[go: up one dir, main page]

WO2019128849A1 - Composé organique, haut polymère, mélange organique, composition et application associée dans un dispositif électronique organique - Google Patents

Composé organique, haut polymère, mélange organique, composition et application associée dans un dispositif électronique organique Download PDF

Info

Publication number
WO2019128849A1
WO2019128849A1 PCT/CN2018/122488 CN2018122488W WO2019128849A1 WO 2019128849 A1 WO2019128849 A1 WO 2019128849A1 CN 2018122488 W CN2018122488 W CN 2018122488W WO 2019128849 A1 WO2019128849 A1 WO 2019128849A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
organic
atoms
organic compound
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/122488
Other languages
English (en)
Chinese (zh)
Inventor
杨曦
潘君友
王璞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Chinaray Optoelectronic Materials Ltd
Original Assignee
Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Chinaray Optoelectronic Materials Ltd filed Critical Guangzhou Chinaray Optoelectronic Materials Ltd
Priority to CN201880069730.3A priority Critical patent/CN111278813B/zh
Publication of WO2019128849A1 publication Critical patent/WO2019128849A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to the field of organic electroluminescence technology, and in particular to an organic compound, a mixture and a composition thereof, and its use in the field of organic electroluminescence.
  • OLEDs Organic light-emitting diodes
  • OLEDs are regarded as the most promising next-generation display technology by the industry because of their light weight, active illumination, wide viewing angle, high contrast ratio, high luminous efficiency, low energy consumption, easy preparation of flexible and large-sized panels. .
  • OLEDs Organic light-emitting diodes
  • the host material is the key.
  • OLED light-emitting devices are generally prepared by using a single-host material in combination with an illuminant, but a single-host material causes a different carrier transport rate, causing device efficiency to be rolled off at high brightness, resulting in shortened device life.
  • the use of a double-body material can alleviate some of the problems caused by a single body, especially through a suitable material combination, the selected dual-body material can effectively form a composite exciplex, greatly improving the luminous efficiency and lifetime of the device.
  • One technique achieves low-roll-off, high-efficiency OLEDs by utilizing a co-host capable of forming a composite exciplex and a metal complex as a phosphorescent emitter.
  • the vapor deposition process can be greatly simplified, and the device life can be remarkably improved.
  • the organic electroluminescent element exhibits good efficiency and longevity, is easy to repeat in the manufacture and operation of the device, and the material synthesis is simple.
  • An embodiment of the invention provides an organic compound of the formula (I):
  • L 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • S is 0 or 1.
  • A is a structure represented by the general formula (II), and B is a structure represented by the general formula (III):
  • X 1 is selected from the group consisting of O, S, CR 105 R 106 and SiR 108 R 109 .
  • X 2 is selected from the group consisting of NR 110 , CR 111 R 112 , and SiR 113 R 114 .
  • n is an integer from 0 to 5.
  • p is an integer from 0-8.
  • t is an integer from 0-8.
  • the present invention also provides a high polymer comprising a repeating unit comprising a structure as shown in the formula (1).
  • the present invention also provides an organic mixture comprising an organic compound as described above, and at least another organic functional material, the other organic functional material being selectable from a hole (also called a hole) injection or Transmission material, hole blocking material, electron injecting or transporting material, electron blocking material, organic matrix material, singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent illuminant), thermally excited delayed fluorescent material (TADF) Materials) and organic dyes.
  • a hole also called a hole
  • hole also called a hole
  • hole also called a hole injection or Transmission material
  • hole blocking material electron injecting or transporting material
  • electron blocking material electron blocking material
  • organic matrix material organic matrix material
  • singlet illuminant fluorescent illuminant
  • triplet illuminant phosphorescent illuminant
  • thermally excited delayed fluorescent material (TADF) Materials thermally excited delayed fluorescent material
  • the organic mixture as described above contains at least one organic compound as described above as the first organic compound (H1) and one second organic compound (H2) having electron transporting properties.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.
  • the present invention also provides a composition comprising an organic compound or polymer as described above, or an organic mixture as described above, and at least one organic solvent.
  • the present invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • the organic electronic device may be selected from an organic light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and Organic plasmon emitting diode.
  • the organic electronic device as described above is an organic electroluminescent device comprising a light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • An organic compound according to the present invention has excellent hole transport properties and stability, and forms a co-host with another body having electron transport properties or bipolar properties, thereby obtaining improved electroluminescence efficiency and device. life.
  • FIG. 1 is a structural view of a light emitting device according to an embodiment of the present invention, in which 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL) or a hole transport layer (HTL), and 104 is a light emitting layer, 105 It is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • ETL electron transport layer
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • the present invention provides an organic compound of the formula (I):
  • L 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aryloxy group having 5 to 30 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy group having 5 to 20 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, and is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aryloxy group having 5 to 15 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 10 ring atoms, or an aryloxy group having 5 to 10 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is benzene, naphthalene, phenanthrene, triphenylene, diphenyl, terphenyl, or one or more carbon atoms of these structures are replaced by an N atom.
  • L 1 is diphenyl. In a preferred embodiment, L 1 is naphthalene. In a preferred embodiment, L 1 is benzene.
  • the aromatic ring system of the present invention is included in the ring system More carbon atoms, better Carbon atoms, heteroaromatic ring systems are included in the ring system More carbon atoms, better One carbon atom, and at least one hetero atom, provided that the total number of carbon atoms and heteroatoms is at least 4.
  • the heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S, more particularly preferably from N, O or S.
  • the above aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroaromatic ring or heteroaromatic group described above refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, snail, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole , thiazole, tetrazole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole , benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone,
  • S is 0 or 1.
  • S is zero.
  • A is a structure represented by the general formula (II), and B is a structure represented by the general formula (III):
  • X 1 is selected from the group consisting of O, S, CR 105 R 106 , SiR 108 R 109 ; preferably, X 1 is selected from O or S.
  • X 2 is selected from NR 110 , CR 111 R 112 , SiR 113 R 114 ; preferably, X 2 is selected from NR 110 or CR 111 R 112 ; more preferably, X 2 is selected from NR 110 .
  • At least one set of adjacent R 104 of formula (III) can be bonded to the ring.
  • R 101 -R 114 are D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or from 3 to 10 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 10 C atoms, or 2 to 10
  • n is an integer of 0-8, preferably an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • n is an integer of 0-5, preferably an integer of 0-4, more preferably an integer of 0-2.
  • p is an integer of 0-8, preferably an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • t is an integer from 0-8. Preferably, it is an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • the organic compound according to the invention is selected from the group consisting of:
  • X1 is selected from the group consisting of O, S, and CR 105 R 106 . It is preferably O or S.
  • Ar 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aromatic oxygen having 5 to 30 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aromatic oxygen having 5 to 20 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aromatic oxygen having 5 to 15 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is benzene, naphthalene, phenanthrene, triphenylene, diphenyl, terphenyl, or one or more carbon atoms of these structures are replaced by an N atom.
  • Ar 1 is diphenyl. In a preferred embodiment, Ar 1 is benzene. In other preferred embodiments, Ar 1 is dibenzofuran. In other preferred embodiments, Ar 1 is dibenzothiophene. In other preferred embodiments, Ar 1 is ⁇ . In other preferred embodiments, Ar 1 is a thread.
  • the L 1 or Ar 1 are each independently selected from one or more of the following structural groups:
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 respectively represent CR 501 or N;
  • R 501 -R 505 is H, or D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or from 3 to 10 C atoms
  • a branched or cyclic alkyl, alkoxy or thioalkoxy group is either a silyl group, or a substituted keto group having from 1 to 10 C atoms, or from 2 to 10
  • the above L 1 or Ar 1 is selected from one or more combinations comprising structural groups wherein the H on the ring can be optionally substituted:
  • a described in the general formula (I) is selected from the structures shown below:
  • the broken line is a single bond in which the structure shown is connected to L 1 .
  • the B described in the formula (I) is selected from the structures shown below:
  • the broken line is a single bond in which the structure shown is connected to L 1 .
  • the compound according to the invention is at least partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, very preferably 30% H It is best to be replaced by 40% of H.
  • the present invention also relates to a method for synthesizing the organic compound, wherein the reaction is carried out using a raw material containing a reactive group.
  • active materials comprise at least one leaving group, for example, bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature.
  • Particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
  • the organic compound according to any one of the embodiments of the present invention has excellent hole transport properties and stability, and forms a co-host with another body having electron transport properties or bipolar properties, thereby obtaining improved electroluminescence. Efficiency and device lifetime.
  • the invention still further relates to a high polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (I).
  • the method for synthesizing the high polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.
  • the polymer according to the invention has a glass transition temperature (Tg) ⁇ 100 ° C, preferably ⁇ 120 ° C, more preferably ⁇ 140 ° C, more preferably ⁇ 160 ° C, optimal. It is ⁇ 180 °C.
  • the polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably 1 ⁇ 2 is most preferably 1 to 1.5.
  • PDI molecular weight distribution
  • the weight average molecular weight (Mw) of the high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 40. More preferably, it is 150,000 to 300,000, and most preferably 200,000 to 250,000.
  • the invention also provides an organic mixture comprising an organic compound or polymer as described above, and at least another organic functional material, the other organic functional material being selectable in a cavity (also called electricity) Hole) injection or transport material, hole blocking material, electron injecting or transporting material, electron blocking material, organic matrix material, singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent illuminant), thermal excitation delay Fluorescent materials (TADF materials) and organic dyes.
  • Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the organic mixture comprises at least one organic compound or polymer and electron transport material (ETM) according to the invention.
  • ETM electron transport material
  • the organic mixture comprises at least one organic compound or polymer according to the invention and a luminescent material selected from the group consisting of singlet illuminants (fluorescent luminescence) Body), a triplet emitter (phosphorescent emitter) or a TADF emitter.
  • a luminescent material selected from the group consisting of singlet illuminants (fluorescent luminescence) Body), a triplet emitter (phosphorescent emitter) or a TADF emitter.
  • the organic mixture comprises at least one organic compound or polymer according to the present invention and a fluorescent illuminant, wherein the fluorescent illuminant has a weight percentage of ⁇ 10% by weight, preferably It is ⁇ 9 wt%, more preferably ⁇ 8 wt%, particularly preferably ⁇ 7 wt%, and most preferably ⁇ 5 wt%.
  • the organic mixture comprises at least one organic compound or polymer according to the invention and a phosphorescent emitter, wherein the phosphorescent emitter has a weight percentage of ⁇ 25 wt%, Preferably, it is ⁇ 20 wt%, more preferably ⁇ 15 wt%.
  • the organic mixture comprises at least one organic compound or polymer according to the invention, a phosphorescent emitter and a host material.
  • the organic compound according to the invention is co-hosted with said host material in a weight ratio of from 1:9 to 9:1; in a preferred embodiment, according to the invention
  • the organic compound forms an exciplex with the host material and has an energy level higher than that of the phosphorescent emitter.
  • the mixture comprises one less organic compound or polymer according to the invention, and a TADF material.
  • the function of the TADF material is preferably 1) forming a phosphorescent co-host material with the organic compound according to the invention, wherein the weight ratio is from 1:9 to 9:1; 2) the illuminant, wherein the weight percentage of the TADF material It is ⁇ 15 wt%, preferably ⁇ 10 wt%, more preferably ⁇ 8 wt%.
  • the organic mixture as described above comprises at least one organic compound as described above as the first organic compound (H1) and a second organic compound (H2), said at least The diorganic compound (H2) has an electron transporting property.
  • the at least second organic compound has electron transport properties and also has hole transport properties.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 3:7 to 7:3.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 4:6 to 6:4.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 5:5.
  • the second organic compound (H2) comprises a fluorine group, or a cyano group or has any one of the following formulas:
  • a is an integer of 1-3;
  • X 1 -X 8 is selected from CR 801 or N, and at least one is N;
  • Z 1 -Z 3 is a single bond or C(R 801 ) 2 or O or S.
  • R 801 may be selected from the group consisting of hydrogen, hydrazine, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
  • the second organic compound (H2) has a structure represented by the formula (IV).
  • Z 4 , Z 5 , Z 6 are selected from N or CR 901 , and at least one of Z 4 , Z 5 , and Z 6 is an N atom.
  • Ar 13 to Ar 15 are the same or different, and are an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, wherein the one or more groups may be further substituted with R 902, or R 902 form a ring system may be further substituted with the group.
  • each of Ar 13 to Ar 15 may be independently selected from the above groups.
  • Ar 13 to Ar 15 are the same or different, and are substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or Deuterated or undeuterated aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be bonded to each other and/or to the group
  • the combined ring forms a monocyclic or polycyclic aliphatic or aromatic ring system.
  • Ar 13 to Ar 15 are the same or different, and are substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 15 ring atoms, or Is a deuterated or undeuterated aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these systems, wherein one or more groups may be and/or with the group
  • the bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system.
  • b, u, v are independently 1 or 2 or 3, preferably 1.
  • Ar 13 -Ar 15 in the formula (IV), when multiple occurrences, may be the same or differently selected from one of the following structural groups or Their combination:
  • d is 1 or 2 or 3 or 4.
  • Suitable examples of the second organic compound (H2) are listed below, but are not limited to:
  • the organic mixture is used in a luminescent layer in an organic electroluminescent device. Due to stability or process considerations, there are sometimes some special requirements for H1 and H2.
  • the organic mixture according to the invention wherein at least one of H1 and H2, preferably H2, ((LUMO+1)-LUMO) ⁇ 0.1 eV, preferably ⁇ 0.15 eV, More preferably, it is ⁇ 0.20 eV, more preferably ⁇ 0.25 eV, and most preferably ⁇ 0.30 eV.
  • the organic mixture according to the invention wherein at least one of H1 and H2, preferably H1, (HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV More preferably, it is ⁇ 0.30 eV, more preferably ⁇ 0.35 eV, and most preferably ⁇ 0.40 eV.
  • the organic mixture wherein the molar ratio of H1 to H2 is from 2:8 to 8:2; the preferred molar ratio is from 3:7 to 7:3; a more preferred molar ratio is 4:6 to 6:4, the best is 5:5.
  • the organic mixture of H1 and H2 which has at least a glass transition temperature T g ⁇ 100 °C, in a preferred embodiment, at least one of its T g ⁇ 120 °C in a more preferred embodiment, which has a T g ⁇ 140 °C at least, in a more preferred embodiment, at least one of its T g ⁇ 160 °C, in a most preferred embodiment, at least There is a T g ⁇ 180 ° C.
  • the sublimation temperature of the first organic compound (H1) and the second organic compound (H2) does not differ by more than 30K.
  • the organic mixture, the first organic compound (H1) and the second organic compound (H2) have a sublimation temperature difference of not more than 20K.
  • the organic mixture, the first organic compound (H1) and the second organic compound (H2) have a sublimation temperature difference of not more than 10K.
  • the first organic compound (H1) and the second organic compound (H2) have the same sublimation temperature.
  • the first organic compound (H1) and the second organic compound (H2) have a molecular weight difference of not more than 100 g/mol, preferably not more than 90 g/mol, in accordance with the organic mixture of the present invention. It is preferably not more than 80 g/mol, preferably not more than 60 g/mol.
  • the present invention also provides another organic mixture comprising a first organic compound (H1) and a second organic compound (H2) as described above, and at least another organic functional material, said another organic function Materials can be selected for hole (also known as hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix Host, singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and organic dye; preferably selected from phosphorescent emitters and TADF materials.
  • hole also known as hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix Host singlet emitter
  • phosphorescent emitter triplet emitter
  • TADF material thermally excited delayed fluorescent material
  • organic dye preferably selected from phosphorescent emitters and TADF materials.
  • organic functional materials are described
  • ETM ETM
  • fluorescent or singlet emitters phosphorescent or triplet emitters
  • TADF materials are described in more detail below (but are not limited thereto).
  • ETM material examples are not particularly limited, and any metal complex or organic compound may be used as the ETM as long as they can transport electrons.
  • the preferred organic ETM material may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, anthracene, diterpene, spirobifluorene, p-phenylacetylene, pyridazine, pyrazine.
  • the compound useful as an ETM is a molecule comprising at least one of the following groups
  • R 1 may be selected from the group consisting of hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl,
  • the aryl group and the heteroaryl group when R 1 is selected from an aryl group or a heteroaryl group, R 1 has the same meaning as Ar 1 , and Ar 1 to Ar 5 have the same meanings as described above.
  • N2 is an integer from 0 to 20;
  • X 1 -X 8 is selected from CR 1 or N.
  • examples of metal complexes that can be used as ETM include, but are not limited to, the following general structures.
  • (ON) or (NN) is a bidentate ligand in which the metal is coordinated to O, N or N, N;
  • L is an ancillary ligand;
  • r1 is an integer from 1 to the maximum of the metal Number of digits.
  • L 3-r1 r1 is 1 or 2 or 3; when r1 is 3, the subscript 3-r1 of L is 0, indicating that L is absent.
  • L 2-r1 r1 is 1 or 2; when r1 is 2, the subscript 2-r1 of L is 0, indicating that L is absent.
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy level is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:
  • M3 is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • r2 is a An integer whose value ranges from 1 to the maximum coordination number of this metal
  • the metal complex that can be used as the triplet host has the following form:
  • (ON) is a bidentate ligand in which the metal is coordinated to the O and N atoms, and r2 is an integer having a value from 1 to the maximum coordination number of the metal; in one embodiment, M3 is optional. Ir and Pt.
  • Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazin
  • each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 2 -R 7 have the same meaning as R 1
  • X 9 is selected from CR 1 R 2 or NR 1
  • Y is selected from CR 1 R 2 or NR 1 or O or S.
  • R 1 , n 2 , X 1 - X 8 and Ar 1 to Ar 3 have the same meanings as described above.
  • triplet host materials examples include:
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindoles and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847, and disclosed in US Pat. No. 7,233,019, KR2006-0006760 A quinone triarylamine derivative.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • Further preferred singlet emitters are selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.
  • More preferred singlet emitters may be selected from the derivatives of hydrazine, such as those disclosed in US2013175509A1; triarylamine derivatives of hydrazine, such as triarylamine derivatives of hydrazine containing dibenzofuran units disclosed in CN102232068B; A triarylamine derivative of hydrazine having a specific structure, as disclosed in CN105085334A, CN105037173A.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondarily ⁇ Est ⁇ 0.25 eV, more preferably ⁇ Est ⁇ 0.20 eV, and most preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;
  • Ar 1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar 2 may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • the organic compound according to the invention has a molecular weight of ⁇ 1100 g/mol, preferably ⁇ 1000 g/mol, very preferably ⁇ 950 g/mol, more preferably ⁇ 900 g/mol, most preferably ⁇ 800 g/mol.
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the organic compound according to the invention has a molecular weight of ⁇ 700 g/mol, preferably ⁇ 800 g/mol, very preferably ⁇ 900 g/mol, more preferably ⁇ 1000 g/mol, most preferably ⁇ 1100 g/mol.
  • the organic compound according to the invention has a solubility in toluene of > 2 mg/ml, preferably > 3 mg/ml, more preferably > 4 mg/ml, most preferably > 5 mg/ml at 25 °C.
  • Another object of the invention is a solution for providing materials for printing OLEDs.
  • the present invention also provides a composition comprising an organic compound or polymer as described above, or an organic mixture as described above, and at least one organic solvent.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the embodiment of the present invention may include 0.01% by weight to 20% by weight of the organic compound, preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, most preferably 0.25% by weight. Up to 5 wt% of organic compound.
  • a composition according to the invention wherein said solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, fat a cyclic or olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • said solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, fat a cyclic or olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • a composition according to the invention comprises at least 50% by weight of an aromatic or heteroaromatic solvent; preferably at least 80% by weight of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight Aromatic or heteroaromatic solvents.
  • aromatic or heteroaromatic solvents are, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropyl Benzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, Diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene , 1-methylnaphthalene, 1,2,4-trichlorobenzene,
  • suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.
  • the alcohol represents a suitable class of solvent.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.
  • the solvent may be a cycloalkane such as decalin.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • the composition according to the present invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, and examples of another organic solvent include (but not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, methylene Toluene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, hydra
  • the solvent particularly suitable for the present invention is a solvent having Hansen solubility parameters in the following ranges:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 1/2 ;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the organic solvent is selected in consideration of its boiling point parameter.
  • the organic solvent has a boiling point of ⁇ 150 ° C; preferably ⁇ 180 ° C; more preferably ⁇ 200 ° C; more preferably ⁇ 250 ° C; optimally ⁇ 275 ° C or ⁇ 300 ° C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the organic solvent can be evaporated from the solvent system to form a film comprising the functional material.
  • composition in accordance with the present invention a composition in accordance with the present invention
  • the organic solvent is selected in consideration of its surface tension parameter. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method.
  • the organic solvent has a surface tension at 25 ° C of from about 19 dyne / cm to 50 dyne / cm; more preferably from 22 dyne / cm to 35 dyne / cm; Most preferably in the range of 25 dyne/cm to 33 dyne/cm.
  • the ink according to the invention has a surface tension at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; preferably in 25 dyne/ Cm to the 33dyne/cm range.
  • compositions according to the invention wherein the organic solvent is selected taking into account the viscosity parameters of the ink.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable organic solvent and concentration of functional materials in the ink.
  • the organic solvent has a viscosity of less than 100 cps; more preferably less than 50 cps; most preferably from 1.5 to 20 cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C.
  • Compositions so formulated will be particularly suitable for ink jet printing.
  • the composition according to the invention has a viscosity at 25 ° C in the range of from about 1 cps to about 100 cps; more preferably in the range of from 1 cps to 50 cps; more preferably in the range of from 1.5 cps to 20 cps.
  • the ink obtained by the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
  • the present invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • the organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor. , organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • organic lasers organic spintronic devices
  • organic sensors and organic plasmon emitting diodes Organic Plasmon Emitting Diode.
  • the organic electronic device as described above is an organic electroluminescent device comprising at least one light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • Another object of the present invention is to provide a method of producing the above electronic device.
  • the above compound or mixture is formed into a functional layer on a substrate by evaporation, or a functional layer is formed on a substrate together with at least one other organic functional material by a co-evaporation method, Or coating the above composition on a substrate by printing or coating to form a functional layer, wherein the printing or coating method may be selected from, but not limited to, inkjet printing, Nozzle Printing, Typography, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit type extrusion Coating, etc.
  • the invention further relates to the use of the composition as a printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the functional layer is formed to have a thickness of 5 nm to 1000 nm.
  • the invention further relates to an organic electronic device comprising at least one organic compound or polymer according to the invention, or at least a functional layer prepared using the composition according to the invention.
  • an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above.
  • the organic electronic device described above is an electroluminescent device, particularly an OLED (shown in Figure 1), comprising a substrate (101), an anode (102), at least A light emitting layer (104), a cathode (106).
  • OLED shown in Figure 1
  • the substrate (101) may be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-
  • the anode (102) may comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode (106) can comprise a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further comprise other functional layers such as a hole injection layer (HIL) or a hole transport layer (HTL) (103), an electron blocking layer (EBL), an electron injection layer (EIL) or an electron transport layer (ETL) (105). ), a hole blocking layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light-emitting layer (104) is vacuum-deposited, the evaporation source of which comprises a compound or mixture according to the invention.
  • the light-emitting layer (104) is prepared by printing the composition according to the present invention.
  • the electroluminescent device according to the invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the invention further relates to the use of an organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • the invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.
  • reaction solution was neutralized to a pH of about 9 with a 5% Na solution, and then extracted with dichloromethane and water and then aqueous three portions. The organic phase was combined, washed with brine, dried and concentrated. /PE (1:10) was purified by column to give white solid compound 4.1 (12.0 g , yield 40%).
  • Example 1 Example 15, Comparative Example 1: Preparation and Characterization of OLED Devices:
  • OLED device structure and materials used in each layer are OLED device structure and materials used in each layer:
  • HIL MoO 3
  • HTL a triarylamine derivative; specifically NPD
  • Host Compound 1-15, Comparative Compound 1 as the first host; Compound A-Compound C as the second host; molar ratio of 1:1; Dopant: Ir(ppy) 3 .
  • the energy level of the organic compound material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 09W Gaussian Inc.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 and the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO levels are calculated according to the following calibration formula, and S1, T1 and the resonance factor f(S1) are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO (G) and LUMO (G) are direct calculation results of Gaussian 09W, the unit is Hartree. The results are shown in the following table:
  • Example First subject Second subject Example 1 Compound 1 Compound A
  • Example 2 Compound 2 Compound A
  • Example 3 Compound 3 Compound B
  • Example 4 Compound 4 Compound B Example 5 Compound 5 Compound B Example 6 Compound 6 Compound B Example 7 Compound 7 Compound C Example 8 Compound 8 Compound C Example 9 Compound 9 Compound C Example 10 Compound 10 Compound C Example 11 Compound 11 Compound C Example 12 Compound 12 Compound C Example 13 Compound 13 Compound C Comparative Example 1 Comparative compound 1 Compound A
  • the device structure used is as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HIL 5 nm
  • HTL 50 nm
  • Host 10%
  • Dopant 40 nm
  • ETL 40 m
  • thermally evaporated in a high vacuum (1 x 10 -6 mbar, mbar).
  • cathode Liq / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • J-V current-voltage
  • Example 2 3.6 73 12080
  • Example 3 3.6 73 12000
  • Example 4 3.6 70 12120
  • Example 5 3.7 75 11080
  • Example 6 3.6 73 11000
  • Example 7 3.6 78 12110
  • Example 8 3.6 71 12050
  • Example 9 3.6 71 11990
  • Example 10 3.6 75 12090
  • Example 13 3.6 73 12110 Comparative Example 1 3.9 59 6180

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un composé organique et une application de celui-ci dans un dispositif électronique organique, en particulier dans des diodes électroluminescentes organiques. L'invention concerne également un dispositif électronique organique comprenant ledit composé organique selon la présente invention, en particulier une diode électroluminescente organique, et son application dans des technologies d'affichage et d'éclairage. La présente invention concerne en outre un dispositif électronique organique préparé à l'aide d'une composition selon la présente invention et un procédé de préparation. La présente invention permet d'améliorer la performance du dispositif par l'optimisation de la structure de ce dernier, en particulier pour des dispositifs OLED à haute performance, ce qui permet de fournir de meilleures options pour des matériaux et des techniques de préparation pour des applications d'affichage polychrome et d'éclairage.
PCT/CN2018/122488 2017-12-27 2018-12-20 Composé organique, haut polymère, mélange organique, composition et application associée dans un dispositif électronique organique Ceased WO2019128849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201880069730.3A CN111278813B (zh) 2017-12-27 2018-12-20 有机化合物、高聚物、有机混合物、组合物及有机电子器件

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711451356 2017-12-27
CN201711451356.7 2017-12-27

Publications (1)

Publication Number Publication Date
WO2019128849A1 true WO2019128849A1 (fr) 2019-07-04

Family

ID=67063131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/122488 Ceased WO2019128849A1 (fr) 2017-12-27 2018-12-20 Composé organique, haut polymère, mélange organique, composition et application associée dans un dispositif électronique organique

Country Status (2)

Country Link
CN (1) CN111278813B (fr)
WO (1) WO2019128849A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116891477A (zh) * 2023-07-13 2023-10-17 长春海谱润斯科技股份有限公司 一种吲哚并咔唑化合物及其有机电致发光器件
US20240090323A1 (en) * 2019-11-21 2024-03-14 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082238A (ja) * 2009-10-05 2011-04-21 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
CN105579551A (zh) * 2013-10-02 2016-05-11 罗门哈斯电子材料韩国有限公司 有机电致发光化合物和包含所述化合物的有机电致发光装置
CN106537634A (zh) * 2014-07-22 2017-03-22 罗门哈斯电子材料韩国有限公司 有机电致发光装置
CN107305925A (zh) * 2016-04-21 2017-10-31 三星Sdi株式会社 用于有机光电器件的组合物和包含其的有机光电器件和显示器器件

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6774432B2 (ja) * 2016-01-20 2020-10-21 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子、表示装置及び照明装置
CN108976212A (zh) * 2017-06-02 2018-12-11 北京鼎材科技有限公司 芴衍生物及其在有机发光材料中的应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082238A (ja) * 2009-10-05 2011-04-21 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
CN105579551A (zh) * 2013-10-02 2016-05-11 罗门哈斯电子材料韩国有限公司 有机电致发光化合物和包含所述化合物的有机电致发光装置
CN106537634A (zh) * 2014-07-22 2017-03-22 罗门哈斯电子材料韩国有限公司 有机电致发光装置
CN107305925A (zh) * 2016-04-21 2017-10-31 三星Sdi株式会社 用于有机光电器件的组合物和包含其的有机光电器件和显示器器件

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAO, XIAO ET AL.: "Palladium-Catalyzed Direct Arylation of C-H Bond to Construct Quaternary Carbon Centers: The Synthesis of Diarylfluorene", ORGANIC LETTERS, vol. 15, no. 12, 21 June 2013 (2013-06-21), pages 3102 - 3105, XP055622474, ISSN: 1523-7052 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240090323A1 (en) * 2019-11-21 2024-03-14 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
US12441699B2 (en) * 2019-11-21 2025-10-14 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
CN116891477A (zh) * 2023-07-13 2023-10-17 长春海谱润斯科技股份有限公司 一种吲哚并咔唑化合物及其有机电致发光器件

Also Published As

Publication number Publication date
CN111278813B (zh) 2023-05-12
CN111278813A (zh) 2020-06-12

Similar Documents

Publication Publication Date Title
CN111278838B (zh) 含硼杂环化合物、高聚物、混合物、组合物及其用途
CN108137618B (zh) D-a型化合物及其应用
WO2019105327A1 (fr) Film composite organique et application associée dans un dispositif électronique organique
WO2017092495A1 (fr) Matériaux à fluorescence retardée par excitation thermique, polymère, mélange, composition, et dispositif électronique organique
CN109638171B (zh) 有机混合物、高聚物、组合物及其用途
CN108137634B (zh) 一种金属有机配合物及其在电子器件中的应用
WO2018095390A1 (fr) Composé organique, ses applications, mélange organique et dispositif électronique organique
CN116685580B (zh) 有机混合物及其在有机电子器件的应用
CN109790087B (zh) 氘代稠环化合物、高聚物、混合物、组合物以及有机电子器件
WO2019114668A1 (fr) Matériau d'un complexe de métaux de transition et son application dans des dispositifs électroniques
CN109705100B (zh) 含萘咔唑类有机光化合物、混合物、组合物及其用途
WO2017118137A1 (fr) Dérivé de carbazole et polymère élevé, mélange, composition et dispositif électronique organique le comprenant et utilisation correspondante
WO2019120177A1 (fr) Composé permettant de fabriquer un dispositif d'affichage organique, dispositif d'affichage organique et son application
WO2019128875A1 (fr) Dérivé d'amine aromatique et dispositif électronique organique
WO2018095386A1 (fr) Composé cyclique fusionné, haut polymère, mélange, composition et composant électronique organique
WO2018095385A1 (fr) Composé cyclique fusionné, haut polymère, mélange, composition et composant électronique organique
WO2017118252A1 (fr) Composé hétérocyclique condensé contenant une fonction sulfone et application correspondante
WO2019128599A1 (fr) Composé hétérocyclique contenant de l'azote, haut polymère, mélange, composition et utilisation associée
CN109659448B (zh) 有机混合物、组合物及有机电子器件
CN114763475B (zh) 一种有机混合物及其在有机电子器件的应用
CN109705018B (zh) 有机化合物、有机混合物、组合物及有机电子器件
CN114751892A (zh) 一种有机混合物及其在有机电子器件的应用
WO2019128849A1 (fr) Composé organique, haut polymère, mélange organique, composition et application associée dans un dispositif électronique organique
WO2018099432A1 (fr) Composé cyclique fusionné, son procédé de préparation et son application
WO2018099433A1 (fr) Composé cyclique fusionné et son utilisation, mélange et dispositif électronique organique associés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18893758

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18893758

Country of ref document: EP

Kind code of ref document: A1