WO2019090462A1 - Couche de transfert de charge polymère et dispositif électronique organique la comprenant - Google Patents

Couche de transfert de charge polymère et dispositif électronique organique la comprenant Download PDF

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Publication number
WO2019090462A1
WO2019090462A1 PCT/CN2017/109672 CN2017109672W WO2019090462A1 WO 2019090462 A1 WO2019090462 A1 WO 2019090462A1 CN 2017109672 W CN2017109672 W CN 2017109672W WO 2019090462 A1 WO2019090462 A1 WO 2019090462A1
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Prior art keywords
substituted
unsubstituted
arylene
alkylene
charge transfer
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PCT/CN2017/109672
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English (en)
Inventor
Zhengming TANG
Anatoliy Sokolov
Chun Liu
Sukrit MUKHOPADHYAY
Peter Trefonas Iii
Minrong ZHU
Chong XING
David D Devore
Hong Yeop NA
Emad Aqad
Yoo Jin Doh
Yang Li
John W Kramer
Liam P Spencer
Robert Wright
Shaoguang Feng
Original Assignee
Dow Global Technologies Llc
Rohm And Haas Electronic Materials Llc
Rohm And Haas Electronic Materials Korea Ltd.
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Application filed by Dow Global Technologies Llc, Rohm And Haas Electronic Materials Llc, Rohm And Haas Electronic Materials Korea Ltd. filed Critical Dow Global Technologies Llc
Priority to PCT/CN2017/109672 priority Critical patent/WO2019090462A1/fr
Publication of WO2019090462A1 publication Critical patent/WO2019090462A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present disclosure relates to a polymeric charge transfer layer composition
  • a polymeric charge transfer layer composition comprising a polymer comprising, as polymerized units, at least one Monomer A and at least one Monomer B.
  • the present disclosure further relates to an organic electronic device, especially, a light emitting device containing the polymeric charge transfer layer.
  • Organic electronic devices are devices that carry out electrical operations using at least one organic material. They are endowed with advantages such as flexibility, low power consumption, and relatively low cost over conventional inorganic electronic devices.
  • Organic electronic devices usually include organic light emitting devices, organic solar cells, organic memory devices, organic sensors, organic thin film transistors, and power generation and storage devices such as organic batteries, fuel cells, and organic supercapacitors.
  • Such organic electronic devices are prepared from hole injection or transportation materials, electron injection or transportation materials, or light emitting materials.
  • a typical organic light emitting device is an organic light emitting diode (OLED) having a multi-layer structure, and typically includes an anode, and a metal cathode. Sandwiched between the anode and the metal cathode are several organic layers such as a hole injection layer (HIL) , a hole transfer layer (HTL) , an emitting layer (EML) , an electron transfer layer (ETL) , and an electron injection layer (EIL) .
  • HIL hole injection layer
  • HTL hole transfer layer
  • EML emitting layer
  • ETL electron transfer layer
  • EIL electron injection layer
  • the present disclosure provides a polymeric charge transfer layer composition
  • a polymeric charge transfer layer composition comprising a polymer comprising, as polymerized units, at least one Monomer A and at least one Monomer B.
  • Monomer A has the following Structure A:
  • Ar 1 through Ar 3 and Ar 1 ’through Ar 3 ’ are each independently selected from a substituted or unsubstituted aromatic moiety, and a substituted or unsubstituted heteroaromatic moiety;
  • L 1 and L 1 ’ are each independently selected from the group consisting of a covalent bond, a substituted or unsubstituted C 6 -C 60 arylene, and a substituted or unsubstituted C 6 -C 60 heteroarylene, a substituted or unsubstituted C 6 -C 60 aryloxylene, a substituted or unsubstituted C 1 -C 50 alkylene, a substituted or unsubstituted C 1 -C 50 alkoxylene, and a substituted or unsubstituted C 1 -C 50 alkoxycarbonylene; and
  • R 2 , R 3 , R 2 ’, and R 3 ’ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C 1 -C 50 alkyl, a substituted or unsubstituted C 1 -C 50 alkoxy, a substituted or unsubstituted C 1 -C 50 alkoxycarbonyl, a substituted or unsubstituted C 6 -C 60 aryl, a substituted or unsubstituted C 1 -C 60 heteroaryl, a substituted or unsubstituted C 6 -C 60 aryloxy, a substituted or unsubstituted C 6 -C 50 arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl with the provision that at least one of R 2 and R 3 contains an ether group
  • the present disclosure further provides an organic light emitting device and an organic electronic device comprising the polymeric charge transfer layer.
  • the polymeric charge transfer layer composition of the present disclosure comprises a polymer and an optional p-dopant.
  • the polymer comprises, as polymerized units, at least one Monomer A and at least one Monomer B.
  • the polymer comprises Monomer A having the following Structure A:
  • Ar 1 through Ar 3 and Ar 1 ’through Ar 3 ’ are each independently selected from a substituted or unsubstituted aromatic moiety, and a substituted or unsubstituted heteroaromatic moiety.
  • L 1 and L 1 ’ are each independently selected from the group consisting of a covalent bond, a substituted or unsubstituted C 6 -C 60 arylene, and a substituted or unsubstituted C 6 -C 60 heteroarylene, a substituted or unsubstituted C 6 -C 60 aryloxylene, a substituted or unsubstituted C 1 -C 50 alkylene, a substituted or unsubstituted C 1 -C 50 alkoxylene, and a substituted or unsubstituted C 1 -C 50 alkoxycarbonylene.
  • R 2 , R 3 , R 2 ’, and R 3 ’ are each independently selected from the group consisting of hydrogen, deuterium ( “D” ) , a substituted or unsubstituted C 1 -C 50 alkyl, a substituted or unsubstituted C 1 -C 50 alkoxy, a substituted or unsubstituted C 1 -C 50 alkoxycarbonyl, a substituted or unsubstituted C 6 -C 60 aryl, a substituted or unsubstituted C 1 -C 60 heteroaryl, a substituted or unsubstituted C 6 -C 60 aryloxy, a substituted or unsubstituted C 6 -C 50 arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl with the provision that at least one of R 2 and R 3 contains below ether group
  • the ether group could be selected from, but are not limited to below groups:
  • R 1 and R 1 ’ each independently has the functional group represented by Structure I, so that the polymer obtained therefrom has a polymerization site.
  • R 4 to R 6 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C 1 -C 50 hydrocarbyl, a substituted or unsubstituted C 1 -C 50 heterohydrocarbyl, a halogen, a cyano, a substituted or unsubstituted C 6 -C 50 aryl, and a substituted or unsubstituted C 4 -C 50 heteroaryl.
  • L 2 ’ is selected from the group consisting of a covalent bond; -O-; -alkylene-; -arylene-; -alkylene-arylene-; -arylene-alkylene-; -O-alkylene-; -O-arylene-; -O-alkylene-arylene-; -O-alkylene-O-; -O-alkylene-O-alkylene-O-; -O-arylene-O-; -O-alkylene-arylene-O-; -O- (CH 2 CH 2 -O) n -, wherein n is an integer from 2 to 20; -O-alkylene-O-alkylene-; -O-alkylene-O-arylene-; -O-arylene-O-; -O-arylene-O-alkyene-; and -O-arylene-O-arylene.
  • L 2 ’ is -alkylene-, -arylene-, -alkylene-arylene-, -arylene-alkylene-, or a covalent bond. More preferably, L 2 ’is -arylene-, -arylene-alkylene-, or a covalent bond.
  • Structure I includes the following Structures (I-1) through (I-12) :
  • Structure I is selected from Structures (I-4) , (I-5) , (I-11) , and (I-12) .
  • Monomer A is selected from the following Compounds (A1) through (A8) :
  • Monomer A useful in the present disclosure has a molecular weight of from 500 g/mole to 28,000 g/mole, preferably from 800 g/mole to 14,000 g/mole, and preferably from 1,000 g/mole to 7,000 g/mole.
  • Monomer A is further purified through ion exchange beads to remove cationic and anionic impurities, such as metal ion, sulfate ion, formate ion, oxalate ion and acetate ion.
  • the purity of Monomer A is equal to or above 99%, equal to or above 99.4%, or even equal to or above 99.5%.
  • the said purification is achieved through well-known methods in the art including fractionation, sublimation, chromatography, crystallization and precipitation methods.
  • Monomer A is present in the present disclosure in an amount of at most 50%by mole, or 30%by mole or less, 20%by mole or less, 10%by mole or less, or even 5%by mole or less, based on the total moles of all monomers in the polymer.
  • Monomer B is present in the present disclosure in an amount of at least 50%by mole, 70%by mole or more, 80%by mole or more, 90%by mole or more, or even 95%by mole, based on the total moles of all monomers in the polymer.
  • the polymer comprises at least 90%by mole of Monomer B based on the total moles of all monomers in the composition.
  • Monomer B is selected from the following Compounds (B1) through (B8) :
  • the polymer may be blended with one or more p-dopants to make the polymeric charge transfer layer composition.
  • P-dopants are selected from ionic compounds including trityl salts, ammonium salts, iodonium salts, tropylium salts, imidazolium salts, phosphonium salts, oxonium salts, and mixtures thereof.
  • the ionic compounds are selected from trityl borates, ammonium borates, iodonium borates, tropylium borates, imidazolium borates, phosphonium borates, oxonium borates, and mixtures thereof.
  • PEDOT polymer based mixtures
  • PSS poly (3, 4-ethylenedioxythiophene) /poly (styrenesulfonate)
  • Plexcore TM OC RG-1200 Poly (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2, 5-diyl) available from Sigma-Aldrich, could also be selected.
  • Suitable examples of p-dopants used in the present disclosure include the following Compounds (p-1) through (p-13) :
  • the p-dopant is the following compound (p-1) :
  • the p-dopant is present in the present disclosure at an amount of 1%by weight or more, 3%by weight or more, 5%by weight or more, or even 7%by weight or more, and at the same time, 20%by weight or less, 15%by weight or less, 12%by weight or less, or even 10%by weight or less, based on the total weight of the polymeric charge transfer layer composition.
  • the p-dopant of the present disclosure is at least 99%pure, as measured by liquid chromatography/mass spectrometry (LC/MS) on a solids weight basis, more preferably at least 99.5%, more preferably at least 99.7%.
  • LC/MS liquid chromatography/mass spectrometry
  • the p-dopant may form a separate layer in adjacent to the layer of polymeric charge transfer materials, or blended with polymeric charge transfer materials of the present disclosure to form a single layer.
  • the present disclosure provides a method of making an organic electronic device.
  • the method comprises providing the polymeric charge transfer layer composition of the present disclosure, and dissolving or dispersing the polymeric charge transfer layer composition in any of the organic solvents known or proposed to be used in the fabrication of an organic electronic device by solution process.
  • organic solvents include tetrahydrofuran (THF) , cyclohexanone, chloroform, 1, 4-dioxane, acetonitrile, ethyl acetate, tetralin, chlorobenzene, toluene, xylene, anisole, mesitylene, tetralone, and mixtures thereof.
  • THF tetrahydrofuran
  • cyclohexanone chloroform
  • 1, 4-dioxane acetonitrile
  • ethyl acetate tetralin
  • chlorobenzene toluene
  • xylene anisole, mesitylene, t
  • the polymeric charge transfer layer solution is then deposited over a first electrode.
  • the deposition may be performed by any of various types of solution processing techniques known or proposed to be used for fabricating organic electronic devices.
  • the polymeric charge transfer layer solution can be deposited using a printing process, such as inkjet printing, nozzle printing, offset printing, transfer printing, or screen printing; or for example, using a coating process, such as spray coating, spin coating, or dip coating.
  • the solvent is removed, which may be performed by using conventional method such as vacuum drying and/or heating.
  • the polymeric charge transfer layer solution is further cross-linked to form the polymeric charge transfer layer.
  • Cross-linking may be performed by exposing the layer solution to heat and/or actinic radiation, including UV light, gamma rays, or x-rays.
  • Cross-linking may be carried out in the presence of an initiator that decomposed under heat or irradiation to produce free radicals or ions that initiate the cross-linking reaction.
  • the cross-linking may be performed in-situ during the fabrication of a device.
  • the polymeric charge transfer layer made thereof is preferably free of residual moieties which are reactive or decomposable with exposure to light, positive charges, negative charges or excitons.
  • the process of solution deposition and cross-linking can be repeated to create multiple layers.
  • an OLED contains the following layers in contact with each other in order as follows: a substrate, a first conductive layer, optionally one or more hole injection layers, one or more hole transport layers, optionally one or more electron blocking layers, an emitting layer, optionally one or more hole blocking layers, optionally one or more electron transport layer, an electron injection layer, and a second conductive layer.
  • the polymeric charge transfer layer is used as the hole transport layer in the OLED.
  • the first conductive layer is used as an anode and in general is a transparent conducting oxide, for example, fluorine-doped tin oxide, antimony-doped tin oxide, zinc oxide, aluminum-doped zinc oxide, indium tin oxide, metal nitride, metal selenide and metal sulfide. It is preferred that the material has a good thin film-forming property to ensure sufficient contact between the first conductive layer and hole transport layer to promote hole injection under low voltage and provide better stability.
  • the hole transport layer is in contact with the emitting layer.
  • an electron blocking layer may be placed between the hole transport layer and the emitting layer.
  • the emitting layer plays a very important role in the whole structure of the light emitting device. In addition to determining the color of the device, the emitting layer also has an important impact on the luminance efficiency in a whole. Common emitter materials can be classified as fluorescent and phosphorescent depending on the light emitting mechanism.
  • the second conductive layer is a cathode and comprises a conductive material.
  • the material of the cathode can be a metal such as aluminum and calcium, a metal alloy such as magnesium/silver and aluminum/lithium, and any combinations thereof.
  • an extremely thin film of lithium quinolate as an electron injection layer may be optionally placed between the cathode and the emitting layer.
  • Lithium quinolate can effectively reduce the energy barrier of injecting electrons from the cathode to the emitting layer.
  • an electron transport layer may be placed between the emitting layer and the electron injection layer.
  • a hole blocking layer may be placed between the electron transporting layer and the emitting layer.
  • organic electronic device refers to a device that carries out an electrical operation with the presence of organic materials.
  • organic electronic devices include organic photovoltaics; organic sensors; organic thin film transistors; organic memory devices; organic field effect transistors; and organic light emitting devices such as OLED devices; and power generation and storage devices such as organic batteries, fuel cells, and organic super capacitors.
  • organic light emitting device refers to a device that emits light when an electrical current is applied across two electrodes. Specific example includes light emitting diodes.
  • p-dopant refers to an additive that can increase the hole conductivity of a charge transfer layer.
  • polymeric charge transfer layer refers to a polymeric material that can transport charge, either holes or electrons. Specific example includes a hole transport layer.
  • anode typically refers to a metal, a metal oxide, a metal halide, an electro-conductive polymer, and combinations thereof, that injects holes into either the emitting layer or a layer that is located between the emitting layer and the anode, such as a hole injection layer or a hole transport layer.
  • the anode is disposed on a substrate.
  • blocking layer refers to a layer providing a barrier that significantly inhibits transport of one type of charge carriers and/or excitons through the device, without suggesting that the layer necessarily completely blocks all charge carriers and/or excitons.
  • the presence of such a blocking layer in a device may result in higher efficiencies as compared to a similar device lacking a blocking layer.
  • a blocking layer may be used to confine emission to a desired region of an OLED. Blocking layers, when present, are generally present on either side of the emitting layer.
  • Electron blocking may be accomplished in various ways including, for example, by using a blocking layer that has a LUMO energy level that is significantly higher than the LUMO energy level of the emissive layer. The greater difference in LUMO energy levels results in better electron blocking properties. Suitable materials for use in the blocking layer are dependent upon the material of emissive layer.
  • a layer that primarily performs electron blocking is an electron blocking layer (EBL) . Electron blocking may occur in other layers, for example, a hole transport layer (HTL) .
  • EBL electron blocking layer
  • HTL hole transport layer
  • Hole blocking may be accomplished in various ways including, for example, by using a blocking layer that has a HOMO energy level that is significantly lower than the HOMO energy level of the emissive layer. The greater difference in HOMO energy levels results in better hole blocking properties. Suitable materials for use in the blocking layer are dependent upon the material of emissive layer.
  • a layer that primarily performs hole blocking is a hole blocking layer (HBL) . Hole blocking may occur in other layer, for example, an electron transport layer (ETL) .
  • HBL hole blocking layer
  • ETL electron transport layer
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer by using a blocking layer that has a triplet energy level that is significantly higher than the triplet energy level of the EML dopant or the EML host. Suitable materials for use in the blocking layer are dependent upon the material composition of emissive layer.
  • cathode typically refers to a metal, a metal oxide, a metal halide, an electroconductive polymer, or a combination thereof, that injects electrons into the emitting layer or a layer that is located between the emitting layer and the cathode, such as an electron injection layer or an electron transport layer.
  • electron injection layer refers to a layer which improves injection of electrons injected from the cathode into the electron transport layer.
  • the emitting layer typically consists of host and emitter.
  • the host material could be preferentially hole or electron transporting or can be similarly transporting of both holes and electrons, and may be used alone or by combination of two or more host materials.
  • the opto-electrical properties of the host material may differ to which type of emitter (Phosphorescent or Fluorescent) is used.
  • the emitter is a material that undergoes radiative emission from an excited state.
  • the excited state can be generated, for example, by charges on the emitter molecule or by energy transfer from the excited state of another molecule.
  • electron transport layer refers to a layer made from a material, which exhibits properties including high electron mobility for efficiently transporting electrons injected from the cathode or the EIL and favorable injection of those electrons into the hole blocking layer or the emitting layer.
  • hole injection layer refers to a layer for efficiently transporting or injecting holes from the anode into the emissive layer, the electron blocking layer, or more typically into the hole transport layer. Multiple hole injection layers may be used to accomplish hole injection from the anode to the hole transporting layer, electron blocking layer or the emitting layer.
  • hole transport layer. or “HTL, ” and the like, refers to a layer made from a material, which exhibits properties including high hole mobility for efficiently transporting holes injected from the anode or the HIL and favorable injection of those holes into the electron blocking layer or the emitting layer.
  • aromatic moiety refers to an organic moiety derived from aromatic hydrocarbyl by deleting at least one hydrogen atom therefrom.
  • An aromatic moiety may be a monocyclic and/or fused ring system, each ring of which suitably contains from 4 to 7, preferably from 5 or 6 atoms. Structures wherein two or more aromatic moieties are combined through single bond (s) are also included.
  • the naphthyl may be 1-naphthyl or 2-naphthyl
  • the anthryl may be 1-anthryl, 2-anthryl or 9-anthryl
  • the fluorenyl may be any one of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • heteroaromatic moiety refers to an aromatic moiety, in which at least one carbon atom or CH group or CH 2 group is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • the heteroaromatic moiety may be a 5-or 6-membered monocyclic heteroaryl, or a polycyclic heteroaryl which is fused with one or more benzene ring (s) , and may be partially saturated.
  • the structures having one or more heteroaromatic moieties bonded through a single bond are also included.
  • monocyclic heteroaryl groups such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups, such as benzofuranyl, fluoreno [4, 3-b] benzofuranyl, benzothiophenyl, fluoreno [4, 3-b] benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindo
  • hydrocarbyl refers to a chemical group containing only hydrogen and carbon atoms.
  • substituted hydrocarbyl refers to a hydrocarbyl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • heterohydrocarbyl refers to a chemical group containing hydrogen and carbon atoms, and wherein at least one carbon atom or CH group or CH 2 group is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • substituted heterohydrocarbyl refers to a heterohydrocarbyl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • aryl refers to an organic radical derived from aromatic hydrocarbyl by deleting one hydrogen atom therefrom.
  • An aryl group may be a monocyclic and/or fused ring system, each ring of which suitably contains from 4 to 7, preferably from 5 or 6 atoms. Structures wherein two or more aryl groups are combined through single bond (s) are also included. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, benzofluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphtacenyl, and fluoranthenyl.
  • the naphthyl may be 1-naphthyl or 2-naphthyl
  • the anthryl may be 1-anthryl, 2-anthryl or 9-anthryl
  • the fluorenyl may be any one of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • substituted aryl refers to an aryl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • heteroaryl refers to an aryl group, in which at least one carbon atom or CH group or CH 2 group is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • the heteroaryl may be a 5-or 6-membered monocyclic heteroaryl or a polycyclic heteroaryl which is fused with one or more benzene ring (s) , and may be partially saturated.
  • the structures having one or more heteroaryl group (s) bonded through a single bond are also included.
  • the heteroaryl groups may include divalent aryl groups of which the heteroatoms are oxidized or quarternized to form N-oxides, quaternary salts, or the like.
  • monocyclic heteroaryl groups such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups, such as benzofuranyl, fluoreno [4, 3-b] benzofuranyl, benzothiophenyl, fluoreno [4, 3-b] benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazoly
  • substituted heteroaryl refers to a heteroaryl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom.
  • the term “monomer” refers to a compound containing one or more functional groups that is able to be polymerized into a polymer.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into and/or within the polymer structure) , and the term copolymer as defined hereinafter.
  • copolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
  • solvents and reagents are available from commercial vendors, for example, Sigma-Aldrich, TCI, and Alfa Aesar, and are used in the highest available purities, and/or when necessary, distilled or recrystallized before use. Dry solvents were obtained from in-house purification/dispensing system (hexane, toluene, and tetrahydrofuran) , or purchased from Sigma-Aldrich. All experiments involving “water sensitive compounds” are conducted in “oven dried” glassware, under nitrogen atmosphere, or in a glovebox.
  • GPC Gel permeation chromatography
  • LC/MS Routine liquid chromatography/mass spectrometry (LC/MS) studies were carried out as follows.
  • One microliter aliquots of the sample as “1mg/ml solution in tetrahydrofuran (THF) , ” are injected on an Agilent 1200SL binary liquid chromatography (LC) , coupled to an Agilent 6520 quadruple time-of-flight (Q-TOF) MS system, via a dual electrospray interface (ESI) , operating in the PI mode.
  • LC binary liquid chromatography
  • Q-TOF quadruple time-of-flight
  • AIBN anisole solution 4 mg/mL azodiisobutyronitrile (AIBN) anisole solution was firstly prepared in glove-box.
  • Monomer B1 900 mg, 1.277 mmol
  • Monomer A1 106 mg, 0.142 mmol
  • 0.65 mL 8mg/mL AIBN anisole solution were added into 3.5 mL anisole in seal tube in glove-box and then stirred overnight at 70 °C.
  • 1 H NMR was checked, which shows very poor signal from unreacted vinyl group.
  • 8mg/mL AIBN anisole solution was freshly prepared. 0.3 mL was added and stirred overnight at 70 °C to ensure the complete conversion.
  • the resulted copolymer has a M n of 19, 480, an M w of 78, 468, an M z of 539, 314, an M z+1 of 2, 673, 848, and a PDI of 4.03.
  • AIBN anisole solution 4 mg/mL AIBN anisole solution was firstly prepared in glove-box.
  • Monomer B8 1.0 g, 0.88 mmol
  • Monomer A1 73 mg, 0.098 mmol
  • 0.65 mL 4mg/mL AIBN anisole solution were added into 0.4 mL anisole in seal tube in glove-box and then stirred overnight at 70 °C.
  • 1 H NMR was checked, which shows very poor signal from unreacted vinyl group.
  • 8 mg/mL AIBN anisole solution was freshly prepared. 0.3 mL was added and stirred overnight at 70 °C to ensure the complete conversion.
  • the resulted copolymer has a M n of 17, 849, an M w of 87, 273, an M z of 384, 048, an M z+1 of 2, 127, 117, and a PDI of 4.89.
  • HTL polymer solution HTL polymer solid powders were directly dissolved into anisole to make a 2 wt%stock solution. The solution was stirred at 80°C for 5 to 10 min in N 2 for complete dissolution. The resulting formulation solution was filtered through 0.2 ⁇ m PTFE syringe filter prior to depositing onto Si wafer.
  • Preparation of thermally annealed HTL polymer film Si wafer was pre-treated by UV-ozone for 2 to 4 min prior to use. Several drops of the above filtered formulation solution were deposited onto the pre-treated Si wafer. The thin film was obtained by spin coating at 500rpm for 5s and then 2000rpm for 30s. The resulting film was then transferred into the N 2 purging box. The “wet” film was prebaked at 100°C for 1min to remove most of residual anisole. Subsequently, the film was thermally annealed at 160, 180°C for 20min, and 205, 220, 235°C for 10min in N 2 atmosphere.
  • the total film loss after solvent stripping should be ⁇ 1 nm, preferably ⁇ 0.5nm.
  • Copolymer 1 and copolymer 2 showed good solvent resistance to o-xylene for even 5 minutes in wide annealing temperature range, which is a critical requirement for solution process applications.
  • OLED devices were constructed as follows. Glass substrates (20 mm ⁇ 15 mm) with pixelated tin-doped indium oxide (ITO) electrodes (Ossila Inc. ) were used. The ITO was treated using oxygen plasma.
  • ITO indium oxide
  • HTL each material was individually dissolved in electronic grade anisole (2%w/w) at elevated temperature ( ⁇ 100°C) to ensure complete dissolution and passed through a 0.2 ⁇ m PTFE filter.
  • EML each material was individually dissolved in o-xylene (2%w/w) at elevated temperature ( ⁇ 100°C) to ensure complete dissolution and passed through a 0.2 ⁇ m PTFE filter.
  • the materials were deposited into a layer by dynamic spin coating whereby 20 ⁇ L of the solution was dispensed onto a spinning substrate.
  • the spin speed (approximately 2000 RPM) was adjusted for each material to achieve a film thickness of approximately 40 nm.
  • Some portions of the deposited film which covered sections of the electrodes were removed with toluene using a foam swab.
  • the HTL layer on the substrate was annealed at 205°C for 10 minutes on a hot plate in an inert atmosphere.
  • the EML layer on the substrate was annealed at 120°C for 15 minutes on a hot plate in an inert atmosphere.
  • the emitting layer was a host/emitter mixture having 2 mole%emitter Iridium, bis [2, 4-dimethyl-6- [5- (2-methylpropyl) -2-quinolinyl- ⁇ N] phenyl- ⁇ C] (2, 4-pentanedionato- ⁇ O 2 , ⁇ O 4 ) - in a host 9-phenyl-9′- (4-phenylquinazolin-2-yl) -9H, 9′H-3, 3′-bicarbazole.
  • HBL hole blocking layer
  • ETL electron transport layer
  • cathode cathode
  • a 5 nm layer of 5- (4- ( [1, 1′-biphenyl] -3-yl) -6-phenyl-1, 3, 5-triazin-2-yl) -7, 7-diphenyl-5, 7-dihydroindeno [2, 1-b] carbazole as HBL material was deposited by thermal evaporation under high vacuum from an alumina crucible through an active area shadow mask.
  • a 35 nm layer of 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1, 3, 5-triazine as ETL material was deposited by thermal evaporation under high vacuum from an alumina crucible through an active area shadow mask.
  • a 2 nm layer of lithium quinolate (liq) was deposited by thermal evaporation under high vacuum from an alumina crucible through a cathode shadow mask.
  • a 100 nm layer of aluminum was deposited by thermal evaporation under high vacuum from a graphite crucible through a cathode shadow mask.
  • the OLED devices were tested as follows. Current-Voltage-Light (JVL) data was collected on un-encapsulated devices inside a N 2 glovebox using a custom-made test board from Ossila Inc.
  • the board contained two components: 1) X100 Xtralien TM precision testing source, and 2) Smart PV and OLED Board; in combination, these components were used to test OLED devices over a voltage range of -2 V to 8 V at increments of 0.1 V while measuring current and light output.
  • the light output was measured using an eye response photodiode which includes an optical filter that mimics photopic eye sensitivity (Centronic E Series) .
  • the devices were placed inside of the testing chamber on the board and covered with the photodiode assembly.
  • OLED devices of the present invention had higher luminous efficiencies compared to that of Comparative Device.

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  • Manufacturing & Machinery (AREA)
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  • General Physics & Mathematics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne des composions de couche de transfert de charge polymère appropriées pour des couches organiques de dispositifs électroniques qui présentent une efficacité lumineuse accrue.
PCT/CN2017/109672 2017-11-07 2017-11-07 Couche de transfert de charge polymère et dispositif électronique organique la comprenant WO2019090462A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
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US6200715B1 (en) * 1999-06-04 2001-03-13 Xerox Corporation Imaging members containing arylene ether alcohol polymers
CN101638377A (zh) * 2008-07-30 2010-02-03 三星移动显示器株式会社 胺类化合物、有机发光装置和平板显示设备
CN101993410A (zh) * 2009-08-10 2011-03-30 三星移动显示器株式会社 杂环化合物和包括该杂环化合物的有机发光装置
CN102163014A (zh) * 2010-02-23 2011-08-24 富士施乐株式会社 图像形成设备和处理盒
CN103365129A (zh) * 2012-03-28 2013-10-23 富士施乐株式会社 电荷输送膜形成用组合物、感光体、处理盒和图像形成设备
CN104076625A (zh) * 2013-03-26 2014-10-01 富士施乐株式会社 电子照相感光体、处理盒和成像装置
WO2017031622A1 (fr) * 2015-08-21 2017-03-02 Dow Global Technologies Llc Couche de transfert de charge polymère et dispositif électronique organique la contenant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6200715B1 (en) * 1999-06-04 2001-03-13 Xerox Corporation Imaging members containing arylene ether alcohol polymers
CN101638377A (zh) * 2008-07-30 2010-02-03 三星移动显示器株式会社 胺类化合物、有机发光装置和平板显示设备
CN101993410A (zh) * 2009-08-10 2011-03-30 三星移动显示器株式会社 杂环化合物和包括该杂环化合物的有机发光装置
CN102163014A (zh) * 2010-02-23 2011-08-24 富士施乐株式会社 图像形成设备和处理盒
CN103365129A (zh) * 2012-03-28 2013-10-23 富士施乐株式会社 电荷输送膜形成用组合物、感光体、处理盒和图像形成设备
CN104076625A (zh) * 2013-03-26 2014-10-01 富士施乐株式会社 电子照相感光体、处理盒和成像装置
WO2017031622A1 (fr) * 2015-08-21 2017-03-02 Dow Global Technologies Llc Couche de transfert de charge polymère et dispositif électronique organique la contenant

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