[go: up one dir, main page]

WO2018095395A1 - 高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体 - Google Patents

高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体 Download PDF

Info

Publication number
WO2018095395A1
WO2018095395A1 PCT/CN2017/112716 CN2017112716W WO2018095395A1 WO 2018095395 A1 WO2018095395 A1 WO 2018095395A1 CN 2017112716 W CN2017112716 W CN 2017112716W WO 2018095395 A1 WO2018095395 A1 WO 2018095395A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
homo
organic
high polymer
electron
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/CN2017/112716
Other languages
English (en)
French (fr)
Inventor
潘君友
黄宏
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 EP17874343.1A priority Critical patent/EP3547384B1/en
Priority to US16/463,273 priority patent/US11453745B2/en
Priority to CN201780059565.9A priority patent/CN109791992B/zh
Publication of WO2018095395A1 publication Critical patent/WO2018095395A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/149—Side-chains having heteroaromatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/417—Organometallic coupling reactions magnesium-based, e.g. Grignard or McCullough reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/722—Sulfonation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/95—Use in organic luminescent diodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • 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
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to the field of electroluminescent materials, and in particular to a high polymer, a mixture comprising the same, a composition and an organic electronic device, and a polymerizable monomer.
  • organic light-emitting diodes Due to the synthetic diversity of organic semiconductor materials, the possibility of implementing large-area flexible devices, low manufacturing costs and excellent optical and electrical properties, organic light-emitting diodes (OLEDs) are realized in novel optoelectronic devices, for example, Flat panel displays and lighting applications have great potential.
  • OLEDs organic light-emitting diodes
  • various systems based on fluorescent and phosphorescent materials have been developed.
  • Organic light-emitting diodes using phosphorescent materials have achieved relatively high performance, such as nearly 100% internal luminescence quantum efficiency.
  • the phosphorescent host material with practical use value is a bipolar transport compound or a co-host compound. The material composition is complicated, and it is applied to the device to cause hole and electron transport imbalance.
  • Kim proposed the concept of exciplex as a phosphorescent host material, so that two different organic compounds can be used to form an intermediate state, an exciplex, to achieve a long lifetime of phosphorescent OLED devices. This can be achieved by excimer complex host materials, see Kim et al., Adv. Mater., Vol 26, 5864, (2014).
  • the existing organic materials capable of forming an exciplex are small molecular materials, and have a relatively low molecular weight, which is not suitable for a printing process.
  • a high polymer comprising a repeating unit represented by the formula (1), wherein n and m are integers greater than or equal to 1, min((LUMO(E1)-HOMO(E2), LUMO(E2)-HOMO( E1)) ⁇ min (E T (E1), E T (E2)) + 0.1 eV, wherein LUMO (E1), HOMO (E1) and E T (E1) are the highest occupied orbital energy levels of the E1 group, respectively.
  • the lowest unoccupied orbital level and triplet level, LUMO(E2), HOMO(E2) and E T (E2) are the highest occupied orbital energy levels of the E2 group, the lowest unoccupied orbital level and the triplet level. .
  • the ratio of n:m in the high polymer is from 3:7 to 7:3. .
  • the E1 group contains an electron donating group D, and/or the E2 group contains an electron withdrawing group.
  • the E1 group and/or the E2 group (HOMO-(HOMO-1) ⁇ 0.3 eV.
  • the E1 group and the E2 group have the following general formula (I) or Structural unit shown in (II):
  • Ar is an aromatic or heteroaromatic structural unit, and the electron-donating group D may be the same or different when it occurs multiple times, and the electron-withdrawing group A may be the same or different when it occurs multiple times, and p and r are 1 to An integer between 6 and q, s is 0 or 1;
  • n is an integer greater than or equal to 1:
  • the E1 group (HOMO-(HOMO-1) ⁇ 0.3 eV.
  • a polymerizable monomer comprising the above E1 group or the above E2 group, and combinations thereof.
  • a composition comprising any of the polymers described above, and at least one organic solvent.
  • An organic electronic device comprising at least any of the high polymers described above.
  • the polymer of the formula (1) is easy to form an exciplex, and when used for a phosphorescent host, the efficiency of the device can be improved, and at the same time, due to better solubility in an organic solvent, Good film properties provide a better material solution for printing OLEDs.
  • the high polymer according to the general formula (4) has high stability and is easy to be processed by a solution.
  • a high polymer comprising a repeating unit represented by the formula (1), n and m are integers greater than or equal to 1, min((LUMO(E1)-HOMO(E2), LUMO(E2)-HOMO( E1)) ⁇ min (E T (E1), E T (E2)) + 0.1 eV, wherein LUMO (E1), HOMO (E1) and E T (E1) are the highest occupied orbital energy levels of the E1 group, respectively. The lowest unoccupied orbital energy level and triplet energy level, LUMO (E2), HOMO (E2) and E T (E2) are the highest occupied orbital energy level, the lowest unoccupied orbital energy level and the triplet energy level of the E2 group, respectively. .
  • the energy level structure of the organic material plays a key role.
  • the following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet energy level E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.
  • the absolute values of HOMO, LUMO, E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • the high polymer according to the present application has the advantage that the E1 group and the E2 group are linked as a side chain structure through a non-conjugated polymer backbone to achieve a higher molecular weight while maintaining a single repeat unit energy structure, That is, the HOMO, LUMO, and E T of a single repeat unit remain substantially unchanged relative to the E1 group or the E2 group, while forming an exciplex in the polymer.
  • (HOMO-1) is defined as the second highest occupied orbital level
  • (HOMO-2) is the third highest occupied orbital level
  • (LUMO+1) is defined as the second lowest unoccupied orbital level
  • (LUMO+2) is the third lowest occupied orbital level, and so on.
  • the repeating unit in which the E1 group is located is defined as the repeating unit E1
  • the repeating unit in which the E2 group is located is defined as the repeating unit E2.
  • the ratio n:m between the number of repeating units E1 and repeating units E2 in the high polymer is from 3:7 to 7:3.
  • the ratio n:m between the number of repeating units E1 and repeating units E2 in the polymer is from 4:6 to 7:3, more preferably from 4:6 to 6:4, More preferably, it is from 5:5 to 6:4, preferably 5:5.
  • an additional group R is generally attached to the main chain of the polymer to increase the solubility of the polymer while increasing the molecular weight of the polymer to have Better luminescence performance and device performance.
  • a repeating unit as shown in the formula (2) is included.
  • R is selected from the group consisting of a linear alkane having 1 to 15 carbon atoms, a branched alkane, and a cycloalkane, an aromatic, heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms; o is greater than or equal to An integer of 0.
  • R has a structural unit corresponding to an organic functional material
  • the organic functional material may be selected from the group consisting of HTM, ETM, a fluorescent luminescent material, a phosphorescent luminescent material, and a host material.
  • R has a structural unit corresponding to a fluorescent luminescent material or a phosphorescent luminescent material.
  • an exciplex can be formed between the repeating unit E1 and the repeating unit E2, and can be used as a host material or an illuminant in the light-emitting layer.
  • the excimer complex formed by the repeating unit E1 and the repeating unit E2 has a specific gravity in the high polymer of from 70% to 99.9%;
  • the content of the repeating unit E1 or the repeating unit E2 in the high polymer is from 30 mol% to 50 mol%, preferably from 35 mol% to 50 mol%, more preferably from 40 mol% to 50 mol%, More preferably, it is from 40 mol% to 48 mol%, preferably from 41 mol% to 46 mol%.
  • the R group in formula (2) further comprises an emitter unit.
  • the content of repeating unit R in the high polymer is from 0.1 mol% to 30 mol%.
  • a repeating unit in which an R group is located is defined as a repeating unit R.
  • the content of the repeating unit R containing the illuminant in the high polymer is from 1 mol% to 52 mol%, preferably from 2 mol% to 20 mol%, more preferably from 3 mol% to 81 mol%. More preferably, it is from 4 mol% to 61 mol%, preferably from 5 mol% to 15 mol%.
  • the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable; the singlet state, the singlet state have the same meaning, and can be interchanged; the triplet state, the triplet state has the same meaning, Can be interchanged.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer, and blend. In particular, there are no repeating unit structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 3000 g/mol, preferably ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol.
  • the high polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Also in the present application, the high polymer also includes a dendrimer.
  • a dendrimer For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].
  • the main chain backbone of conjugated polymer is mainly composed of sp2 hybrid orbitals of C atoms.
  • Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene), and the C atom in the main chain can also It is replaced by other non-C atoms, and when the sp2 hybridization in the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer.
  • the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the high polymer according to the present application may also be a non-conjugated high polymer.
  • At least one of the E1 group and the E2 group ((HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, more preferably ⁇ 0.35 eV, very preferably ⁇ 0.4 eV, preferably ⁇ 0.45 eV, wherein ⁇ ((HOMO-(HOMO-1))) is the E1 group and/or the E2 group Larger, which is conducive to the stability of hole transport.
  • the E1 group contains one or more of the structural units represented by the following formulae (2)-(9):
  • L 1 represents a single bond, an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms, and the linking position of L 1 may be any carbon atom on the benzene ring;
  • Ar, Ar 1 and Ar 2 each independently represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;
  • a 1 and A 2 each independently represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;
  • L 2 and L 3 each independently represent an aromatic group of 6 to 30 or an aromatic hetero group having 3 to 30 carbon atoms;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R each independently represent H, D (fluorene atom), F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl
  • An aromatic heterocyclic group in which R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be bonded to any one of the carbon atoms on the condensed ring.
  • n an integer of 1 to 6.
  • the E1 group contains an electron-donating group D and/or an E2 group containing an electron-withdrawing group A.
  • the E1 group contains the structural unit represented by the following formula I:
  • Ar is an aromatic or heteroaromatic structural unit
  • D may be independently selected from the same or different electron-donating groups when present multiple times
  • p is an integer between 1 and 6, and q is 0 or equal to 1;
  • Suitable electron donating groups D may be selected from the group consisting of any of the following general formulae I-1, I-2 and I-3:
  • Z 1 H, O, S or Si
  • a 1 and A 2 may independently form an aromatic ring, a heteroaromatic ring, an aliphatic ring or a non-aromatic heterocyclic ring
  • R 20 represents H, an aryl group, or forms A 4
  • the atomic groups necessary for the ring shown, A 3 and A 4 may each independently form a heteroaromatic ring or a non-heteroaromatic ring
  • Z 2 , Z 3 , Z 4 , and Z 5 each independently represent O or S.
  • the electron-donating group D described above is selected from the group having at least one of the following structural formulas D1-D15:
  • the E2 group contains the structure represented by the following formula II:
  • Ar is an aromatic or heteroaromatic structural unit, and the electron-withdrawing group A may be independently selected from the same or different electron withdrawing groups when it is present multiple times, r is an integer between 1 and 6, and s is 0 or 1 .
  • a suitable electron withdrawing group A may be selected from at least one of F, a cyano group or a group having a skeleton shown below:
  • n1 is an integer from 1 to 3;
  • X 1 -X 8 is selected from CR 12 or N, and at least one is N, wherein R 12 may be selected from the group consisting of hydrogen, alkyl, alkoxy, Amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
  • Z 1 -Z 3 is a single bond or C(R 12 ) 2 or O or S.
  • a suitable electron withdrawing group A is selected from the group consisting of cyano and s is 1.
  • Ar is selected from the group consisting of:
  • n2 is 1 or 2 or 3 or 4.
  • Ar in the general formula I and the general formula II may be the same or different.
  • examples of structural units useful for E2 groups in the high polymers described herein are:
  • the plurality of E1 groups in the plurality of repeating units E1 may be the same or different, and the plurality of E2 groups in the plurality of repeating units E2 may be the same or different.
  • the high polymer according to the present application also contains another organic functional group.
  • the high polymer according to the present application has a structure represented by the following formula (3):
  • G is the other organic functional group, and n and m have the same meanings in the general formula (3) as in the general formula (1) and the general formula (2), and t is greater than or equal to An integer of 0.
  • the other organic functional group G when present in plurality, may be selected from holes (also called holes) injection or transport groups, hole blocking groups, electron injection, independently or differently from each other. Or a transport group, an electron blocking group, an organic matrix group, Singlet luminescent groups (fluorescent luminescent groups), triplet luminescent groups (phosphorescent luminescent groups), and thermally excited delayed fluorescent (TADF) luminescent groups.
  • the small molecular organic functional materials corresponding to these organic functional groups are respectively hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM).
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet illuminant phosphorescent illuminant
  • TADF illuminant TADF illuminant
  • Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole, aniline , carbazole, azide and azepine and their derivatives.
  • suitable HIMs also include fluorocarbon-containing polymers, conductive doped polymers, conductive polymers such as PEDOT/PSS; self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal oxides Such as MoOx; metal complexes and cross-linking compounds.
  • An electron blocking layer is used to block electrons from adjacent functional layers, particularly the luminescent layer.
  • the electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function.
  • HIM/HTM materials that typically have high LUMO levels can be used as EBMs.
  • cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM include, but are not limited to, the following general structures:
  • Each of Ar1 to Ar9 may be independently selected from a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalylene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; aromatic heterocyclic ring Compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole , dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine, oxadiazine, hydrazine, benzimi
  • Ar1 to Ar9 can be independently selected from the group consisting of:
  • n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M is a metal having an atomic weight greater than 40
  • (Y 1 -Y 2 ) is a two-dentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to The maximum coordination number of this metal; m+n is the maximum coordination number of this metal.
  • (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.
  • (Y 1 -Y 2 ) is a carbene ligand.
  • M is selected from the group consisting of Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
  • EIM/ETM material examples are not particularly limited, and any metal complex or organic compound may be used as the EIM/ETM as long as they can transport electrons.
  • the preferred organic EIM/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, triazine, triazole, imidazole, quinoline, isoquinoline, quinoxaline, oxazole, isoxazole, oxadiazole, thiadiazole, pyridine, pyrazole, pyrrole, pyrimidine, acridine, pyrene , hydrazine, ruthenium, fluorene, hydrazine, dibenzo-in
  • a hole blocking layer is typically used to block holes from adjacent functional layers, particularly the luminescent layer.
  • the presence of HBL typically results in an increase in luminous efficiency.
  • the hole blocking material (HBM) of the hole blocking layer (HBL) needs to have a lower HOMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant.
  • the HBM has an electronic transmission function. EIM/ETM materials that typically have deep HOMO levels can be used as HBM.
  • the compound useful as EIM/ETM/HBM is a molecule comprising at least one of the following groups:
  • R 1 may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aryl or heteroaryl , they are the same meaning Ar 1 and Ar 2 in the HTM above; same as Ar and Ar 1 -Ar 5 HTM described in a sense; n is an integer from 0 to 20; X 1 -X 8 is selected from CR1 to Or N.
  • examples of metal complexes that can be used as EIM/ETM include, but are not limited to, the following general structures:
  • (ON) or (NN) is a two-tooth ligand in which the metal is coordinated to O, N or N, N; L is an ancillary ligand; m is an integer from 1 to the maximum coordination of the metal number.
  • an organoalkali metal compound can be used as the EIM.
  • an organic alkali metal compound is understood to be a compound which has at least one alkali metal, i.e., lithium, sodium, potassium, rubidium, cesium, and further contains at least one organic ligand.
  • Suitable organic alkali metal compounds include the compounds described in US Pat. No. 7,776,317 B2, EP 1 194 562 B1 and EP 1 144 543 B1.
  • Preferred organic alkali metal compounds are compounds of the following chemical formula:
  • R 1 has the meaning as described above, the arc represents two or three atoms and a bond, so as to form a 5- or 6-membered ring with the metal M if necessary, wherein the atom may also be substituted by one or more R1, M It is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium and cesium.
  • the organic alkali metal compound may be in the form of a monomer, as described above, or in the form of an aggregate, for example, a two alkali metal ion and two ligands, 4 alkali metal ions and 4 ligands, 6 alkali metal ions and 6 ligands or in other forms.
  • Preferred organic alkali metal compounds are compounds of the following chemical formula:
  • o each time it appears can be the same or different, is 0, 1, 2, 3 or 4;
  • p each occurrence may be the same or different, is 0, 1, 2 or 3;
  • the alkali metal M is selected from the group consisting of lithium, sodium, potassium, more preferably lithium or sodium, and most preferably lithium.
  • the organic alkali metal compound is electron-injected into the layer. More preferably, the electron injecting layer is composed of an organic alkali metal compound.
  • the organoalkali metal compound is doped into other ETMs to form an electron transport layer or an electron injection layer. More preferably, it is the electron transport layer.
  • 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 is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4) is a two teeth ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • m is an integer , the value from 1 to the maximum coordination number of this metal
  • m + n is the maximum coordination number of this metal.
  • the metal complex that can be used as the triplet host has the following form:
  • (O-N) is a two-tooth ligand in which the metal coordinates with the O and N atoms.
  • M is optional for 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, triphenyl, benzo, anthracene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, three Azole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine Anthracen
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 -R 7 may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aromatic Or a heteroaryl group, which has the same meaning as Ar 1 and Ar 2 described above; n is an integer from 0 to 20; X 1 -X 8 is selected from CH or N; and X 9 is selected from CR 1 R 2 or NR. 1 .
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is an aryl group Or a heteroaryl group, which has the same meaning as Ar 1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 is selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 Or NR 1 .
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • 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 preferentially 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.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.
  • 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.
  • 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 ( ⁇ Est), preferably ⁇ Est ⁇ 0.3 eV, and secondarily ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • ⁇ Est small singlet-triplet energy level difference
  • the TADF material has a relatively small ⁇ Est
  • 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.
  • 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 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 transition metal elements or lanthanides or actinides
  • 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; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand Preferred is a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1, or 2, preferably 0 or 1, Particularly preferred is 0;
  • the organic functional group G is selected from the group consisting of triplet matrix groups.
  • the organic functional group G is selected from the group consisting of TADF luminescent groups.
  • the organic functional group G is selected from the group consisting of triplet luminescent groups.
  • the organic functional group G is selected from the group consisting of singlet luminescent groups.
  • the organic functional group G comprises organic functional groups G1 and G2, wherein the organic functional group G1 is selected from a triplet matrix group and the organic functional group G2 is selected from a triplet luminescent group.
  • the organic functional group G comprises organic functional groups G1 and G2, wherein the organic functional group G1 is selected from a hole transporting group and the organic functional group G2 is selected from an electron transporting group.
  • the application also provides a first monomer having the following general formula (5),
  • the E1 group (HOMO-(HOMO-1) ⁇ 0.3 eV.
  • the E1 group (HOMO-(HOMO-1) ⁇ 0.3 eV, preferably ⁇ 0.35 eV, more preferably ⁇ 0.4 eV, more preferably ⁇ 0.45 eV, preferably ⁇ 0.5eV.
  • the present application also provides a mixed monomer comprising the first monomer and the second monomer, wherein the second monomer has the following general formula (6):
  • min((LUMO(E1)-HOMO(E2), LUMO(E2)-HOMO(E1))-min(E T (E1), E T (E2)) ⁇ 0eV
  • it is ⁇ 0.05 eV, more preferably ⁇ 0.10 eV, more preferably ⁇ 0.15 eV, and most preferably ⁇ 0.20 eV.
  • the E1 group in the first monomer and the E2 group in the second monomer are respectively the same as the E1 group and the E2 group in the high polymer, and are not described herein again.
  • the present application also relates to a high polymer represented by the following formula (4), wherein n is an integer greater than or equal to 1:
  • E1 group (HOMO-(HOMO-1)) ⁇ 0.3 eV; and when n is greater than 1, E1 may take a different group as long as each E1 (HOMO-(HOMO-1)) ⁇ 0.3 eV can be.
  • (EHO-(HOMO-1)) ⁇ 0.35 eV, preferably ⁇ 0.4 eV, more preferably ⁇ 0.45 eV, and most preferably ⁇ 0.5, of the E1 group in the formula (4) eV.
  • the E1 group in the formula (4) contains a structural unit represented by one of the formulae (2) to (5) as described above.
  • the E1 group of formula (4) contains the following structural units:
  • Each of Ar 1 to Ar 9 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • the E1 group may contain one or more of the following structural units:
  • the present application also provides a mixture comprising one of the high polymers represented by the general formulae (1) to (4) and another organic functional material, which can be selected from holes (also called holes).
  • Injection or transport material HIM/HTM
  • hole blocking material HBM
  • electron injecting or transporting material EIM/ETM
  • electron blocking material EBM
  • organic matrix material Host
  • singlet illuminant Fluorescent emitters, triplet emitters (phosphorescent emitters), and TADF materials.
  • the organic functional material is a fluorescent illuminant; in another preferred embodiment, the organic functional material is a phosphorescent illuminant; in another preferred embodiment, the organic function
  • the material is a TADF material.
  • the present application also relates to a composition comprising one of the high polymers represented by the general formulae (1) to (4) and an organic solvent.
  • organic solvents include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, O-xylene, m-xylene, 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, naphthalene Alkanes,
  • the composition according to the present application is a solution.
  • composition according to the present application is a suspension.
  • composition in the examples of the present application may comprise 0.01 to 20% by weight of a high polymer, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably 0.25 to 5% by weight of a high polymer. .
  • the present application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particularly preferred It is a preparation method 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.
  • 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 present application also provides an application of the high polymer as described above, that is, the high polymer is applied to an organic electronic device, and the organic electronic device may be selected from, but not limited to, organic light emission.
  • Diodes OLEDs
  • OLEDs Organic Photovoltaic Cells
  • OLEDs Organic Light Emitting Cells
  • OFETs Organic Field Effect Transistors
  • Organic Light Emitting Fields Organic Lasers, Organic Spintronics, Organic Sensors and Organic Plasmons Organic Plasmon Emitting Diode, etc., especially OLED.
  • the organic compound is preferably used in the light-emitting layer of the OLED device.
  • the high polymer represented by the general formula (1) is used for the light-emitting layer of the OLED device.
  • the high polymer represented by the general formula (4) is used for a hole transport layer of an OLED device.
  • the application further relates to an organic electronic device comprising at least one high polymer as described above.
  • an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein said functional layer comprises at least one of the polymers described above.
  • the organic electronic device may be selected from, but not limited to, 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, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • the organic electronic device is an OLED comprising a substrate, an anode, at least one luminescent layer, and a cathode.
  • the substrate can 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-na
  • the anode can 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 work function of the anode and the hair in the luminescent layer is less than 0.5 eV, preferably less than 0.3 eV, 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 application.
  • the cathode can include 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 present application.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/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 include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer.
  • 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 contains the high polymer represented by the general formula (1) of the present application.
  • the hole transport layer thereof contains the high polymer represented by the formula (4) of the present application.
  • the light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the present application also relates to the use of the organic electronic device according to the present application in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors, and the like.
  • the application also relates to an electronic device incorporating an organic electronic device in accordance with the present application, including, but not limited to, a display device, a lighting device, a light source, a sensor, and the like.
  • the synthesis step of monomer E1-3 is similar to the synthesis step of monomer E1-2, except that compound 5 is used in the first step, and the aldehyde-containing intermediate formed next is 6.
  • the finally obtained intermediate E1-3 was a white solid powder.
  • MS (ASAP) 681.2.
  • the synthesis step of monomer E1-4 is similar to the synthesis step of monomer E1-2, except that compound 5-1 is used in the first step, and the aldehyde-containing intermediate formed next is 6-1.
  • the synthesis step of monomer E2-1 is similar to the synthesis step of monomer E1-1 except that compound 7 is used in the first step, and the aldehyde-containing intermediate formed next is 8.
  • the finally obtained intermediate E2-1 was an off-white solid powder.
  • MS (ASAP) 660.3.
  • the synthesis step of the monomer E2-2 was similar to the synthesis step of the monomer E1-1 except that the first step used was the compound 9, and the next aldehyde-containing intermediate was formed to be 10.
  • the finally obtained intermediate E2-2 was an off-white solid powder.
  • MS (ASAP) 662.3.
  • the synthesis step of monomer E2-3 is similar to the synthesis step of monomer E1-1, except that compound 11 is used in the first step, and the aldehyde-containing intermediate formed next is 12.
  • the finally obtained intermediate E2-3 was an off-white solid powder.
  • MS (ASAP) 647.3.
  • the synthesis step of monomer E2-4 is similar to the synthesis step of monomer E1-1, except that compound 13 is used in the first step, and the aldehyde-containing intermediate formed next is 14.
  • the finally obtained intermediate E2-4 was an off-white solid powder.
  • MS (ASAP) 434.4.
  • the energy structure of the organic repeating structural unit can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • 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 and T1 are used directly
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the main synthetic steps are as follows: taking the synthesis of P1 polymer as an example, 0.5mmol E1-1, 0.50mmol E2-1 monomer is dissolved in toluene solvent under nitrogen protection conditions, and simultaneously 0.01 mmol of 2,2-azobisisobutyronitrile (AIBN initiator) was added to the syringe, sealed, and reacted at 60 ° C for 4 hours. When the reaction was completed, it was cooled to room temperature, and the polymer was precipitated with methanol. The precipitate was dissolved in tetrahydrofuran (THF) and precipitated with methanol. Repeat this way The vacuum was dried to give a solid of the polymer P1.
  • AIBN initiator 2,2-azobisisobutyronitrile
  • P1-9 is a high polymer represented by the general formula (1) in the present application
  • P10-17 is a high polymer represented by the general formula (4) in the present application.
  • the preparation process of the OLED device using the above high polymer will be described in detail below by way of a specific embodiment.
  • the structure of the OLED device is: ITO/HIL/HTL/EML/ETL/cathode, and the preparation steps are as follows:
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • HIL hole injection layer, 60nm
  • 60nm is of PEDOT (polyethylene dioxythiophene, Clevios TM AI4083) in a clean room as HIL spin coated from, and heat-treated at 180 [deg.] C for 10 minutes plate ;
  • HTL hole transport layer, 20 nm
  • 20 nm TFB or PVK (Sigma Aldrich, average Mn 25,000-50,000) was prepared by spin coating in a nitrogen glove box, and the solution used was TFB added to the toluene solvent.
  • PVK Sigma Aldrich
  • solution solubility 5mg / ml was treated on a hot plate at 180 ° C for 60 minutes;
  • TFB H.W.SandsCorp.
  • EML organic light-emitting layer
  • EML is formed by spin coating in a nitrogen glove box, and the solution used is a high polymer (P1-P10) added to a toluene solvent and a certain amount of Ir(PPy) 3 .
  • the solution solubility was 10 mg/ml, and then treated on a hot plate at 180 ° C for 10 minutes; Table 2 lists the composition and thickness of the EML of the device;
  • OLED device HTL EML composition and thickness OLED1 PVK P1 (15%) Ir(ppy) 3 (80nm) OLED2 PVK P2: (15%) Ir(ppy) 3 (65nm) OLED3 TFB P3: (15%) Ir(ppy) 3 (80nm) OLED4 TFB P4: (15%) Ir(ppy) 3 (80nm) OLED5 TFB P5: (15%) Ir(ppy) 3 (80nm) OLED6 PVK P6: (15%) Ir(ppy) 3 (65nm) OLED7 PVK P7: (15%) Ir(ppy) 3 (65nm) OLED8 TFB P8 (15%) Ir(ppy) 3 (65nm) OLED9 TFB P9 (15%) Ir(ppy) 3 (65nm)
  • cathode Ba / Al (2nm / 100nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device was encapsulated in a UV glove box with a UV curable resin.
  • the current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and drive voltage.
  • the performance of OLED devices is summarized in Table 3.
  • P10-P17 can be used as a HTL for OLEDs instead of TFB or PVK.
  • the high polymer represented by the general formulae (1) to (3) of the present application is liable to form an exciplex, and when used for a phosphorescent host, the efficiency of the device can be improved, and at the same time, it has good solubility in an organic solvent.
  • the film forming performance is good, which provides a better material solution for printing OLED.
  • the high polymer represented by the formula (4) of the present application has high stability and is easy to be processed by a solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

一种高聚物、包含其的混合物、组合物和有机电子器件以及聚合单体，其中，所述高聚物包括重复单元E1和重复单元E2，所述重复单元E1侧链上的E1基团和所述重复单元E2侧链上的E2基团具有形成激基络合物（Exciplex）特性，即其中min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≦min(E T(E1),E T(E2))+0.1eV，从而提供了一种适合于印刷工艺的高聚物，进而降低OLED制造成本。

Description

高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体
相关申请
本申请要求2016年11月23日申请的，申请号为201611047040.7，名称为“一种基激络合物高聚物、包含其的有机电子器件及应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及电致发光材料领域，尤其涉及一种高聚物、包含其的混合物、组合物和有机电子器件以及聚合单体。
背景技术
因为有机半导体材料的在合成上的多样性，实现大面积柔性器件的可能，低的制造成本和优异的光学和电学性能，有机发光二极管(OLED)在新颖的光电器件的实现中，例如，在平板显示器和照明应用，有很大的潜力。为了提高有机发光二极管的发光效率，各种基于荧光和磷光发光材料体系已被开发出来。使用磷光材料的有机发光二极管已经取得相当高的性能，如已取得了几乎100％的内部发光量子效率。但迄今为止，有实际使用价值的磷光主体材料是双极传输化合物或共主体化合物，材料搭配较为复杂，应用于器件中引起空穴、电子传输不平衡，因此磷光器件寿命一直不长。Kim提出激基络合物(exciplex)用作磷光发光主体材料的概念，这样可以利用两个不同的有机化合物形成一个中间态，即激基络合物，实现磷光OLED器件的长寿命。这可通过激基络合物主体材料，参见Kimet al.,Adv.Mater.,Vol 26,5864,(2014),得以实现。
为了充分利用有机材料的优点，人们希望通过打印的方法，低成本，大面积地制备OLED。现有报道的能形成激基络合物的有机材料都是小分子材料，分子量比较低，不适合于印刷工艺。
因此，新的适合于印刷的新材料体系有待于开发。
发明内容
鉴于上述现有技术的不足，本申请的目的在于提供一种新的高聚物材料，解决现有激基络化物(Exciplex)材料不适合于印刷工艺的问题。
本申请的技术方案如下：
一种高聚物，包括通式(1)所示的重复单元，其中n和m是大于或等于1的整数，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))+0.1eV，其中LUMO(E1)，HOMO(E1)及ET(E1)分别是E1基团的最高占有轨道能级，最低未占有轨道能级以 及三线态能级，LUMO(E2)，HOMO(E2)及ET(E2)分别是E2基团的最高占有轨道能级，最低未占有轨道能级以及三线态能级。
Figure PCTCN2017112716-appb-000001
优选地，所述高聚物中n:m的比例从3:7到7:3。。
优选地，E1基团含有供电子基D，和/或E2基团含有吸电子基。优选地，E1基团和/或E2基团的(HOMO-(HOMO-1)≥0.3eV。在某些优先的实施方案中，E1基团与E2基团分别具有如下通式(I)或(II)所示的结构单元：
Figure PCTCN2017112716-appb-000002
其中Ar为芳香族或杂芳族结构单元，所述供电子基D在多次出现时可相同或不同，所述吸电子基A在多次出现时可相同或不同，p、r为1到6之间的整数，且q、s为0或1；
另一种相关但不同的高聚物，如下通式(4)所示，其中n是大于或等于1的整数：
Figure PCTCN2017112716-appb-000003
其中，E1基团的(HOMO-(HOMO-1)≥0.3eV。
一种包含有上述E1基团或上述E2基团的可聚合单体，以及它们的组合。
一种组合物，包括如上所述的任一高聚物，及至少一种有机溶剂。
一种根据如上所述的任一高聚物在有机电子器件中的应用。
一种有机电子器件，至少包括如上所述的任一高聚物。
有益效果：本申请按照通式(1)的高聚物易于形成激基络合物，在用于磷光主体时，可以提高器件的效率，同时由于在有机溶剂中具有较好的溶解性，成膜性能好，从而为印刷OLED提供了较好的材料解决方案。按照通式(4)的高聚物具有较高的稳定性，并易于溶液加工。
具体实施方式
为使本申请的目的、技术方案及效果更加清楚、明确，以下对本申请进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
一种高聚物，包括有如通式(1)所示的重复单元，n和m是大于或等于1的整数，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))+0.1eV，其中LUMO(E1)、HOMO(E1)及ET(E1)分别是E1基团的最高占有轨道能级、最低未占有轨道能级及三线态能级，LUMO(E2)、HOMO(E2)及ET(E2)分别是E2基团的最高占有轨道能级、最低未占有轨道能级及三线态能级。
Figure PCTCN2017112716-appb-000004
在一个优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))；
在一个较为优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))-0.05eV；
在一个更为优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))-0.1eV；
在一个非常优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))-0.15eV；
在一个最为优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))-0.2eV；
在本申请实施例中，有机材料的能级结构，三线态能级ET、HOMO、LUMO起着关键的作用。以下对这些能级的确定做一介绍。
HOMO和LUMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级ET可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110或如下在实施例中所述。
应该注意，HOMO、LUMO、ET的绝对值取决于所用的测量方法或计算方法，甚至对于相 同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本申请实施例的描述中，HOMO、LUMO、ET的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
按照本申请的高聚物，其好处是，E1基团与E2基团作为侧链结构通过非共轭的高聚物主链连接起来，达到较高的分子量，同时保持单个重复单元能量结构，即单个重复单元的HOMO、LUMO及ET相对于E1基团或E2基团基本保持不变，同时在高聚物中形成激基络合物。
在发明中，(HOMO-1)定义为第二高的占有轨道能级，(HOMO-2)为第三高的占有轨道能级，以此类推。(LUMO+1)定义为第二低的未占有轨道能级，(LUMO+2)为第三低的占有轨道能级，以此类推。
在本申请中，将E1基团所在的重复单元定义为重复单元E1，将E2基团所在的重复单元定义为重复单元E2。一般地，高聚物中重复单元E1与重复单元E2的数量之间的比例n:m是从3:7至7:3。
在一个优先的实施例中，高聚物中重复单元E1与重复单元E2的数量之间的比例n:m是从4:6到7:3，更好是从4:6到6:4，更更好是从5:5到6:4，最好是5:5。
为了使高聚物具有更好的溶解性以及可加工性，一般在高聚物的主链上接上额外的基团R，增加高聚物溶解度，同时提高高聚物的分子量，使其具有更好的发光性能与器件性能。按照本申请的高聚物，在一个优选的实施例中，包括有如通式(2)所示的重复单元。
Figure PCTCN2017112716-appb-000005
其中，R选自含1-15个碳原子的直链烷烃、支链烷烃以及环烷烃，具有2-20个碳原子的芳香族、杂芳香族或者非芳香族环系；o是大于或等于0的整数。
在一个优先的实施例中，R具有有机功能材料对应的结构单元，所述的有机功能材料可选自HTM、ETM、荧光发光材料、磷光发光材料及主体材料。
在一个较为优先的实施例中，R具有荧光发光材料或磷光发光材料对应的结构单元。
按照本申请的高聚物，重复单元E1与重复单元E2之间可形成激基络合物，在发光层中可用作主体材料或者发光体。用于主体材料时，在某些实施例中，重复单元E1与重复单元E2所形成的激基络合物在高聚物的比重是从70％至99.9％；
在一个优先的实施例中，重复单元E1或重复单元E2在高聚物中的含量是从30mol％到50mol％，较好是从35mol％到50mol％，更好是从40mol％到50mol％，更更好是从40mol％到48mol％，最好是从41mol％到46mol％。
在一个优先的实施例中，通式(2)中的R基团还包含有发光体单元。在某些的实施例中，重复单元R在高聚物中的含量是从0.1mol％到30mol％。在本申请中，将R基团所在的重复单元定义为重复单元R。
在一个较为优先的实施例中，包含有发光体的重复单元R在高聚物中的含量是从1mol％到52mol％，较好是从2mol％到20mol％，更好是从3mol％到81mol％，更更好是从4mol％到61mol％，最好是从5mol％到15mol％。
在本申请中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，可以互换；单线态，单重态具有相同的含义，可以互换；三线态，三重态具有相同的含义，可以互换。
本申请中所定义的术语“小分子”是指不是聚合物、低聚物、树枝状聚合物和共混物的分子。特别是，小分子中没有重复单元结构。小分子的分子量≤3000克/摩尔，较好是≤2000克/摩尔，最好是≤1500克/摩尔。
高聚物，即Polymer，包括均聚物(homopolymer)、共聚物(copolymer)和镶嵌共聚物(block copolymer)。另外在本申请中，高聚物也包括树状物(dendrimer)，有关树状物的合成及应用请参见【Dendrimers and Dendrons,Wiley-VCH Verlag GmbH & Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle.】。
共轭高聚物(conjugated polymer)的主链backbone主要是由C原子的sp2杂化轨道构成，著名的例子有：聚乙炔polyacetylene和poly(phenylene vinylene)，其主链上的C原子的也可以被其他非C原子取代，而且当主链上的sp2杂化被一些自然的缺陷打断时，仍然被认为是共轭高聚物。另外在本申请中共轭高聚物也包括主链上包含有芳基胺(aryl amine)、芳基磷化氢(aryl phosphine)及其他杂环芳烃(heteroarmotics)、有机金属络合物(organometallic complexes)等。按照本申请的高聚物也可以是一种非共轭高聚物。
在某些实施例中，按照本申请的高聚物，E1基团和E2基团中至少有一个((HOMO-(HOMO-1))≥0.2eV，较好是≥0.25eV，更好是≥0.3eV，更更好是≥0.35eV，非常好是≥0.4eV，最好是≥0.45eV。其中，当E1基团和/或E2基团的Δ((HOMO-(HOMO-1))较大，有利于空穴传输的稳定性。
在某个优先的实施例中，E1基团含有如下通式(2)-(9)所示结构单元中的一种或多种：
Figure PCTCN2017112716-appb-000006
其中，L1表示单键、碳原子数为6～30的芳香基团或碳原子数为3～30的芳杂基团，L1的连接位置可以是苯环上任意一碳原子上；
Ar、Ar1以及Ar2分别独立地表示碳原子数为6～30的芳香基团或碳原子数为3～30的芳杂基团；
A1、A2分别独立地表示碳原子数为6～30的芳香基团或碳原子数为3～30的芳杂基团；
L2、L3分别独立表示6～30的芳香基团或碳原子数为3～30的芳杂基团；
X1、X2分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O或SO2；
X3、X4分别独立表示单键、N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O或SO2，但不能同为单键；
Y1～Y8分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O 或SO2；
R1、R2、R3、R4、R5、R6、R分别独立表示H、D(氘原子)、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、碳原子数1～30的烷基、碳原子数3～30的环烷基、碳原子数为6～60芳香族烃基或碳原子数为3～60的芳香族杂环基，其中，R1、R2、R3、R4、R5、R6的连接位置可以是稠环上任意一碳原子上。
n表示1～6的整数。
在一个优选的实施例中，按照本申请的高聚物，E1基团含有供电子基D和/或E2基团含有吸电子基A。
在一个更加优选的实施例中，按照本申请的高聚物，E1基团含有以下通式I代表的结构单元：
Figure PCTCN2017112716-appb-000007
其中Ar为芳香族或杂芳族结构单元，D在多次出现时可相互独立地选自相同或不同的供电子基，p为1到6之间的整数，q是0或等于1；
合适的供电子基D可选自具有以下通式I-1、I-2和I-3中任一骨架的基团：
Figure PCTCN2017112716-appb-000008
其中：Z1＝H、O、S或Si，A1及A2可分别独立形成芳香环、杂芳香环、脂肪环或非芳香族杂环；R20表示H、芳基、或形成A4所示之环所必需的原子群，A3及A4也可分别独立形成杂芳香环或非杂芳香环；Z2、Z3、Z4、Z5分别独立表示O或S。
在一个优选的实施方案中，以上所述的供电子基D选自具有以下结构式D1-D15中至少一种骨架的基团：
Figure PCTCN2017112716-appb-000009
Figure PCTCN2017112716-appb-000010
在另一个更加优选的实施例中，按照本申请的高聚物，E2基团含有以下通式II代表的结构：
Figure PCTCN2017112716-appb-000011
其中Ar为芳香族或杂芳族结构单元，吸电子基A在多次出现时可相互独立地选自相同或不同的吸电子基，r为1到6之间的整数，s是0或1。
在一个优选的实施方案中，合适的吸电子基A可选自F、氰基或具有以下所示骨架的基团中的至少一种：
Figure PCTCN2017112716-appb-000012
其中n1是一个从1到3的整数；X1-X8选于CR12或N，并且至少有一个是N，其中R12可选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。Z1-Z3为单键或C(R12)2或O或S。当吸电子基A为F或氰基时，s为1。
在一个优选的实施方案中，合适的吸电子基A选自氰基，且s为1。
在一个优先的实施例中，按照本申请的高聚物，在通式I与通式II中，Ar选自如下基团：
Figure PCTCN2017112716-appb-000013
Figure PCTCN2017112716-appb-000014
其中n2为1或2或3或4。通式I和通式II中的Ar可以相同，也可以不相同。
按照本申请所述的高聚物中，可用于E1基团的结构单元的例子有：
Figure PCTCN2017112716-appb-000015
Figure PCTCN2017112716-appb-000016
Figure PCTCN2017112716-appb-000017
在一个优选的实施例中，按照本申请所述的高聚物中，可用于E2基团的结构单元的例子有：
Figure PCTCN2017112716-appb-000018
Figure PCTCN2017112716-appb-000019
Figure PCTCN2017112716-appb-000020
在本申请中，多个重复单元E1中的多个E1基团可以相同，也可以不相同；多个重复单元E2中的多个E2基团可以相同，也可以不相同。
按照本申请的高聚物还包含有另一种的有机功能基团。
在某些实施例中，按照本申请的高聚物具有如下通式(3)所示结构：
Figure PCTCN2017112716-appb-000021
其中G为所述的另一种的有机功能基团，n和m在通式(3)中的含义与在通式(1)和通式(2)中的含义相同，t为大于或等于0的整数。
所述另一种的有机功能基团G，在多个出现时，可相互独立地相同或不同地选于空穴(也称电洞)注入或传输基团、空穴阻挡基团、电子注入或传输基团、电子阻挡基团、有机基质基团、 单重态发光基团(荧光发光基团)、三重态发光基团(磷光发光基团)和热激发延迟荧光(TADF)发光基团。这些有机功能基团对应的小分子有机功能材料分别为空穴(也称电洞)注入或传输材料(HIM/HTM)、空穴阻挡材料(HBM)、电子注入或传输材料(EIM/ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、单重态发光体(荧光发光体)、三重态发光体(磷光发光体)和TADF发光体。例如在WO2010135519A1、US20090134784A1和WO 2011110277A1中对这些有机功能材料有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
下面对这些功能材料作一些较详细的描述(但不限于此)。
1.HIM/HTM/EBM
合适的有机HIM/HTM材料可选包含有如下结构单元的化合物:酞菁、卟啉、胺、芳香胺、联苯类三芳胺、噻吩、并噻吩如二噻吩并噻吩和并噻吩、吡咯、苯胺、咔唑、氮茚并氮芴及它们的衍生物。另外，合适的HIM也包括含有氟烃的聚合物、含有导电掺杂的聚合物、导电聚合物，如PEDOT/PSS；自组装单体,如含有膦酸和sliane衍生物的化合物；金属氧化物，如MoOx；金属络合物和交联化合物等。
电子阻挡层(EBL)用来阻挡来自相邻功能层，特别是发光层的电子。对比一个没有阻挡层的发光器件,EBL的存在通常会导致发光效率的提高。电子阻挡层(EBL)的电子阻挡材料(EBM)需要有比相邻功能层，如发光层更高的LUMO。在一个优先的实施方案中，HBM有比相邻发光层更大的激发态能级,如单重态或三重态,取决于发光体，同时，EBM有空穴传输功能。通常具有高的LUMO能级的HIM/HTM材料可以作为EBM。
可用作HIM，HTM或EBM的环芳香胺衍生化合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2017112716-appb-000022
每个Ar1到Ar9可独立选自环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、非那烯、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅 原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个方面，Ar1到Ar9可独立选自包含如下组的基团:
Figure PCTCN2017112716-appb-000023
n是1到20的整数；X1到X8是CH或N；Ar1如以上所定义。
环芳香胺衍生化合物的另外的例子可参见US3567450,US4720432,US5061569,US3615404,和US5061569.
可用作HTM或HIM的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2017112716-appb-000024
M是一金属,有大于40的原子量；
(Y1-Y2)是一两齿配体,Y1和Y2独立地选自C、N、O、P和S；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个实施例中，(Y1-Y2)是2-苯基吡啶衍生物。
在另一个实施例中,(Y1-Y2)是一卡宾配体。
在另一个实施例中,M选于Ir、Pt、Os和Zn。
在另一个方面，金属络合物的HOMO大于-5.5eV(相对于真空能级)。
在下面的表中列出合适的可作为HIM/HTM化合物的例子:
Figure PCTCN2017112716-appb-000025
Figure PCTCN2017112716-appb-000026
2.EIM/ETM/HBM
EIM/ETM材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能被用作为EIM/ETM，只要它们可以传输电子。优先的有机EIM/ETM材料可选自三(8-羟基喹啉)铝(AlQ3)、吩嗪、菲罗啉、蒽、菲、芴、二芴、螺二芴、对苯乙炔、哒嗪、吡嗪、三嗪、三唑、咪唑、喹啉、异喹啉、喹噁啉、噁唑、异噁唑、噁二唑、噻二唑、吡啶、吡唑、吡咯、嘧啶、吖啶、芘、苝、反茚并芴、顺茚并、二苯并-茚并芴、茚并萘、苯并蒽、氮磷杂环戊二烯、氮硼杂环戊二烯、芳香酮类、内酰胺及它们的衍生物。
空穴阻挡层(HBL)通常用来阻挡来自相邻功能层,特别是发光层的空穴。对比一个没有阻挡层的发光器件,HBL的存在通常会导致发光效率的提高。空穴阻挡层(HBL)的空穴阻挡材料(HBM)需要有比相邻功能层,如发光层更低的HOMO。在一个优先的实施方案中,HBM有比相邻发光层更大的激发态能级,如单重态或三重态,取决于发光体。在另一个优先的实施方案中，HBM有电子传输功能。通常具有深的HOMO能级的EIM/ETM材料可以做为HBM。
另一方面,可用作EIM/ETM/HBM的化合物是至少包含一个以下基团的分子：
Figure PCTCN2017112716-appb-000027
R1可选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基，当它们是芳基或杂芳基时，它们与上述HTM中的Ar1和Ar2意义相同；Ar1-Ar5与在HTM 中所描述的Ar1意义相同；n是一个从0到20的整数；X1-X8选于CR1或N。
另一方面，可用作EIM/ETM的金属络合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2017112716-appb-000028
(O-N)或(N-N)是一两齿配体,其中金属与O,N或N,N配位；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数。
在下面的表中列出合适的可作ETM化合物的例子:
Figure PCTCN2017112716-appb-000029
在另一个优先的实施方案中,有机碱金属化合物可用作EIM。在本申请中,有机碱金属化合物可以理解挖为如下的化合物，其中至少有一个碱金属，即锂，钠，钾，铷，铯，并进一步包含至少一个有机配体。
合适的有机碱金属化合物，包括US7767317B2，EP1941562B1和EP 1144543B1中所描述的化合物。
优先选择的有机碱金属化合物是下列化学式的化合物:
Figure PCTCN2017112716-appb-000030
其中R1的含义如上所述，弧线代表两个或三个原子及键接，以便必要时的与金属M形成5 元或六元环，其中原子也可以由一个或多个R1取代，M为碱金属，选自锂、钠、钾、铷和铯。
有机碱金属化合物可以有单体的形式，如以上所述的，或有聚集体的形式，例如，两碱金属离子与两个配体,4碱金属离子和4配体，6碱金属离子和6配体或在其他的形式。
优先选择的有机碱金属化合物是下列化学式的化合物:
Figure PCTCN2017112716-appb-000031
其中使用的符号有上述定义相同,另外：
o，每次出现时可以是相同或不同，是0、1、2、3或4；
p，每次出现时可以是相同或不同，是0、1、2或3；
在一个优先的实施方案中,碱金属M选自锂，钠，钾，更好是锂或钠，最好是锂。
在一个优先的实施方案中,有机碱金属化合物电子注入层中.更好地,电子注入层由有机碱金属化合物组成。
在另一个优先的实施方案中,有机碱金属化合物掺杂到其他ETM中形成电子传输层或电子注入层中。更好地，是电子传输层。
在下面的表中列出合适的有机碱金属化合物的例子:
Figure PCTCN2017112716-appb-000032
3.三重态基质材料(TripletHost):
三重态主体材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能被用作为主体,只要其三重态能量比发光体,特别是三重态发光体或磷光发光体更高。可用作三重态主体(Host)的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2017112716-appb-000033
M是一金属；(Y3-Y4)是一两齿配体,Y3和Y4独立地选自C,N,O,P,和S；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个优先的实施方案中，可用作三重态主体的金属络合物有如下形式：
Figure PCTCN2017112716-appb-000034
(O-N)是一两齿配体,其中金属与O和N原子配位.
在某一个实施方案中,M可选于Ir和Pt.
可作为三重态主体的有机化合物的例子选自包含有环芳香烃基的化合物，例如苯、联苯、三苯基、苯并、芴；包含有芳香杂环基的化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三唑类、恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮杂萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩苯并二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个优先的实施方案中,三重态主体材料可选于包含至少一个以下基团的化合物:
Figure PCTCN2017112716-appb-000035
R1-R7可相互独立地选于如下的基团:氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基，当它们是芳基或杂芳基时，它们与上述的Ar1和Ar2意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9选于CR1R2或NR1。
在下面的表中列出合适的三重态主体材料的例子:
Figure PCTCN2017112716-appb-000036
4.单重态基质材料(Singlet Host):
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为单重态主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。
在一个优先的实施方案中，单重态主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2017112716-appb-000037
其中，R1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；Ar1是芳基或杂芳基，它与上述的HTM中定义的Ar1意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9和X10选于CR1R2或NR1。
在下面的表中列出一些蒽基单重态主体材料的例子：
Figure PCTCN2017112716-appb-000038
5.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今,已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，和在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。
在一个优先的实施方案中,单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物,它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物,它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物,它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物,它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯,其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环 系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上,最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上,最好是在9,10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似,其中二元芳基胺基团最好联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子,也是优选的例子,可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603),环戊二烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料可在下述专利文件中找到:US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1。特此将上述列出的专利文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的单重态发光体的例子:
Figure PCTCN2017112716-appb-000039
6.热激活延迟荧光发光材料(TADF)：
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。
TADF材料需要具有较小的单线态-三线态能级差(ΔEst)，较好是ΔEst≤0.3eV，次好是ΔEst≤0.2eV，最好是ΔEst≤0.1eV。在一个优先的实施方案中，TADF材料有比较小的ΔEst，在另一个优先的实施方案中,TADF有较好的荧光量子效率。一些TADF发光的材料可在下述专利文件中找到: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.Commun.,48,2012,11392，Adachi,et.al.Nature Photonics,6,2012,253，Adachi,et.al.Nature,492,2012,234，Adachi,et.al.J.Am.Chem.Soc,134,2012,14706，Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311，Adachi,et.al.Chem.Commun.,48,2012,9580，Adachi,et.al.Chem.Commun.,48,2013,10385，Adachi,et.al.Adv.Mater.,25,2013,3319，Adachi,et.al.Adv.Mater.,25,2013,3707，Adachi,et.al.Chem.Mater.,25,2013,3038，Adachi,et.al.Chem.Mater.,25,2013,3766，Adachi,et.al.J.Mater.Chem.C.,1,2013,4599，Adachi,et.al.J.Phys.Chem.A.,117,2013,5607，特此将上述列出的专利或文章文件中的全部内容并入本文作为参考。
7.三重态发光体(Triplet Emitter)
三重态发光体也称磷光发光体。在一个优先的实施方案中，三重态发光体是有通式M(L)n的金属络合物,其中M是一金属原子，L每次出现时可以是相同或不同，是一有机配体，它通过一个或多个位置键接或配位连接到金属原子M上,n是一个大于1的整数，较好选是1，2，3，4，5或6。可选地，这些金属络合物通过一个或多个位置联接到一个聚合物上，最好是通过有机配体。
在一个优先的实施方案中,金属原子M选于过渡金属元素或镧系元素或锕系元素,优先选择Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优先选择Os,Ir,Ru,Rh,Re,Pd或Pt。
优先地,三重态发光体包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优先考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的例子可选自苯基吡啶衍生物，7,8-苯并喹啉衍生物，2(2-噻吩基)吡啶衍生物，2(1-萘基)吡啶衍生物，或2苯基喹啉衍生物。所有这些有机配体都可能被取代，例如被含氟或三氟甲基取代。辅助配体可优先选自乙酸丙酮或苦味酸。
在一个优先的实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2017112716-appb-000040
其中M是一金属,选于过渡金属元素或镧系元素或锕系元素；
Ar1每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个施主原子，即有一孤对电子的原子，如氮或磷，通过它环状基团与金属配位连接；Ar2每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个C原子,通过它环状基团与金属连接；Ar1和Ar2由共价键联接在一起,可各自携带一个或多个取代基团，它们也可再通过取代基团联接在一起；L每次出现时可以是相同或不同,是一个辅助配体,优选于双齿螯合配体，最好是单阴离子双齿螯合配体；m是1,2或3,优先地是2或3,特别优先地是3；n是0,1,或2,优先地是0或1,特别优先地是0；
一些三重态发光体的材料极其应用的例子可在下述专利文件和文献中找到:WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido et al.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1。特此将上述列出的专利文件和文献中的全部内容并入本文作为参考。
在一个优先的实施例中，有机功能基团G选自三重态基质基团。
在一个优先的实施例中，有机功能基团G选自TADF发光基团。
在另一个优先的实施例中，有机功能基团G选自三重态发光基团。
在另一个优先的实施例中，有机功能基团G选自单重态发光基团。
在另一个优先的实施例中，有机功能基团G包括有机功能基团G1和G2，其中有机功能基团G1选自三重态基质基团，有机功能基团G2选自三重态发光基团。
在另一个优先的实施例中，有机功能基团G包括有机功能基团G1和G2，其中有机功能基团G1选自空穴传输基团，有机功能基团G2选自电子传输基团。
本申请还提供第一单体，具有如下通式(5)，
Figure PCTCN2017112716-appb-000041
其中，E1基团的(HOMO-(HOMO-1)≥0.3eV。
在一个优先的实施例中，E1基团的(HOMO-(HOMO-1)≥0.3eV，较好是≥0.35eV，更好是≥0.4eV，更更好是≥0.45eV，最好是≥0.5eV。
本申请还提供一种混合单体，包括所述第一单体和第二单体，其中，所述第二单体具有如下通式(6)：
Figure PCTCN2017112716-appb-000042
其特征在于，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))+0.1eV。
在一个优先的实施例中，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))-min(ET(E1),ET(E2))≤0eV，较好是≤0.05eV，更好是≤0.10eV，更更好是≤0.15eV，最好是≤0.20eV。
第一单体中的E1基团和第二单体中的E2基团分别与所述高聚物中的E1基团和E2基团相同，在此不再赘述。
以下列出合适的第一单体的一些例子：
Figure PCTCN2017112716-appb-000043
Figure PCTCN2017112716-appb-000044
Figure PCTCN2017112716-appb-000045
Figure PCTCN2017112716-appb-000046
以下列出合适的可作为所述第二单体的一些例子：
Figure PCTCN2017112716-appb-000047
Figure PCTCN2017112716-appb-000048
Figure PCTCN2017112716-appb-000049
Figure PCTCN2017112716-appb-000050
本申请还涉及一种如下通式(4)所示的高聚物，其中n是大于或等于1的整数：
Figure PCTCN2017112716-appb-000051
其中，E1基团的(HOMO-(HOMO-1))≥0.3eV；并且当n大于1时，E1可以取不同的基团，只要每个E1的(HOMO-(HOMO-1))≥0.3eV即可。
在某些实施例中，通式(4)中E1基团的((HOMO-(HOMO-1))≥0.35eV，较好是≥0.4eV，更好是≥0.45eV，最好是≥0.5eV。
在某个优先的实施例中，通式(4)中的E1基团含有如上所述的通式(2)-(5)之一所示的结构单元。
在另一个优先的实施例中，通式(4)中E1基团含有如下的结构单元：
Figure PCTCN2017112716-appb-000052
每个Ar1到Ar9可独立选自环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、非那烯、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
优选的，按照通式(4)的高聚物，E1基团可含有以下结构单元中的一种或多种：
Figure PCTCN2017112716-appb-000053
Figure PCTCN2017112716-appb-000054
本申请还提供一种混合物，包括通式(1)～(4)代表的高聚物中的一种和另一种有机功能材料，所述有机功能材料可选于空穴(也称电洞)注入或传输材料(HIM/HTM)，空穴阻挡材料(HBM)，电子注入或传输材料(EIM/ETM)，电子阻挡材料(EBM)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)，及TADF材料。这些功能材料前面已有所述。在一个优先的实施例中，所述有机功能材料为荧光发光体；在另一个优先的实施例中，所述有机功能材料为磷光发光体；在另一个优先的实施例中，所述有机功能材料为TADF材料。
本申请还涉及一种组合物，包含通式(1)～(4)代表的高聚物中的一种及有机溶剂。有机溶剂的例子，包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
在一个优选的实施方案中，按照本申请的组合物是溶液。
在另一个优选的实施方案中，按照本申请的组合物是悬浮液。
本申请实施例中的组合物中可以包括0.01至20wt％的高聚物，较好的是0.1至15wt％，更好的是0.2至10wt％，最好的是0.25至5wt％的高聚物。
本申请还涉及所述组合物作为涂料或印刷油墨在制备有机电子器件时的用途，特别优选的 是通过打印或涂布的制备方法。
其中，适合的打印或涂布技术包括(但不限于)喷墨打印，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布等。首选的是凹版印刷，丝网印刷及喷墨印刷。溶液或悬浮液可以另外包括一个或多个组份例如表面活性化合物，润滑剂，润湿剂，分散剂，疏水剂，粘接剂等，用于调节粘度，成膜性能，提高附着性等。有关打印技术，及其对有关溶液的相关要求，如溶剂及浓度，粘度等，的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
基于上述高聚物，本申请还提供一种如上所述的高聚物的应用，即将所述高聚物应用于有机电子器件，所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)等，特别是OLED。本申请实施例中，优选地将所述有机化合物用于OLED器件的发光层中。
在一个优先的实施例中，通式(1)所代表的高聚物用于OLED器件的发光层。
在另一个优先的实施例中，通式(4)所代表的高聚物用于OLED器件的空穴传输层。
本申请进一步涉及一种有机电子器件，至少包含一种如上所述的高聚物。一般的，此种有机电子器件至少包含一个阴极，一个阳极及位于阴极和阳极之间的一个功能层，其中所述的功能层中至少包含一种如上所述的高聚物。所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
在一个特别优选的实施例中，所述的有机电子器件是OLED，其中包括一基片，一阳极，至少一发光层，一阴极。
基片可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料，金属，半导体晶片或玻璃。最好是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较好是超过200℃，更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包括一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发 光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本申请的器件。
阴极可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本申请器件的阴极材料。阴极材料的例子包括但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包含其他功能层，如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
在一个优选的实施例中，按照本申请的发光器件中，其发光层包含有按照本申请通式(1)所代表的高聚物。
在另一个优选的实施例中，按照本申请的发光器件中，其空穴传输层包含有按照本申请通式(4)所代表的高聚物。
按照本申请的发光器件，其发光波长在300到1000nm之间，较好的是在350到900nm之间，更好的是在400到800nm之间。
本申请还涉及按照本申请的有机电子器件在各种电子设备中的应用，包括，但不限于，显示设备，照明设备，光源，传感器等等。
本申请还涉及包含有按照本申请的有机电子器件的电子设备，包括，但不限于，显示设备，照明设备，光源，传感器等等。
下面将结合优选实施例对本申请进行了说明，但本申请并不局限于下述实施例，应当理解，所附权利要求概括了本申请的范围在本申请构思的引导下本领域的技术人员应意识到，对本申请的各实施例所进行的一定的改变，都将被本申请的权利要求书的精神和范围所覆盖。
具体实施例
1.单体的合成
Figure PCTCN2017112716-appb-000055
⑴单体E1-1的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000056
合成步骤如下：
a.氮气环境保护下，将10mmol的化合物1溶解于250ml的干燥DMF溶液中，所得反应溶液置入冰浴中搅拌，逐滴加入11.0mmol的三氯氧磷(POCl3)溶液，滴加完毕后，继续反应30分钟，逐渐升至室温并反应2小时，加水淬灭反应，二氯甲烷萃取，水洗涤，合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，得化合物2的粗产物，粗产物用二氯甲烷与正已烷重结晶得产品8mmol。真空干燥待用。MS(ASAP)＝685.2。
b.将上述所得5.0mmol化合物2溶解于200ml干燥的四氢呋喃(THF)溶液中，氮气环境保护下，反应液置于-78℃的温度下搅拌，逐滴加入8.0mmol亚甲基三苯基磷(Wittig试剂)，待加入完毕后，逐渐升至室温，继续在室温下搅拌过夜，加水淬灭反应，所有反应液用二氯甲烷萃取，有机相用水洗涤，最后合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，所得产物用硅胶柱纯化，流动相为二氯甲烷：石油醚＝1:2,最后得到4.1mmol单体E1-1。真空环境下干燥待用。MS(ASAP)＝683.2
⑵单体E1-2的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000057
合成步骤如下：
a.氮气环境保护下，将10mmol的化合物3溶解于250ml的干燥DMF溶液中，所得反应溶液置入冰浴中搅拌，逐滴加入11.0mmol的三氯氧磷(POCl3)溶液，滴加完毕后，继续反应30分钟，逐渐升至室温并反应2小时，加水淬灭反应，二氯甲烷萃取，水洗涤，合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，得化合物4的粗产物，粗产物用二氯甲烷与正已烷重结晶得产品8.4mmol。真空干燥待用。MS(ASAP)＝641.3。
b.将上述所得5.0mmol化合物4溶解于200ml干燥的四氢呋喃(THF)溶液中，氮气环境保护下，反应液置于-78℃的温度下搅拌，逐滴加入8.0mmol亚甲基三苯基磷(Wittig试剂)，待加入完毕后，逐渐升至室温，继续在室温下搅拌过夜，加水淬灭反应，所有反应液用二氯甲烷萃取，有机相用水洗涤，最后合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，所得产物用硅胶柱纯化，流动相为二氯甲烷：石油醚＝4:1,最后得到4.5mmol单体E1-2。真空环境下干燥待用。MS(ASAP)＝639.4。
⑶单体E1-3的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000058
单体E1-3的合成步骤与单体E1-2的合成步骤类似，所不同的是其第一步用到的是化合物5，接下来生成的含醛基中间体为6。最后得到的中间体E1-3为白色固体粉末。MS(ASAP)＝681.2。
⑷单体E1-4的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000059
单体E1-4的合成步骤与单体E1-2的合成步骤类似，所不同的是其第一步用到的是化合物5-1，接下来生成的含醛基中间体为6-1。最后得到的中间体E1-4为白色固体粉末。MS(ASAP)＝ 637.2。
⑸单体E2-1的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000060
单体E2-1的合成步骤与单体E1-1的合成步骤类似，所不同的是其第一步用到的是化合物7，接下来生成的含醛基中间体为8。最后得到的中间体E2-1为米白色固体粉末。MS(ASAP)＝660.3。
⑹单体E2-2的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000061
单体E2-2的合成步骤与单体E1-1的合成步骤类似，所不同的是其第一步用到的是化合物9，接下来生成的含醛基中间体为10。最后得到的中间体E2-2为米白色固体粉末。MS(ASAP)＝662.3。
⑺单体E2-3的合成
合成实验路线如下图所示：
Figure PCTCN2017112716-appb-000062
单体E2-3的合成步骤与单体E1-1的合成步骤类似，所不同的是其第一步用到的是化合物11，接下来生成的含醛基中间体为12。最后得到的中间体E2-3为米白色固体粉末。MS(ASAP)＝647.3。
⑻单体E2-4的合成
Figure PCTCN2017112716-appb-000063
单体E2-4的合成步骤与单体E1-1的合成步骤类似，所不同的是其第一步用到的是化合物13，接下来生成的含醛基中间体为14。最后得到的中间体E2-4为米白色固体粉末。MS(ASAP)＝434.4。
2.单体的能量结构
有机重复结构单元的能量结构可通过量子计算得到，比如利用TD-DFT(含时密度泛函理论)通过Gaussian03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。首先用半经验方法“Ground State/Semi-empirical/Default Spin/AM1”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 03W的直接计算结果，单位为Hartree。结果如表一所示，其中ΔHOMO＝HOMO-(HOMO-1)：
表一
Figure PCTCN2017112716-appb-000064
3.高聚物的合成
对于高聚物的合成，其主要合成步骤如下：以P1聚合物的合成为例，在氮气保护条件下，将0.5mmolE1-1、0.50mmol E2-1的单体溶解于甲苯溶剂中，同时用注射器加入0.01mmol 2,2- 偶氮二异丁腈(AIBN引发剂)，密封，在60℃下反应4小时，当反应完成后，冷却至室温，用甲醇来沉淀出聚合物。沉淀用四氢呋喃(THF)溶解，再用甲醇沉淀。如此重复
Figure PCTCN2017112716-appb-000065
次，真空干燥，得到聚合物P1的固体。
对于P2～P17合成步骤与P1类似，不同的是含不同比例的乙烯基单体，对于P2～P17所包含的单体及比例如下表所示：
Figure PCTCN2017112716-appb-000066
其中P1-9是本申请中通式(1)所代表的高聚物，P10-17是本申请中通式(4)所代表的高聚物。
4.OLED器件的制备及测量
下面通过具体实施例来详细说明采用上述高聚物的OLED器件的制备过程，该OLED器件的结构为：ITO/HIL/HTL/EML/ETL/阴极，制备步骤如下：
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理；
b、HIL(空穴注入层，60nm):60nm的PEDOT(聚乙撑二氧噻吩，CleviosTM AI4083)作为HIL 在超净室旋转涂布而成，并在180℃的热板上处理10分钟；
c、HTL(空穴传输层，20nm):20nm的TFB或PVK(Sigma Aldrich,平均Mn 25,000-50,000)是在氮气手套箱中通过旋转涂布而成，所用的溶液是加入至甲苯溶剂的TFB或PVK(Sigma Aldrich)，溶液溶度5mg/ml，随后在180℃的热板上处理60分钟；
其中，TFB(H.W.SandsCorp.)是一种空穴传输材料，用于HTL，其结构式如下：
Figure PCTCN2017112716-appb-000067
d、EML(有机发光层):EML是在氮气手套箱中通过旋转涂布而成，所用的溶液是加入至甲苯溶剂的高聚物(P1-P10)以及一定量的Ir(PPy)3，溶液溶度10mg/ml，随后在180℃的热板上处理10分钟；表二列出器件的EML的组分和厚度；
表二
OLED器件 HTL EML组成及厚度
OLED1 PVK P1:(15％)Ir(ppy)3(80nm)
OLED2 PVK P2:(15％)Ir(ppy)3(65nm)
OLED3 TFB P3:(15％)Ir(ppy)3(80nm)
OLED4 TFB P4:(15％)Ir(ppy)3(80nm)
OLED5 TFB P5:(15％)Ir(ppy)3(80nm)
OLED6 PVK P6:(15％)Ir(ppy)3(65nm)
OLED7 PVK P7:(15％)Ir(ppy)3(65nm)
OLED8 TFB P8(15％)Ir(ppy)3(65nm)
OLED9 TFB P9(15％)Ir(ppy)3(65nm)
e、阴极:Ba/Al(2nm/100nm)在高真空(1×10-6毫巴)中热蒸镀而成；
f、封装:器件在氮气手套箱中用紫外线固化树脂封装。
各OLED器件的电流电压及发光(IVL)特性通过表征设备来表征，同时记录重要的参数如效率，寿命及驱动电压。OLED器件的性能总结在表三中。
表三
Figure PCTCN2017112716-appb-000068
Figure PCTCN2017112716-appb-000069
类似的，P10-P17可以取代TFB或PVK，用作OLED的HTL。
本申请通式(1)～(3)所代表的高聚物易于形成激基络合物，在用于磷光主体时，可以提高器件的效率，同时由于在有机溶剂中具有较好的溶解性，成膜性能好，从而为印刷OLED提供了较好的材料解决方案。本申请通式(4)所代表的高聚物具有较高的稳定性，并易于溶液加工。

Claims (20)

  1. 一种高聚物，其特征在于，包括通式(1)所示的重复单元：
    Figure PCTCN2017112716-appb-100001
    其中，n和m是大于或等于1的整数；
    min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))+0.1eV，其中，LUMO(E1)、HOMO(E1)及ET(E1)分别是E1基团的最高占有轨道、最低未占有轨道及三线态的能级，LUMO(E2)、HOMO(E2)及ET(E2)分别是E2基团的最高占有轨道、最低未占有轨道及三线态的能级。
  2. 根据权利要求1所述的高聚物，其特征在于，HOMO(E1)-(HOMO-1)(E1)≥0.3eV和/或HOMO(E2)-(HOMO-1)(E2)≥0.3eV，其中，(HOMO-1)(E1)是所述E1基团的第二高的占有轨道能级，(HOMO-1)(E2)是所述E2基团的第二高的占有轨道能级。
  3. 根据权利要求1-2中任何一个所述的高聚物，其特征在于，n:m的比例为从3:7到7:3。
  4. 根据权利要求1-3中任何一个所述的高聚物，其特征在于，包括通式(2)所示的重复单元:
    Figure PCTCN2017112716-appb-100002
    其中，R选自具有1-15个碳原子的直链烷烃、具有1-15个碳原子的支链烷烃、具有2-20个碳原子的芳香族、杂芳香族以及非芳香族环系中的至少一种；o是大于或等于0的整数。
  5. 根据权利要求1-4中任何一个所述的高聚物，其特征在于，所述E1基团含有供电子基D，和/或所述E2基团含有吸电子基A。
  6. 根据权利要求1-5中任何一个所述的高聚物，其特征在于，所述E1基团含有通式(I)所代表的结构单元：
    Figure PCTCN2017112716-appb-100003
    其中，Ar为芳香族或杂芳族结构单元，所述供电子基D在多次出现时相同或不相同，p为1到6之间的整数，q是0或1。
  7. 根据权利要求6所述的高聚物，其特征在于，所述供电子基D含有取代或未取代的、结构式D1至D15所代表的结构单元的至少一种：
    Figure PCTCN2017112716-appb-100004
  8. 根据权利要求1-7中任何一个所述的高聚物，其特征在于，所述E2基团含有通式(II)所代表的结构单元：
    Figure PCTCN2017112716-appb-100005
    其中，Ar为芳香族或杂芳族结构单元，所述吸电子基A在多次出现时相同或不相同，r为1到6之间的整数，s等于0或1。
  9. 根据权利要求8所述的高聚物，其特征在于，所述吸电子基A选自F或氰基，此时，s等于1；或所述吸电子基A包括取代或未取代的如下结构单元中的至少一种：
    Figure PCTCN2017112716-appb-100006
    其中，n1是一个从1到3的整数；X1-X8选于CR12或N，并且至少有一个是N，其中R12为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基；Z1-Z3为单键或C(R12)2、O或S。
  10. 根据权利要求6和8中任何一个所述的高聚物，其特征在于，Ar含有如下结构单元中的至少一种：
    Figure PCTCN2017112716-appb-100007
    Figure PCTCN2017112716-appb-100008
    其中n2为1、2、3或4。
  11. 根据权利要求1-10中任何一个所述的高聚物，其中，所述E1基团包含有如下结构式的结构单元中的至少一种：
    Figure PCTCN2017112716-appb-100009
    Figure PCTCN2017112716-appb-100010
  12. 根据权利要求1-11中任何一个所述的高聚物，其中，所述E2基团包含有如下结构式的结构单元中的至少一种：
    Figure PCTCN2017112716-appb-100011
    Figure PCTCN2017112716-appb-100012
    Figure PCTCN2017112716-appb-100013
  13. 根据权利要求1-12中任何一个所述的高聚物，在侧链上进一步包括空穴注入或传输基团、空穴阻挡基团、电子注入或传输基团、电子阻挡基团、有机基质基团、单重态发光基团(荧光发光基团)、三重态发光基团(磷光发光基团)和TADF发光基团中的至少一种。
  14. 一种高聚物，包括通式(4)所示的重复单元：
    Figure PCTCN2017112716-appb-100014
    其中，n是大于或等于1的自然数，其特征在于，E1基团是供电子基团，HOMO(E1)–(HOMO-1)(E1)≥0.3eV，其中，HOMO(E1)为所述E1基团的最高占有轨道的能级，(HOMO-1)(E1)为第二高的占有轨道的能级。
  15. 一种混合物，其特征在于，包括如权利要求1至14任一项所述的高聚物，并且进一步包括空穴(也称电洞)注入或传输材料(HIM/HTM)、空穴阻挡材料(HBM)、电子注入或传输材料(EIM/ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、单重态发光体(荧光发光体)、三重态发光体(磷光发光体)和TADF发光体中的至少一种。
  16. 一种组合物，包括如权利要求1至14任一项所述的高聚物以及有机溶剂。
  17. 一种有机电子器件，其特征在于，包括如权利要求1至14任一项所述的高聚物。
  18. 根据权利要求17所述的有机电子器件，其特征在于，所述有机电子器件为有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机自旋电子器件，有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
  19. 一种用于聚合的单体，具有通式(5)：
    Figure PCTCN2017112716-appb-100015
    其特征在于，E1基团的(HOMO–(HOMO-1)≥0.3eV，其中，HOMO为所述E1基团的最高占有轨道能级，HOMO-1为所述E1基团的的第二高占有轨道能级。
  20. 一种混合单体，包括第一单体和第二单体，所述第一单体和所述第二单体分别具有通式(5)和通式(6)：
    Figure PCTCN2017112716-appb-100016
    其特征在于，min((LUMO(E1)-HOMO(E2),LUMO(E2)-HOMO(E1))≤min(ET(E1),ET(E2))+0.1eV，其中，LUMO(E1)、HOMO(E1)及ET(E1)分别是E1基团的最高占有轨道、最低未占有轨道及三线态的能级，LUMO(E2)、HOMO(E2)及ET(E2)分别是E2基团的最高占有轨道、最低未占有轨道及三线态的能级。
PCT/CN2017/112716 2016-11-23 2017-11-23 高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体 Ceased WO2018095395A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17874343.1A EP3547384B1 (en) 2016-11-23 2017-11-23 High polymer, mixture containing same, composition, organic electronic component, and monomer for polymerization
US16/463,273 US11453745B2 (en) 2016-11-23 2017-11-23 High polymer, mixture containing same, composition, organic electronic component, and monomer for polymerization
CN201780059565.9A CN109791992B (zh) 2016-11-23 2017-11-23 高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201611047040.7 2016-11-23
CN201611047040 2016-11-23

Publications (1)

Publication Number Publication Date
WO2018095395A1 true WO2018095395A1 (zh) 2018-05-31

Family

ID=62195747

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/112716 Ceased WO2018095395A1 (zh) 2016-11-23 2017-11-23 高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体

Country Status (4)

Country Link
US (1) US11453745B2 (zh)
EP (1) EP3547384B1 (zh)
CN (1) CN109791992B (zh)
WO (1) WO2018095395A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021135841A1 (zh) 2019-12-30 2021-07-08 广州华睿光电材料有限公司 有机电致发光器件和含稠环的芳香族化合物

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11404644B2 (en) * 2016-12-22 2022-08-02 Guangzhou Chinaray Optoelectronic Materials Ltd. Organic functional compounds, mixtures, formulations, organic functional thin films and preparation methods therefor and organic electronic devices
US11482679B2 (en) * 2017-05-23 2022-10-25 Kyushu University, National University Corporation Compound, light-emitting lifetime lengthening agent, use of n-type compound, film and light-emitting device
KR102717925B1 (ko) * 2018-12-05 2024-10-15 엘지디스플레이 주식회사 유기발광다이오드 및 이를 포함하는 유기발광장치
CN113906577B (zh) * 2019-08-23 2025-02-21 株式会社Lg化学 有机发光器件

Citations (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567450A (en) 1968-02-20 1971-03-02 Eastman Kodak Co Photoconductive elements containing substituted triarylamine photoconductors
US3615404A (en) 1968-04-25 1971-10-26 Scott Paper Co 1 3-phenylenediamine containing photoconductive materials
US4720432A (en) 1987-02-11 1988-01-19 Eastman Kodak Company Electroluminescent device with organic luminescent medium
US4769292A (en) 1987-03-02 1988-09-06 Eastman Kodak Company Electroluminescent device with modified thin film luminescent zone
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
US5121029A (en) 1987-12-11 1992-06-09 Idemitsu Kosan Co., Ltd. Electroluminescence device having an organic electroluminescent element
US5130603A (en) 1989-03-20 1992-07-14 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
JPH0853397A (ja) 1994-08-12 1996-02-27 Toyo Ink Mfg Co Ltd ジアリールアミン誘導体、その製造方法及び用途
JP2913116B2 (ja) 1990-11-20 1999-06-28 株式会社リコー 電界発光素子
US6020078A (en) 1998-12-18 2000-02-01 Eastman Kodak Company Green organic electroluminescent devices
WO2000070655A2 (en) 1999-05-13 2000-11-23 The Trustees Of Princeton University Very high efficiency organic light emitting devices based on electrophosphorescence
WO2001021729A1 (en) 1999-09-21 2001-03-29 Idemitsu Kosan Co., Ltd. Organic electroluminescence and organic luminous medium
WO2001041512A1 (en) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US6251531B1 (en) 1995-02-25 2001-06-26 Toyo Ink Manufacturing Co., Ltd. Light-emitting material for organic electroluminescence device, and organic electroluminescence device for which the light-emitting material is adapted
EP1144543A1 (en) 1998-12-02 2001-10-17 South Bank University Enterprises Ltd. Electroluminescent quinolates
US20010053462A1 (en) 2000-05-02 2001-12-20 Masayuki Mishima Light-emitting device
WO2002002714A2 (en) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
WO2002015645A1 (en) 2000-08-11 2002-02-21 The Trustees Of Princeton University Organometallic compounds and emission-shifting organic electrophosphorescence
EP1191613A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
EP1191614A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device and metal coordination compound therefor
EP1191612A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
US6824895B1 (en) 2003-12-05 2004-11-30 Eastman Kodak Company Electroluminescent device containing organometallic compound with tridentate ligand
US6830828B2 (en) 1998-09-14 2004-12-14 The Trustees Of Princeton University Organometallic complexes as phosphorescent emitters in organic LEDs
US6835469B2 (en) 2001-10-17 2004-12-28 The University Of Southern California Phosphorescent compounds and devices comprising the same
CN1583691A (zh) 2004-06-04 2005-02-23 友达光电股份有限公司 蒽化合物以及包括此蒽化合物的有机电致发光装置
WO2005019373A2 (de) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Übergangsmetallkomplexe mit carbenliganden als emitter für organische licht-emittierende dioden (oleds)
WO2005033244A1 (de) 2003-09-29 2005-04-14 Covion Organic Semiconductors Gmbh Metallkomplexe
US20050258742A1 (en) 2004-05-18 2005-11-24 Yui-Yi Tsai Carbene containing metal complexes as OLEDs
WO2006000388A1 (de) 2004-06-26 2006-01-05 Merck Patent Gmbh Organische elektrolumineszenzvorrichtung
WO2006000389A1 (de) 2004-06-26 2006-01-05 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
US7029766B2 (en) 2003-12-05 2006-04-18 Eastman Kodak Company Organic element for electroluminescent devices
WO2006058737A1 (de) 2004-12-01 2006-06-08 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
US20060210830A1 (en) 2005-03-15 2006-09-21 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescence device using the same
US20060222886A1 (en) 2005-04-04 2006-10-05 Raymond Kwong Arylpyrene compounds
WO2006122630A1 (de) 2005-05-20 2006-11-23 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
US20070087219A1 (en) 2005-10-19 2007-04-19 Eastman Kodak Company Electroluminescent device
US20070092753A1 (en) 2005-10-26 2007-04-26 Eastman Kodak Company Organic element for low voltage electroluminescent devices
DE102005058557A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische Elektrolumineszenzvorrichtung
WO2007065549A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische elektrolumineszenzvorrichtungen
US7250532B2 (en) 2001-03-16 2007-07-31 Idemitsu Kosan Co., Ltd. Method for producing aromatic amino compound
WO2007095118A2 (en) 2006-02-10 2007-08-23 Universal Display Corporation METAL COMPLEXES OF CYCLOMETALLATED IMIDAZO[1,2-f]PHENANTHRIDINE AND DIIMIDAZO[1,2-A:1',2'-C]QUINAZOLINE LIGANDS AND ISOELECTRONIC AND BENZANNULATED ANALOGS THEREOF
WO2007115610A1 (de) 2006-04-01 2007-10-18 Merck Patent Gmbh Materialen für organische elektrolumineszenzvorrichtungen
WO2007119420A1 (ja) * 2006-03-22 2007-10-25 Konica Minolta Holdings, Inc. 有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス素子の発光色度安定化方法、照明装置及び電子ディスプレイ装置
US20070252517A1 (en) 2006-04-27 2007-11-01 Eastman Kodak Company Electroluminescent device including an anthracene derivative
WO2007140847A1 (de) 2006-06-02 2007-12-13 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2008006449A1 (de) 2006-07-11 2008-01-17 Merck Patent Gmbh Neue materialien für organische elektrolumineszenzvorrichtungen
US20080027220A1 (en) 2004-07-16 2008-01-31 Merck Patent Gmbh Metal Complexes
US20080113101A1 (en) 2006-11-09 2008-05-15 Idemitsu Kosan Co., Ltd. Organic-electroluminescence-material-containing solution, method for forming thin film of organic electroluminescence material, thin film of organic electroluminescence material and organic electroluminescence device
EP1941562A1 (en) 2005-10-26 2008-07-09 Eastman Kodak Company Organic element for low voltage electroluminescent devices
US20090061681A1 (en) 2007-09-05 2009-03-05 Mcmunigal Tom Electrical receptacle assembly
US20090134784A1 (en) 2004-10-21 2009-05-28 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
WO2009116414A1 (ja) * 2008-03-19 2009-09-24 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子
WO2009118087A1 (de) 2008-03-25 2009-10-01 Merck Patent Gmbh Metallkomplexe
WO2009146770A2 (de) 2008-06-05 2009-12-10 Merck Patent Gmbh Elektronische vorrichtung enthaltend metallkomplexe
WO2010015307A1 (de) 2008-08-04 2010-02-11 Merck Patent Gmbh Elektronische vorrichtung enthaltend metallkomplexe mit isonitrilliganden
US20100045171A1 (en) * 2006-09-08 2010-02-25 Konica Minolta Holdings, Inc. Organic electroluminescence element, lighting device and display device
WO2010031485A1 (de) 2008-09-22 2010-03-25 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010054731A1 (de) 2008-11-13 2010-05-20 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010054728A1 (de) 2008-11-13 2010-05-20 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
US20100171101A1 (en) * 2006-03-30 2010-07-08 Konica Minolta Holdings, Inc. Organic electroluminescent element, method of manufacturing organic electroluminescent element, lighting device, and display device
US7767317B2 (en) 2005-10-26 2010-08-03 Global Oled Technology Llc Organic element for low voltage electroluminescent devices
WO2010086089A1 (de) 2009-02-02 2010-08-05 Merck Patent Gmbh Metallkomplexe
WO2010099852A1 (de) 2009-03-02 2010-09-10 Merck Patent Gmbh Metallkomplexe mit azaborol-liganden und elektronische vorrichtung damit
WO2010102709A1 (de) 2009-03-13 2010-09-16 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010135519A1 (en) 2009-05-20 2010-11-25 Universal Display Corporation Metal complexes with boron-nitrogen heterocycle containing ligands for use in organic light emitting devices
US20110084601A1 (en) * 2008-07-01 2011-04-14 Konica Minolta Holdings, Inc. White light emission organic electroluminescent element, illuminating device and display
WO2011110277A1 (en) 2010-03-11 2011-09-15 Merck Patent Gmbh Fibers in therapy and cosmetics
WO2011141110A2 (de) 2010-05-12 2011-11-17 Merck Patent Gmbh Photostabilisatoren
CN102270751A (zh) * 2011-07-26 2011-12-07 昆山维信诺显示技术有限公司 一种有机电致磷光发光器件及其制备方法
WO2011157339A1 (de) 2010-06-15 2011-12-22 Merck Patent Gmbh Metallkomplexe
WO2012007087A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
WO2012007088A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
WO2012007086A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
US20120217869A1 (en) 2011-02-28 2012-08-30 Kyushu University National University Corporation Delayed fluorescence material and organic electroluminescence device
TW201309778A (zh) 2011-07-15 2013-03-01 Univ Kyushu Nat Univ Corp 有機電致發光元件及使用於其之化合物
TW201309696A (zh) 2011-07-15 2013-03-01 Univ Kyushu Nat Univ Corp 延遲螢光材料及使用其之有機電致發光元件
WO2013133359A1 (ja) 2012-03-09 2013-09-12 国立大学法人九州大学 発光材料および有機発光素子
WO2013154064A1 (ja) 2012-04-09 2013-10-17 国立大学法人九州大学 有機発光素子ならびにそれに用いる発光材料および化合物
TW201343874A (zh) 2012-04-25 2013-11-01 Univ Kyushu Nat Univ Corp 發光材料及有機發光元件
TW201350558A (zh) 2012-05-17 2013-12-16 Univ Kyushu Nat Univ Corp 化合物、發光材料及有機發光元件
CN103483332A (zh) 2013-09-11 2014-01-01 中山大学 具有热激活延迟荧光和聚集诱导发光性能的新型压致发光材料及其合成方法和应用
CN105679949A (zh) * 2014-12-04 2016-06-15 广州华睿光电材料有限公司 有机发光晶体管及其应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3698067B2 (ja) 2001-03-30 2005-09-21 Ｊｓｒ株式会社 電子吸引性基および電子供与性基を有するモノマー、それを用いた共重合体、ならびにプロトン伝導膜
US7250226B2 (en) * 2001-08-31 2007-07-31 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
US10840450B2 (en) * 2014-12-04 2020-11-17 Guangzhou Chinaray Optoelectronic Materials Ltd. Polymer, and mixture or formulation, and organic electronic device containing same, and monomer thereof
US10319912B2 (en) 2015-01-29 2019-06-11 Samsung Electronics Co., Ltd. Charge-transporting material and organic light-emitting device including the same

Patent Citations (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567450A (en) 1968-02-20 1971-03-02 Eastman Kodak Co Photoconductive elements containing substituted triarylamine photoconductors
US3615404A (en) 1968-04-25 1971-10-26 Scott Paper Co 1 3-phenylenediamine containing photoconductive materials
US4720432A (en) 1987-02-11 1988-01-19 Eastman Kodak Company Electroluminescent device with organic luminescent medium
US4769292A (en) 1987-03-02 1988-09-06 Eastman Kodak Company Electroluminescent device with modified thin film luminescent zone
US5121029A (en) 1987-12-11 1992-06-09 Idemitsu Kosan Co., Ltd. Electroluminescence device having an organic electroluminescent element
US5130603A (en) 1989-03-20 1992-07-14 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
JP2913116B2 (ja) 1990-11-20 1999-06-28 株式会社リコー 電界発光素子
JPH0853397A (ja) 1994-08-12 1996-02-27 Toyo Ink Mfg Co Ltd ジアリールアミン誘導体、その製造方法及び用途
US6251531B1 (en) 1995-02-25 2001-06-26 Toyo Ink Manufacturing Co., Ltd. Light-emitting material for organic electroluminescence device, and organic electroluminescence device for which the light-emitting material is adapted
US6830828B2 (en) 1998-09-14 2004-12-14 The Trustees Of Princeton University Organometallic complexes as phosphorescent emitters in organic LEDs
EP1144543A1 (en) 1998-12-02 2001-10-17 South Bank University Enterprises Ltd. Electroluminescent quinolates
US6020078A (en) 1998-12-18 2000-02-01 Eastman Kodak Company Green organic electroluminescent devices
WO2000070655A2 (en) 1999-05-13 2000-11-23 The Trustees Of Princeton University Very high efficiency organic light emitting devices based on electrophosphorescence
WO2001021729A1 (en) 1999-09-21 2001-03-29 Idemitsu Kosan Co., Ltd. Organic electroluminescence and organic luminous medium
WO2001041512A1 (en) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US20010053462A1 (en) 2000-05-02 2001-12-20 Masayuki Mishima Light-emitting device
WO2002002714A2 (en) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
WO2002015645A1 (en) 2000-08-11 2002-02-21 The Trustees Of Princeton University Organometallic compounds and emission-shifting organic electrophosphorescence
EP1191613A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
EP1191614A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device and metal coordination compound therefor
EP1191612A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
US7250532B2 (en) 2001-03-16 2007-07-31 Idemitsu Kosan Co., Ltd. Method for producing aromatic amino compound
US6835469B2 (en) 2001-10-17 2004-12-28 The University Of Southern California Phosphorescent compounds and devices comprising the same
WO2005019373A2 (de) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Übergangsmetallkomplexe mit carbenliganden als emitter für organische licht-emittierende dioden (oleds)
WO2005033244A1 (de) 2003-09-29 2005-04-14 Covion Organic Semiconductors Gmbh Metallkomplexe
US6824895B1 (en) 2003-12-05 2004-11-30 Eastman Kodak Company Electroluminescent device containing organometallic compound with tridentate ligand
US7029766B2 (en) 2003-12-05 2006-04-18 Eastman Kodak Company Organic element for electroluminescent devices
US20050258742A1 (en) 2004-05-18 2005-11-24 Yui-Yi Tsai Carbene containing metal complexes as OLEDs
CN1583691A (zh) 2004-06-04 2005-02-23 友达光电股份有限公司 蒽化合物以及包括此蒽化合物的有机电致发光装置
WO2006000389A1 (de) 2004-06-26 2006-01-05 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
WO2006000388A1 (de) 2004-06-26 2006-01-05 Merck Patent Gmbh Organische elektrolumineszenzvorrichtung
US20080027220A1 (en) 2004-07-16 2008-01-31 Merck Patent Gmbh Metal Complexes
US20090134784A1 (en) 2004-10-21 2009-05-28 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
WO2006058737A1 (de) 2004-12-01 2006-06-08 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
US20060210830A1 (en) 2005-03-15 2006-09-21 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescence device using the same
US20060222886A1 (en) 2005-04-04 2006-10-05 Raymond Kwong Arylpyrene compounds
WO2006122630A1 (de) 2005-05-20 2006-11-23 Merck Patent Gmbh Verbindungen für organische elektronische vorrichtungen
US20070087219A1 (en) 2005-10-19 2007-04-19 Eastman Kodak Company Electroluminescent device
US7767317B2 (en) 2005-10-26 2010-08-03 Global Oled Technology Llc Organic element for low voltage electroluminescent devices
US20070092753A1 (en) 2005-10-26 2007-04-26 Eastman Kodak Company Organic element for low voltage electroluminescent devices
EP1941562A1 (en) 2005-10-26 2008-07-09 Eastman Kodak Company Organic element for low voltage electroluminescent devices
WO2007065549A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische elektrolumineszenzvorrichtungen
DE102005058557A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische Elektrolumineszenzvorrichtung
EP1957606A1 (de) 2005-12-08 2008-08-20 Merck Patent GmbH Neue materialien für organische elektroluminieszenzvorrichtungen
WO2007095118A2 (en) 2006-02-10 2007-08-23 Universal Display Corporation METAL COMPLEXES OF CYCLOMETALLATED IMIDAZO[1,2-f]PHENANTHRIDINE AND DIIMIDAZO[1,2-A:1',2'-C]QUINAZOLINE LIGANDS AND ISOELECTRONIC AND BENZANNULATED ANALOGS THEREOF
WO2007119420A1 (ja) * 2006-03-22 2007-10-25 Konica Minolta Holdings, Inc. 有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス素子の発光色度安定化方法、照明装置及び電子ディスプレイ装置
US20100171101A1 (en) * 2006-03-30 2010-07-08 Konica Minolta Holdings, Inc. Organic electroluminescent element, method of manufacturing organic electroluminescent element, lighting device, and display device
WO2007115610A1 (de) 2006-04-01 2007-10-18 Merck Patent Gmbh Materialen für organische elektrolumineszenzvorrichtungen
US20070252517A1 (en) 2006-04-27 2007-11-01 Eastman Kodak Company Electroluminescent device including an anthracene derivative
WO2007140847A1 (de) 2006-06-02 2007-12-13 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2008006449A1 (de) 2006-07-11 2008-01-17 Merck Patent Gmbh Neue materialien für organische elektrolumineszenzvorrichtungen
US20100045171A1 (en) * 2006-09-08 2010-02-25 Konica Minolta Holdings, Inc. Organic electroluminescence element, lighting device and display device
US20080113101A1 (en) 2006-11-09 2008-05-15 Idemitsu Kosan Co., Ltd. Organic-electroluminescence-material-containing solution, method for forming thin film of organic electroluminescence material, thin film of organic electroluminescence material and organic electroluminescence device
US20090061681A1 (en) 2007-09-05 2009-03-05 Mcmunigal Tom Electrical receptacle assembly
WO2009116414A1 (ja) * 2008-03-19 2009-09-24 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子
WO2009118087A1 (de) 2008-03-25 2009-10-01 Merck Patent Gmbh Metallkomplexe
WO2009146770A2 (de) 2008-06-05 2009-12-10 Merck Patent Gmbh Elektronische vorrichtung enthaltend metallkomplexe
US20110084601A1 (en) * 2008-07-01 2011-04-14 Konica Minolta Holdings, Inc. White light emission organic electroluminescent element, illuminating device and display
WO2010015307A1 (de) 2008-08-04 2010-02-11 Merck Patent Gmbh Elektronische vorrichtung enthaltend metallkomplexe mit isonitrilliganden
WO2010031485A1 (de) 2008-09-22 2010-03-25 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010054728A1 (de) 2008-11-13 2010-05-20 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010054731A1 (de) 2008-11-13 2010-05-20 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010086089A1 (de) 2009-02-02 2010-08-05 Merck Patent Gmbh Metallkomplexe
CN102282150A (zh) 2009-02-02 2011-12-14 默克专利有限公司 金属络合物
WO2010099852A1 (de) 2009-03-02 2010-09-10 Merck Patent Gmbh Metallkomplexe mit azaborol-liganden und elektronische vorrichtung damit
US20120004407A1 (en) 2009-03-02 2012-01-05 Merck Patent Gmbh Metal complexes having azaborol ligands and electronic device having the same
WO2010102709A1 (de) 2009-03-13 2010-09-16 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2010135519A1 (en) 2009-05-20 2010-11-25 Universal Display Corporation Metal complexes with boron-nitrogen heterocycle containing ligands for use in organic light emitting devices
WO2011110277A1 (en) 2010-03-11 2011-09-15 Merck Patent Gmbh Fibers in therapy and cosmetics
WO2011141110A2 (de) 2010-05-12 2011-11-17 Merck Patent Gmbh Photostabilisatoren
WO2011157339A1 (de) 2010-06-15 2011-12-22 Merck Patent Gmbh Metallkomplexe
WO2012007086A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
WO2012007087A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
WO2012007088A1 (de) 2010-07-16 2012-01-19 Merck Patent Gmbh Metallkomplexe
US20120217869A1 (en) 2011-02-28 2012-08-30 Kyushu University National University Corporation Delayed fluorescence material and organic electroluminescence device
TW201309778A (zh) 2011-07-15 2013-03-01 Univ Kyushu Nat Univ Corp 有機電致發光元件及使用於其之化合物
TW201309696A (zh) 2011-07-15 2013-03-01 Univ Kyushu Nat Univ Corp 延遲螢光材料及使用其之有機電致發光元件
CN102270751A (zh) * 2011-07-26 2011-12-07 昆山维信诺显示技术有限公司 一种有机电致磷光发光器件及其制备方法
WO2013133359A1 (ja) 2012-03-09 2013-09-12 国立大学法人九州大学 発光材料および有機発光素子
WO2013154064A1 (ja) 2012-04-09 2013-10-17 国立大学法人九州大学 有機発光素子ならびにそれに用いる発光材料および化合物
TW201343874A (zh) 2012-04-25 2013-11-01 Univ Kyushu Nat Univ Corp 發光材料及有機發光元件
TW201350558A (zh) 2012-05-17 2013-12-16 Univ Kyushu Nat Univ Corp 化合物、發光材料及有機發光元件
CN103483332A (zh) 2013-09-11 2014-01-01 中山大学 具有热激活延迟荧光和聚集诱导发光性能的新型压致发光材料及其合成方法和应用
CN105679949A (zh) * 2014-12-04 2016-06-15 广州华睿光电材料有限公司 有机发光晶体管及其应用

Non-Patent Citations (24)

* Cited by examiner, † Cited by third party
Title
ADACHI ET AL., APPL. PHYS. LETT., vol. 78, 2001, pages 1622 - 1624
ADACHI, ADV. MATER., vol. 21, 2009, pages 4802
ADACHI, ADV. MATER., vol. 25, 2013, pages 3707
ADACHI, ANGEW. CHEM. INT. ED, vol. 51, 2012, pages 11311
ADACHI, APPL. PHYS. LETT., vol. 101, 2012, pages 093306
ADACHI, APPL. PHYS. LETT., vol. 98, 2011, pages 083302
ADACHI, CHEM. COMMUN., vol. 48, 2013, pages 10385
ADACHI, CHEM. MATER., vol. 25, 2013, pages 3766
ADACHI, J. MATER. CHEM. C., vol. 1, 2013, pages 4599
ADACHI, J. PHYS. CHEM. A., vol. 117, 2013, pages 5607
ADACHI, NATURE PHOTONICS, vol. 6, 2012, pages 253
ADACHI: "134", J. AM CHEM. SOC, 2012, pages 14706
ADACHI: "48", CHEM. COMMUN., vol. 48, 2012, pages 11392
ADACHI: "492", NATURE, 2012, pages 234
BALDO, THOMPSON ET AL., NATURE, vol. 403, 2000, pages 750 - 753
DENDRIMERSDENDRONS: "KGaA", 2002, WILEY-VCH VERLAG GMBH & CO
J. KIDO ET AL., APPL. PHYS. LETT., vol. 65, 1994, pages 2124
JOHNSON ET AL., JACS, vol. 105, 1983, pages 1795
KIDO ET AL., CHEM. LETT., vol. 657, 1990
KIM ET AL., ADV. MATER., vol. 26, 2014, pages 5864
MA ET AL., SYNTH. METALS, vol. 94, 1998, pages 245
OTSUKI, EIJI ET AL.: "Vapor Deposition Polymerization of Vinyl Compounds and Fabrication of OLED Having Double Emmissive Layers", THIN SOLID FILMS, vol. 518, no. 2, 16 July 2009 (2009-07-16), pages 703 - 706, XP026707998, ISSN: 0040-6090 *
See also references of EP3547384A4
WRIGHTON, JACS, vol. 96, 1974, pages 998

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021135841A1 (zh) 2019-12-30 2021-07-08 广州华睿光电材料有限公司 有机电致发光器件和含稠环的芳香族化合物

Also Published As

Publication number Publication date
EP3547384A1 (en) 2019-10-02
CN109791992A (zh) 2019-05-21
US20190292309A1 (en) 2019-09-26
EP3547384A4 (en) 2019-11-27
CN109791992B (zh) 2021-07-23
US11453745B2 (en) 2022-09-27
EP3547384B1 (en) 2022-10-05

Similar Documents

Publication Publication Date Title
US10323180B2 (en) Deuterated organic compound, mixture and composition containing said compound, and organic electronic device
CN107001380B (zh) 化合物、包含其的混合物、组合物和有机电子器件
CN103985822B (zh) 有机混合物、包含其的组合物、有机电子器件及应用
US10840450B2 (en) Polymer, and mixture or formulation, and organic electronic device containing same, and monomer thereof
WO2019105327A1 (zh) 有机复合薄膜及其在有机电子器件中的应用
WO2017092508A1 (zh) D-a型化合物及其应用
CN108368045A (zh) 热激发延迟荧光材料、高聚物、混合物、组合物以及有机电子器件
US10573827B2 (en) Organic metal complex, and polymer, mixture, composition and organic electronic device containing same and use thereof
CN107004778B (zh) 有机混合物、包含其的组合物、有机电子器件及应用
US10510967B2 (en) Organic compound, and mixture, formulation and organic device comprising the same
WO2018095390A1 (zh) 有机化合物及其应用、有机混合物、有机电子器件
CN116685580B (zh) 有机混合物及其在有机电子器件的应用
WO2017118238A1 (zh) 氘代三芳胺衍生物及其在电子器件中的应用
WO2018095395A1 (zh) 高聚物、包含其的混合物、组合物和有机电子器件以及用于聚合的单体
CN104277063B (zh) 一种基于环硼氮烷的化合物及在有机电子器件中的应用
CN107978692B (zh) 有机混合物、包含其的组合物、有机电子器件及应用
CN114763475B (zh) 一种有机混合物及其在有机电子器件的应用
CN109791982B (zh) 有机混合物、有机组合物、有机电子器件及其制备方法
CN105226193B (zh) 一种包含有稠环化合物和金属有机配合物的电致发光器件
WO2018099431A1 (zh) 芘类有机化合物及其制备方法和应用
CN111278819A (zh) 双极性化合物、高聚物、混合物、组合物、有机电子器件及应用

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: 17874343

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017874343

Country of ref document: EP

Effective date: 20190624