to formula 6 the second host compound represented by the formula (2).
  • R 4 , R 5 , R 6 , X 3 , X 4 , L 5 , L 7 , Ar 6 , Ar 8 , l, m and n are as defined above.
  • the present invention provides an organic electroluminescent device comprising, for example, a second host compound represented by Formula 2 including a compound represented by any one of Formulas 7 to 12.
  • R 4 , R 5 , R 6 , L 5 , L 7 , Ar 6 , Ar 8 , l, m and n are as defined above,
  • X is selected from NL 7 -Ar 8 , O, S or CR'R ".
  • the first host compound represented by Chemical Formula 1 includes the following Compounds 1-1 to 1-265.
  • the second host compound represented by Formula 2 in the present invention includes a compound represented by the following compound 2-1 to compound 2-128.
  • the organic electric device 100 includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110.
  • An organic material layer including a compound represented by Chemical Formula 1 is provided between 180.
  • the first electrode 120 may be an anode (anode)
  • the second electrode 180 may be a cathode (cathode)
  • the first electrode may be a cathode and the second electrode may be an anode.
  • the organic material layer may sequentially include the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the light emitting auxiliary layer 151, the electron transport layer 160, and the electron injection layer 170 on the first electrode 120. It may include. At this time, the remaining layers except for the light emitting layer 150 may not be formed.
  • the hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the electron transport auxiliary layer, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
  • the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
  • the organic electroluminescent device may be manufactured using a PVD method.
  • a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 are disposed thereon.
  • the organic material layer including the electron injection layer 170 it can be prepared by depositing a material that can be used as a cathode thereon.
  • the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
  • the present invention includes at least one hole transport band layer between the first electrode and the light emitting layer, the hole transport band layer includes a hole transport layer, a light emitting auxiliary layer or both, the hole transport band layer It provides an organic electric device comprising the compound represented by the formula (1).
  • the present invention provides an organic electroluminescent device included in the light emitting layer by mixing the compound represented by Formula 1 and Formula 2 in any one ratio of 1: 9 to 9: 1, preferably 1: 9 to 5: 5, more preferably, it is mixed in a ratio of 2: 8 or 3: 7 and included in the light emitting layer.
  • the organic electroluminescent device further includes a light efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer.
  • An organic electric device is provided.
  • the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, the organic material layer according to the present invention can be formed in various ways Therefore, the scope of the present invention is not limited by the formation method.
  • the organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
  • WOLED White Organic Light Emitting Device
  • Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
  • CCM color conversion material
  • the present invention is a display device comprising the above-mentioned organic electric element; And a controller for driving the display device.
  • the organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white light emitting device.
  • the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
  • the compound represented by Formula 1 according to the present invention (final product 1) is disclosed in Korean Patent Registration No. 10-1614739 (Registration date of April 18, 2016), Korean Patent Application No. 2016-0110817 (application date of August 30, 2016) It was prepared by the disclosed synthesis method.
  • X 1 , A, B, L 1 to L 4 , M, Ar 1 to Ar 5 are the same as defined above.
  • Sub2-59 (5.30 g, 11.97 mmol) was dissolved in Toluene (120 mL) in a round flask, then Sub1-59 (5.15 g, 11.97 mmol), Pd 2 (dba) 3 (0.33 g, 0.36 mmol), P ( t -Bu) 3 (0.4 mL, 0.72 mmol), NaO t -Bu (3.45 g, 35.90 mmol) was stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 1-59 (7.96 g, yield: 84%).
  • Sub 3-b-2 (47 g, 151.5 mmol) obtained in the above synthesis, Sub 3-c-1 (37 g, 182 mmol), K 2 CO 3 (63 g, 454.5 mmol), Pd (PPh 3 ) 4 (11 g, 9.1 mmol) was obtained using the synthesis method of Sub3-d-1 to obtain 33 g (yield: 72%) of the product Sub3-d-2.
  • Sub3-d-1 (33 g, 108 mmol) and triphenylphosphine (71 g, 270 mmol) obtained in the synthesis were prepared using Sub3-2 (10 g, yield: 35%) and Sub3- using the synthesis method of Sub3-1. 18 (14 g, yield: 47%) was obtained.
  • Sub3-d-3 (33 g, 114 mmol) and triphenylphosphine (75 g, 285 mmol) obtained in the synthesis were synthesized using Sub3-3 (10 g, yield: 34%) and Sub3- using the synthesis method of Sub3-1. 19 (15 g, yield: 52%) was obtained.
  • Sub 3-b-5 (48 g, 130 mmol), Sub 3-c-1 (32 g, 156 mmol) obtained in the above synthesis, K 2 CO 3 (54 g, 390 mmol), Pd (PPh 3 ) 4 (9.0 g, 7.8 mmol) was obtained using the synthesis method of Sub3-d-1 as 36 g (yield: 75%) of the product Sub3-d-5.
  • Sub3-d-5 (36 g, 96 mmol) and triphenylphosphine (63 g, 240 mmol) obtained in the synthesis were synthesized using Sub3-5 (16 g, yield: 51%) and Sub3- using the synthesis method of Sub3-1. 21 (12 g, yield: 37%) was obtained.
  • Sub 3-b-6 (49 g, 157 mmol), Sub 3-c-1 (38 g, 189 mmol) obtained in the above synthesis, K 2 CO 3 (65 g, 472 mmol), Pd (PPh 3 ) 4 34 g (yield: 71%) of product Sub3-d-6 was obtained by using the synthesis method of Sub3-d-1 (11 g, 9.42 mmol).
  • Sub 3-b-8 (48 g, 150 mmol), Sub 3-c-1 (36 g, 180 mmol) obtained in the above synthesis, K 2 CO 3 (62 g, 450 mmol), Pd (PPh 3 ) 4 34 g (yield: 71%) of product Sub3-d-8 was obtained by using the synthesis method of Sub3-d-1.
  • Sub3-d-8 (34 g, 106 mmol) and triphenylphosphine (70 g, 265 mmol) obtained in the synthesis were synthesized using Sub3-8 (14 g, yield: 48%) and Sub3- using the synthesis method of Sub3-1. 23 (11 g, yield: 36%) was obtained.
  • Sub3-d-9 (30 g, 81 mmol) and triphenylphosphine (53 g, 203 mmol) obtained in the above synthesis were obtained by using the synthesis method of Sub3-1, to obtain Sub3-9 (23 g, yield: 84%).
  • Sub 3-b-10 (38 g, 124 mmol), Sub 3-c-1 (30 g, 148 mmol) obtained in the above synthesis, K 2 CO 3 (51 g, 371 mmol), Pd (PPh 3 ) 4 (8.6 g, 7.4 mmol) was obtained using the synthesis method of Sub3-d-1, 22 g (yield: 58%) of the product Sub3-d-10.
  • Sub3-d-10 (22 g, 71 mmol) and triphenylphosphine (47 g, 178 mmol) obtained in the above synthesis were obtained using the synthesis method of Sub3-1, to obtain Sub3-10 (17 g, yield: 86%).
  • Sub3-d-13 (19 g, 52.2 mmol) and triphenylphosphine (34 g, 131 mmol) obtained in the above synthesis were obtained using Sub3-1 (14 g, yield: 79%) using the synthesis method of Sub3-1.
  • Sub3-d-14 (15 g, 49.6 mmol) and triphenylphosphine (33 g, 124 mmol) obtained in the above synthesis were obtained using Sub3-1 (11 g, yield: 82%) using the synthesis method of Sub3-1.
  • Sub 3-b-15 (25 g, 84.8 mmol) obtained in the above synthesis, Sub 3-c-1 (21 g, 102 mmol), K 2 CO 3 (35 g, 254 mmol), Pd (PPh 3 ) 4 (5.9 g, 5.09 mmol) was obtained using the synthesis method of Sub3-d-1 to give 9.8 g (yield: 40%) of the product Sub3-d-15.
  • Sub3-d-15 (9.8 g, 33.9 mmol) and triphenylphosphine (22 g, 84.8 mmol) obtained in the above synthesis were used to obtain Sub3-15 (7.6 g, yield: 87%) using the synthesis method of Sub3-1.
  • the compound belonging to Sub 3 may be, but is not limited to, the following compounds.
  • Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 3.
  • Compounds belonging to Sub 4 may be the following compounds, but are not limited thereto.
  • Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 4.
  • Sub3-1 (3.0 g, 9.02 mmol) obtained in the synthesis was dissolved in toluene (100 mL) in a round bottom flask, then Sub4-1 (1.4 g, 9.02 mmol), Pd 2 (dba) 3 (0.25 g, 0.271 mmol ), P ( t -Bu) 3 (1.8 g, 9.02 mmol), NaO t -Bu (1.7 g, 18.0 mmol) was added and stirred at 120 ° C.
  • N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm.
  • NPB N-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine
  • Vacuum deposition was performed to form a hole transport layer.
  • a mixture of 50:50 of the inventive compound represented by Formula 1 and Formula 2 was used as a host on the hole transport layer, and as a dopant, (piq) 2 Ir (acac) [bis- (1-phenylisoquinolyl) iridium ( III) acetylacetonate] was deposited to a weight of 95: 5 to deposit a 30 nm thick light emitting layer on the hole transport layer.
  • BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum
  • BAlq the electron transport layer Tris (8-quinolinol) aluminum
  • Alq3 the electron transport layer Tris (8-quinolinol) aluminum
  • the electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices prepared as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage.
  • the T95 life was measured using a life measurement instrument manufactured by McScience.
  • the following table shows the results of device fabrication and evaluation.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used alone as a host.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound represented by Formula 2 was used alone as a host.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and Compound 2 were used as a host.
  • Example 17 1-16 2-1 5.8 11.3 2500.0 22.1 114.1
  • Example 18 1-59 2-1 5.9 12.0 2500.0 20.8 115.8
  • Example 19 1-60 2-1 5.9 11.4 2500.0 21.9 112.8
  • Example 20 1-65 2-1 6.0 14.4 2500.0 17.4 105.7
  • Example 21 1-181 2-1 6.0 13.5 2500.0 18.6 109.3
  • Example 22 1-186 2-1 6.0 12.5 2500.0 20.0 108.6
  • Example 23 1-16 2-4 5.1 9.2 2500.0 27.3 123.8
  • Example 24 1-59 2-4 4.9 9.1 2500.0 27.3 124.5
  • Example 25 1-60 2-4 5.2 9.2 2500.0 27.1 121.5
  • Example 26 1-65 2-4 5.4 9.8 2500.0 25.5 118.8
  • Example 27 1-181 2-4 5.1 9.8 2500.0 25.6 121.7
  • Example 28 1-186 2-4 5.2 9.6 2500.0 26.1 119.3
  • Example 29 1-16 2-7 4.6 8.1 2500.0 30.7
  • Comparative Examples 1 to 4 using the compound of the present invention represented by the formula (2) and Comparative Compound 1 alone as phosphorescent hosts Comparative Example 2 using the compound of the present invention (2-117, 2-122) And Comparative Example 3 was confirmed to exhibit a higher efficiency and a higher lifetime than Comparative Example 1 using a comparative compound.
  • Comparative Example 1 and Compound (2-117) were mixed with Comparative Compound 1 and Comparative Example 4 using the phosphorescent host to show a slightly higher efficiency than Comparative Examples 1 to 3 using the single substance.
  • the inventors of the present invention determine that each of the substances of the compound of Formula 1 and the compound of Formula 2 have new characteristics other than those of the substances, based on the experimental results, the substance of Formula 1, the substance of Formula 2 , PL and PL lifetime were measured using the mixture of the present invention, respectively.
  • the compounds of the present invention were mixed with Chemical Formula 1 and Chemical Formula 2, it was confirmed that a new PL wavelength was formed differently from the case of a single compound. It was confirmed that the increase and decrease than the disappearance time.
  • the mixed thin film is an important example showing the exciplex energy transfer and the light emission process.
  • the combination of the present invention is superior to Comparative Example 4, which is used as a phosphorescent host mixed with Comparative Compound 1, because the hole characteristics of the polycyclic ring compound represented by Chemical Formula 2 having characteristics such as electron stability as well as hole, and high T1
  • the electron blocking ability is improved due to the high T1 and the high LUMO energy value, and more holes are quickly and easily moved to the light emitting layer.
  • the charge balance in the light emitting layer of holes and electrons is increased, so that light emission is achieved inside the light emitting layer rather than at the hole transport layer interface.
  • compounds in which M is substituted with Dibenzothiophen and Dibenzofuran were confirmed to have better efficiency and lifespan.
  • the combination of Chemical Formula 1 and Chemical Formula 2 is electrochemically synergistic.
  • Table 5 is a result obtained by fixing the first host with excellent performance as a result obtained in Table 4 and using a mixture of various second host, the first host is a compound 1-16 excellent in driving voltage, efficiency and lifespan , 1-59, 1-60, 1-65, 1-181 and 1-186 and the second host are compounds 2-1, 2-4, 2-7, 2-15, 2-33, 2-42 , 2-43, 2-62, 2-70, 2-82, 2-83, and 2-122 resulted in a drive voltage when two mixed host materials were used rather than a single host material.
  • the efficiency and lifespan can be significantly improved.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except for using a different mixing ratio of materials as described in Table 6.
  • the mixture of the compound of the present invention was measured by manufacturing a device by ratio (2: 8, 3: 7, 4: 6, 6: 4, 7: 3, 8: 2).
  • the results of the mixture of compound 1-16 and compound 2-7 showed similarly excellent driving voltage, efficiency and lifetime for 2: 8 and 3: 7.
  • the ratio of the first host was increased, the results of driving voltage, efficiency, and lifespan were gradually reduced, which was the same in the mixture of Compound 1-59 and Compound 2-7. This may be explained because the charge balance in the light emitting layer is maximized when an appropriate amount of the compound represented by Chemical Formula 1 having strong hole characteristics such as 2: 8 and 3: 7 is mixed.
  • the present invention it is possible to manufacture an organic device having excellent device characteristics of high brightness, high light emission and long life, and there is industrial applicability.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un nouveau mélange pouvant améliorer l'efficience lumineuse, la stabilité, et la durée de vie d'un dispositif, un dispositif électrique organique l'utilisant, et un dispositif électronique associé.
PCT/KR2019/002548 2018-03-05 2019-03-05 Composé pour dispositif électrique organique, dispositif électrique organique l'utilisant, et dispositif électronique associé WO2019172623A1 (fr)

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WO2020058811A1 (fr) * 2018-09-20 2020-03-26 株式会社半導体エネルギー研究所 Composé organique, dispositif électroluminescent, équipement électroluminescent, dispositif électronique et dispositif d'éclairage
CN113816860A (zh) * 2020-06-19 2021-12-21 广州华睿光电材料有限公司 有机化合物、混合物、组合物及有机电子器件

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KR101614739B1 (ko) * 2015-12-01 2016-04-22 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
KR20170083765A (ko) * 2016-01-11 2017-07-19 덕산네오룩스 주식회사 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
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KR101614739B1 (ko) * 2015-12-01 2016-04-22 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
KR20170083765A (ko) * 2016-01-11 2017-07-19 덕산네오룩스 주식회사 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
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WO2020058811A1 (fr) * 2018-09-20 2020-03-26 株式会社半導体エネルギー研究所 Composé organique, dispositif électroluminescent, équipement électroluminescent, dispositif électronique et dispositif d'éclairage
CN113816860A (zh) * 2020-06-19 2021-12-21 广州华睿光电材料有限公司 有机化合物、混合物、组合物及有机电子器件
CN113816860B (zh) * 2020-06-19 2024-01-30 广州华睿光电材料有限公司 有机化合物、混合物、组合物及有机电子器件

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