Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
  • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
  • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
  • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
  • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
  • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C35/48—Halogenated derivatives
  • C07C35/52—Alcohols with a condensed ring system
• • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
• • 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
  • H10K85/115—Polyfluorene; Derivatives thereof
• • 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
• • 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
  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/18—Fluorenes; Hydrogenated fluorenes
• • 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
  • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
  • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
  • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
• • 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
  • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
  • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
  • C08G2261/3162—Arylamines
• • 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
  • C08G2261/52—Luminescence
  • C08G2261/522—Luminescence fluorescent
  • C08G2261/5222—Luminescence fluorescent electrofluorescent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/14—Macromolecular compounds
  • C09K2211/1408—Carbocyclic compounds
  • C09K2211/1416—Condensed systems

Definitions

• the present invention relates to polymers for use in organic light emitting devices, comprising asymmetrically substituted repeat units, methods of making said polymers and devices comprising said polymers.
• OLEDs organic light emitting diodes
• photoresponsive devices in particular organic photovoltaic devices and organic photosensors
• organic transistors in particular organic transistors and memory array devices.
• Devices comprising organic materials offer benefits such as low weight, low power consumption and flexibility.
• use of soluble organic materials allows use of solution processing in device manufacture, for example inkjet printing or spin-coating.
• an OLED may comprise a substrate 1 carrying an anode 2, a cathode 4 and an organic light-emitting layer 3 between the anode and cathode.
• Holes are injected into the device through the anode 2 and electrons are injected through the cathode 4 during operation of the device. Holes in the highest occupied molecular orbital (HOMO) and electrons in the lowest unoccupied molecular orbital (LUMO) of a light-emitting material in the light-emitting layer combine to form an exciton that releases its energy as light.
• HOMO highest occupied molecular orbital
• LUMO unoccupied molecular orbital
• Suitable light-emitting materials include small molecule, polymeric and dendrimeric materials.
• Suitable light-emitting polymers for use in layer 3 include poly(arylene vinylenes) such as poly(p-phenylene vinylenes) and polyarylenes such as polyfluorenes.
• Polymers comprising 9,9-dialkyl substituted fluorene repeat units are disclosed in, for example, WO 99/54385.
• WO 02/092723 discloses polymers comprising 9,9-diaryl substituted fluorene repeat units, which are reported to have longer lifetime that analogous polymers comprising 9,9- dialkyl substituted fluorene repeat units. This increased lifetime is attributed to an increase in thermal stability of the polymer when 9,9-dialkyl substituents are replaced with 9,9-diaryl substituents, which is manifested in higher polymer glass transition temperatures ("lifetime" as used herein means the time taken for luminance of a polymer to fall by a specified percentage, for example 10% or 50%, at constant current).
• WO 2004/039912 discloses a method of forming fluorenes with different substituents in the 9-position, such as a 9-alkyl-9-phenyl fluorenes.
• WO 2009/066061 discloses a hole transport layer comprising a polymer having a repeat unit comprising a 9,9 biphenyl fluorene repeat unit wherein the 9-phenyl rings are independently and optionally substituted.
• the invention provides a polymer comprising a repeat unit of formula (la):
• R 7 represents a substituent bound to the 9-carbon atom of the fluorene ring through a non-aromatic carbon atom
• R 8 ,R 9 and R 11 independently in each occurrence represent H or a substituent with the proviso that at least one R 8 is not H
• R 10 independently in each occurrence is a substituent
• t in each occurrence is independently 0, 1, 2 or 3.
• R 7 is substituted with one or more substituted or unsubstituted aryl groups, optionally one or more groups -(Ar 6 ) w , wherein each Ar 5 independently represents a substituted or unsubstituted aryl or heteroaryl group, and w is at least 1, for example 1, 2 or 3.
• one R 8 group is H
• both R 8 groups are not H.
• At least one R 8 is selected from the group consisting of optionally substituted alkyl and -(Ar 7 ) z , wherein each Ar 7 independently represents an optionally substituted aiyl or heteroaryl gioup and z is at least one, optionally 1, 2 or 3.
• each t is 0.
• R 9 is H.
• R 11 is H
• the polymer further comprises a repeat unit of formula (V):
• Ar and Ar in each occurrence are independently selected from optionally substituted aryl or heteroaryl groups, n is greater than or equal to 1, preferably 1 or 2, R is H or a substituent, preferably a substituent, x and y are each independently 1, 2 or 3, and any two of groups Ar 1 , Ar 2 and R may be linked by a direct bond or a divalent linking group to form a ring.
• R 7 represents a substituent bound to the 9-carbon atom of the fluorene ring through a non-aromatic carbon atom
• R 8 , R 9 and R 11 independently in each occurrence represent H or a substituent with the proviso that at least one R 8 is not H
• each occurrence independently in each occurrence is a substituent; t in each occurrence is independently 0, 1, 2 or 3; and each L is independently a polymerisable group.
• each L is the same or different and is selected from leaving groups capable of participating in metal-mediated cross-coupling.
• each L is the same or different and is selected from halogen, boronic acid and esters thereof.
• the invention provides a method of forming a polymer comprising the step of polymerizing the compound of the second aspect.
• the compound of the second aspect is polymerized in the presence of a metal catalyst.
• the invention provides a polymer comprising a repeat unit of formula
• R 12 independently in each occurrence represent H or a substituent
• At least one R 12 is H.
• At least one R is selected from the group consisting of substituted or unsubstituted alkyl and -(Ar 7 ) z , wherein each Ar 7
• z is at least one, optionally 1, 2 or 3.
• each t is 0.
• the polymer comprises a repeat unit of formula
• Ar 1 and Ar 2 in each occurrence are independently selected from substituted or unsubstituted aryl or heteroaryl groups, n is greater than or equal to 1, preferably 1 or 2, R is H or a substituent, preferably a substituent, x and y are each independently 1, 2 or 3, and any two of groups Ar 1 , Ar 2 and R may be linked by a direct bond or a divalent linking group to form a ring.
• R 12 independently in each occurrence represents H or a substituent
• R 10 independently in each occurrence is a substituent
• t in each occurrence is independently 0, 1, 2 or 3
• each L is independently a polymerisable group.
• each L is the same or different and is selected from leaving groups capable of participating in metal-mediated cross-coupling.
• each L is the same or different and is selected from halogen, boronic acid and esters thereof.
• the invention provides a method of forming a polymer comprising the step of polymerizing the compound of the fifth aspect.
• the compound of the fifth aspect is polymerized in the presence of a metal catalyst.
• the invention provides an organic electronic device comprising a polymer according to the first or fourth aspects.
• the organic electronic device is an organic light-emitting device comprising at least one organic light-emitting layer.
• the at least one organic light-emitting layer comprises the polymer.
• the invention provides use of a repeat unit of formula (III) to increase the stability of a polymer relative to a polymer in which R 7 is present in place of Ar or in which Ar is present in place of R 7 .
• R 7 represents a substituent bound to the polymer through a non-aromatic carbon atom
• Ar represents an optionally substituted aryl or heteroaryl group
• R 10 independently in each occurrence is a substituent
• t in each occurrence is independently 0, 1, 2 or 3.
• the 9-alkyl substituent is selected from branched and straight chain Cl-20 alkyl.
• Ar is substituted with one or more substituents
• Ar is optionally substituted phenyl group.
• At least one meta-position of the phenyl group is substituted.
• Figure 1 illustrates an organic light-emitting device according to an embodiment of the invention.
• Figure 2 illustrates lifetimes of an organic light-emitting device according to an embodiment of the invention and a comparative device
• Figure 3 illustrates lifetimes of an organic light-emitting device according to an embodiment of the invention and a comparative device.
• a polymer comprising 9-aryl-9-alkyl-fluorene repeat units may have longer lifetime that a polymer comprising 9,9-dialkyl and / or 9,9-diaryl fluorene repeat units.
• the device lifetime may depend at least in part on stability of the organic materials of the device, in particular the bonds strengths of those materials.
• the bond strengths of at least some carbon-carbon bonds within the fluorene repeat unit may depend in part on the identity of substituents at the 9- position of the fluorene repeat unit.
• the weakest bonds are believed to be the bonds between the fluorene C9 atom and the alkyl substituents.
• the weakest bonds are believed to be those bonds between the fluorene C9 atom and the adjacent phenyl rings.
• the weakest bond of a fluorene repeat unit of formula (la), (Ha) or (III) may be stronger than the weakest bond of a material such as a 9,9-dialkyl fluorene repeat unit or a corresponding 9,9-di(hetero)aryl fluorene repeat unit, thereby improving overall polymer stability.
• R 7 of formula (la), (lb) or (III) may be optionally substituted alkyl, for example optionally substituted branched or straight chain Ci-2o alkyl or optionally substituted branched or straight chain C 2 . 2 o alkyl.
• This alkyl group may be substituted with one or more groups -(Ar 6 ) w , wherein each Ar 6 independently represents an optionally substituted aryl or heteroaryl group, and w is at least 1, for example 1, 2 or 3. If w is greater than 1 then the Ar 6 groups may form a linear or branched chain of (hetero)aryl groups.
• a group -(Ar 6 )* may be attached to an end of the alkyl group.
• Exemplary Ar 6 groups include phenyl and fluorene.
• Each Ar 5 group may be substituted with one or more substituents for example one or more alkyl groups, in particular one or more Ci. 20 alkyl groups.
• the 9-aryl or 9-heteroaryl group of the repeat unit of formula (Ha) or (III) may be substituted or unsubstituted. In the case where it is substituted it optionally comprises a repeat unit of formula (la) illustrated above.
• substituents e.g. alkyl or aryl
• Exemplary alkyl substituents include Ci.20 alkyl.
• Exemplary aryl or heteroaryl substituents include -(Ar 7 ) Z) wherein each Ar 7 independently represents an optionally substituted aryl or heteroaryl group, for example phenyl, and z is at least one, optionally 1, 2 or 3. If z is greater than 1 then the Ar 7 groups may form a linear or branched chain of (hetero)aryl groups.
• Each Ar 7 group may be substituted with one or more substituents for example one or more alkyl groups, in particular one or more C 1-2 o alkyl groups.
• a substituent in the para- position of a phenyl substituent may serve to stabilize a radical or an ion formed by scission of the C9-phenyl bond whereas meta-substitutions may be less able to mesomerically stabilize radicals or ions and so may encourage bond-breakage less than para-substitutions.
• Exemplary 9-alkyl-9-aryl fluorene repeat units include the following.
• the polymer is a homopolymer comprising repeat units of formula (la), (Ila) or (III).
• the polymer is a copolymer comprising one or more repeat units of formula (la), (Ila) or (III) and optionally one or more further co-repeat units.
• the repeat units of formula (la), (Ila) or (III) may be provided in any amount, for example in the range of about 1 mol % to about 99 mol %.
• the repeat unit of formula (la), (Ila) or (Hl) is present in an amount of at least 5 mol , at least 10 mol % or at least 20 mol %.
• the copolymer may comprise one or more of hole transporting, electron transporting and / or light-emitting repeat units such as disclosed in, for example, WO 00/55927 and US 6353083.
• Electron transporting, hole transporting and / or light-emitting units may be provided as repeat units in the polymer backbone, such as disclosed in US 6353083, or may be provided as functional units pendent from the polymer backbone.
• the polymer is preferably at least partially conjugated along its backbone.
• the fluorene unit is conjugated to at least one, and optionally both, of the repeat units on either side of it in the polymer backbone.
• the unit of formula (la), (Ila) or (III) may be used as, for example: a repeat unit of a light-emitting polymer, in which this repeat unit and / or another repeat unit is emissive; a repeat unit of a hole transporting polymer comprising one or more hole-transporting repeat units; a repeat unit of an electron-transporting polymer; or as a repeat unit of a host polymer for use in combination with a light-emitting dopant.
• An emissive polymer may emit, without limitation, red, green or blue light.
• One class of hole transporting and / or light-emitting repeat units for example blue and / or green light-emitting repeat units, are optionally substituted (hetero)arylamines.
• Suitable repeat units include repeat units of formula (V):
• Ar 1 and Ar 2 in each occurrence are independently selected from optionally substituted aryl or heteroaryl groups, n is greater than or equal to 1, preferably 1 or 2, R in each occurrence is H or a substituent, preferably a substituent, and x and y are each independently 1, 2 or 3.
• Exemplary groups R include alkyl, Ar 3 , or a branched or linear chain of Ar 3 groups, for example -(Ar 3 ) v , wherein Ar 3 in each occurrence is independently selected from aryl or heteroaryl and v is at least 1, optionally 1, 2 or 3.
• Ar 1 , Ar 2 and Ar 3 may independently be substituted with one or more substituents.
• R may comprise a crosslinkable-group, for example a group comprising a polymerisable double bond such and a vinyl or acrylate group, or a benzocyclobutane group.
• any of the aryl or heteroaryl groups in the repeat unit of Formula (V) may be linked by a direct bond or a divalent linking atom or group.
• Preferred divalent linking atoms and groups include O, S; substituted N; and substituted C.
• substituted N or substituted C of R 3 , R 4 or of the divalent linking group may independently in each occurrence be NR 6 or CR 6 2 respectively wherein R 6 is alkyl or optionally substituted aryl or heteroaryl.
• Optional substituents for aryl or heteroaryl groups R 6 may be selected from R 4 or R 5 .
• R is Ar 3 and each of Ar 1 , Ar 2 and Ar 3 are independently and optionally substituted with one or more ⁇ . 20 alkyl groups.
• Particularly preferred units satisfying Formula 1 include units of Formulae 1-3: -
• Ar 1 and Ar 2 are as defined above; and Ar 3 is optionally substituted aryl or heteroaryl.
• preferred substituents for Ar 3 include substituents as described forAr 1 and Ar 2 , in particular alkyl and alkoxy groups.
• Ar 1 , Ar 2 and Ar 3 are preferably phenyl, each of which may independently be substituted with one or more substituents as described above.
• aryl or heteroaryl groups of formula (V) are phenyl, each phenyl group being optionally substituted with one or more alkyl groups.
• Ar 1 and Ar 2 are phenyl, each of which may be substituted with one or more Q. 20 alkyl groups, and R is 3,5-diphenylbenzene wherein each phenyl may be substituted with one or more alkyl groups.
• the polymer may comprise one, two or more different repeat units of formula (V).
• the polymer may comprise one repeat unit of formula (V) to provide hole transport and another repeat unit of formula (V) to provide light-emission.
• the repeat units of formula (V) may be provided in any amount, for example in the range of about 1 mol % to about 70 mol %. In the case where the polymer is used as a light- emitting material, the repeat units of formula (V) may be present in an amount less than 50 mol %, for example less than 20 mol % or less than 10 mol %.
• Electron transport may be provided by a conjugated chain of arylene repeat units, for example a conjugated chain comprising one or more of fluorene, indenofluorene, and phenylene repeat units (including repeat units of formula I and II), each of which may optionally be substituted by, for example, alkyl or alkoxy.
• arylene repeat units for example a conjugated chain comprising one or more of fluorene, indenofluorene, and phenylene repeat units (including repeat units of formula I and II), each of which may optionally be substituted by, for example, alkyl or alkoxy.
• Exemplary fluorene repeat units other than repeat units of formula (1) or (II), include repeat units of formula (IV):
• R 1 and R 2 are independently H or a substituent and wherein R 1 and R 2 may be linked to form a ring. In the case where R and R are different, they do not form a repeat unit of formula (la), (Ila) or (III). In one optional arrangement, R 1 and R 2 are the same.
• R 1 or R 2 comprises alkyl
• substituents of the alkyl group include F, CN, nitro, and aryl or heteroaryl optionally substituted with one or more groups R 4 wherein R 4 is as described above.
• each aryl or heteroaryl group may independently be substituted.
• Preferred optional substituents for the aryl or heteroaryl groups include one or more substituents R 3 .
• substituted N in repeat units of formula (IV) may independently in each occurrence be NR 5 or NR 6 .
• At least one of R 1 and R 2 comprises an optionally substituted C1-C20 alkyl or an optionally substituted aryl group, in particular phenyl substituted with one or more C 1-2 o alkyl groups.
• fluorene repeat units other than repeat units of formula (la), (Ha) or (Ill) may optionally be present in a mol per cent amount that is less than the mol per cent amount of repeat units of formula (la), (Ila) or (III).
• Preferred methods for preparation of conjugated polymers comprise a "metal insertion" wherein the metal atom of a metal complex catalyst is inserted between an aryl or heteroaryl group and a leaving group of a monomer.
• Exemplary metal insertion methods are Suzuki polymerisation as described in, for example, WO 00/53656 and Yamamoto polymerisation as described in, for example, T. Yamamoto, "Electrically Conducting And Thermally Stable ⁇ - Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205.
• Yamamoto polymerisation a nickel complex catalyst is used; in the case of Suzuki polymerisation, a palladium complex catalyst is used.
• a monomer having two reactive halogen groups is used.
• at least one reactive group is a boron derivative group such as a boronic acid or boronic ester and the other reactive group is a halogen.
• Preferred halogens are chlorine, bromine and iodine,preferably bromine and iodine, most preferably bromine. It will therefore be appreciated that repeat units illustrated throughout this application may be derived from a monomer carrying suitable leaving groups. Likewise, an end group or side group may be bound to the polymer by reaction of a suitable leaving group.
• Suzuki polymerisation may be used to prepare regioregular, block and random copolymers.
• homopolymers or random copolymers may be prepared when one reactive group is a halogen and the other reactive group is a boron derivative group.
• block or regioregular, in particular AB, copolymers may be prepared when both reactive groups of a first monomer are boron and both reactive groups of a second monomer are halogen.
• other leaving groups capable of participating in metal insertion include groups include tosylate, mesylate and triflate.
• a polymer comprising a repeat unit of formula (la), (Ila) or (III) may be used as light- emitting polymer in which the fluorene unit or a co-repeat unit may be luminescent.
• the polymer may be used as a host material, or as a component of a host material, for one or more fluorescent or phosphorescent light-emitting dopants.
• Suitable dopants include luminescent metal complexes, for example metal complexes comprising optionally substituted complexes of formula (VI :
• M is a metal; each of L 1 , L 2 and L 3 is a coordinating group; q is an integer; r and s are each independently 0 or an integer; and the sum of (a. q) + (b. r) + (c.s) is equal to the number of coordination sites available on M, wherein a is the number of coordination sites on L 1 , b is the number of coordination sites on L 2 and c is the number of
• Heavy elements M induce strong spin-orbit coupling to allow rapid intersystem crossing and emission from triplet or higher states (phosphorescence).
• Suitable heavy metals include: - lanthanide metals such as cerium, samarium, europium, terbium, dysprosium, thulium, erbium and neodymium; and
• - d-block metals in particular those in rows 2 and 3 i.e. elements 39 to 48 and 72 to 80, in particular ruthenium, rhodium, pallaidum, rhenium, osmium, iridium, platinum and gold. Iridium is particularly preferred.
• Suitable coordinating groups for the f-block metals include oxygen or nitrogen donor systems such as carboxylic acids, 1,3-diketonates, hydroxy carboxylic acids,
• luminescent lanthanide metal complexes require sensitizing group(s) which have the triplet excited energy level higher than the first excited state of the metal ion. Emission is from an f-f transition of the metal and so the emission colour is determined by the choice of the metal. The sharp emission is generally narrow, resulting in a pure colour emission useful for display applications.
• the d-block metals are particularly suitable for emission from triplet excited states.
• Ar 4 and Ar 5 may be the same or different and are independently selected from optionally substituted aryl or heteroaryl; X 1 and Y 1 may be the same or different and are independently selected from carbon or nitrogen; and Ar 4 and Ar 5 may be fused together.
• Ligands wherein X 1 is carbon and Y 1 is nitrogen are particularly preferred.
• Each of AT 4 and Ar 5 may carry one or more substituents. Two or more of these substituents may be linked to form a ring, for example an aromatic ring.
• Particularly preferred substituents include fluorine or trifluoromethyl which may be used to blue-shift the emission of the complex as disclosed in WO 02/45466, WO 02/44189, US 2002- 117662 and US 2002-182441; alkyl or alkoxy groups as disclosed in JP 2002-324679; carbazole which may be used to assist hole transport to the complex when used as an emissive material as disclosed in WO 02/81448; bromine, chlorine or iodine which can serve to functionalise the ligand for attachment of further groups as disclosed in WO
• a light-emitting dendrimer typically comprises a light-emitting core bound to one or more dendrons, wherein each dendron comprises a branching point and two or more dendritic branches.
• the dendron is at least partially conjugated, and at least one of the core and dendritic branches comprises an aryl or heteroaryl group.
• ligands suitable for use with d-block elements include diketonates, in particular acetylacetonate (acac); triarylphosphines and pyridine, each of which may be substituted.
• Main group metal complexes show ligand based, or charge transfer emission.
• the emission colour is determined by the choice of ligand as well as the metal.
• Suitable ligands for di or trivalent metals include: oxinoids, e. g.
• oxygen-nitrogen or oxygen-oxygen donating atoms generally a ring nitrogen atom with a substituent oxygen atom, or a substituent nitrogen atom or oxygen atom with a substituent oxygen atom such as 8- hydroxyquinolate and hydroxyquinoxalinol-10-hydroxybenzo (h) quinolinato (II), benzazoles (III), schiff bases, azoindoles, chromone derivatives, 3-hydroxyflavone, and carboxylic acids such as salicylate amino carboxylates and ester carboxylates.
• Optional substituents include halogen, alkyl, alkoxy, haloalkyl, cyano, amino, amido, sulfonyl, carbonyl, aryl or heteroaryl on the (hetero) aromatic rings which may modify the emission colour.
• the host and the light-emitting dopant may be physically mixed.
• the light- emitting dopant may be chemically bound to the host.
• the light-emitting dopant may be chemically bound as a substituent attached to the polymer backbone, incorporated as a repeat unit in the polymer backbone or provided as an end-group of the polymer as disclosed in, for example, EP 1245659, WO 02/31896, WO 03/18653 and WO 03/22908.
• This binding may result in more efficient transfer of excitons from the host polymer to the light emitting dopant because it may provide intramolecular exciton transfer pathways unavailable to a corresponding mixed system.
• binding may be beneficial for processing reasons. For example, if the light emitting dopant has low solubility then binding it to a soluble polymer allows the light emitting dopant to be carried in solution by the charge transporting material, enabling device fabrication using solution processing techniques. Furthermore, binding the light emitting dopant to the polymer may prevent phase separation effects in solution- processed devices that may be detrimental to device performance.
• More than one light-emitting dopant may be used.
• red, green and blue light-emitting dopants may be used to obtain white light emission.
• the 9-alkyl-9-aryl fluorene unit may also emit light, in particular blue light, that may be combined with emission from one or more further dopants to achieve white light emission.
• a conductive hole injection layer which may be formed from a conductive organic or inorganic material, may be provided between the anode 2 and the light-emitting layer 3 illustrated in Figure 1 to assist hole injection from the anode into the layer or layers of semiconducting polymer.
• doped organic hole injection materials include optionally substituted, doped poly(ethylene dioxythiophene) (PEDT), in particular PEDT doped with a charge-balancing polyacid such as polystyrene sulfonate (PSS) as disclosed in EP 0901176 and EP 0947123, polyacrylic acid or a fluorinated sulfonic acid, for example Nafion ®; polyaniline as disclosed in US 5723873 and US 5798170; and optionally substituted polythiophene or poly(thienothiophene).
• conductive inorganic materials include transition metal oxides such as VOx MoOx and RuOx as disclosed in Journal of Physics D: Applied Physics (1996), 29(11), 2750-2753.
• a hole transporting layer may be provided between the anode 2 and the light-emitting layer 3.
• an electron transporting layer may be provided between the cathode and the light-emitting layer.
• an electron blocking layer may be provided between the anode 2 and the light- emitting layer 3 and a hole blocking layer may be provided between the cathode 4and the light-emitting layer 3.
• Transporting and blocking layers may be used in combination. Depending on its HOMO and LUMO levels, a single layer may both transport one of holes and electrons and block the other of holes and electrons.
• a hole transporting layer located between anode 2 and light-emitting layer 3 preferably has a HOMO level of less than or equal to 5.5 eV, more preferably around 4.8- 5.5 eV. HOMO levels may be measured by cyclic voltammetry, for example.
• an electron transporting layer located between light-emitting layer 3 and cathode 4 preferably has a LUMO level of around 3-3.5 eV.
• a layer of a silicon monoxide or silicon dioxide or other thin dielectric layer having thickness in the range of 0.2-2nm is provided between light-emitting layer 3 and layer 4.
• a hole transporting layer may contain a polymer comprising hole transporting repeat units of formula (I); likewise, an electron transporting layer may contain a polymer comprising electron transporting repeat units of formula (I).
• Cathode Cathode 4 is selected from materials that have a workfunction allowing injection of electrons into the light-emitting layer. Other factors influence the selection of the cathode such as the possibility of adverse interactions between the cathode and the light- emitting material.
• the cathode may consist of a single material such as a layer of aluminium. Alternatively, it may comprise a plurality of metals, for example a bilayer of a low workfunction material and a high workfunction material such as calcium and aluminium as disclosed in WO 98/10621; elemental barium as disclosed in WO
• the cathode preferably has a workfunction of less than 3.5 eV, more preferably less than 3.2 eV, most preferably less than 3 eV. Work functions of metals can be found in, for example, Michaelson, J. Appl. Phys. 48(11), 4729, 1977.
• the cathode may be opaque or transparent.
• Transparent cathodes are particularly advantageous for active matrix devices because emission through a transparent anode in such devices is at least partially blocked by drive circuitry located underneath the emissive pixels.
• a transparent cathode comprises a layer of an electron injecting material that is sufficiently thin to be transparent. Typically, the lateral conductivity of this layer will be low as a result of its thinness. In this case, the layer of electron injecting material is used in combination with a thicker layer of transparent conducting material such as indium tin oxide.
• a transparent cathode device need not have a transparent anode (unless, of course, a fully transparent device is desired), and so the transparent anode used for bottom-emitting devices may be replaced or supplemented with a layer of reflective material such as a layer of aluminium.
• transparent cathode devices are disclosed in, for example, GB 2348316.
• Encapsulation Organic optoelectronic devices tend to be sensitive to moisture and oxygen.
• the substrate preferably has good barrier properties for prevention of ingress of moisture and oxygen into the device.
• the substrate is commonly glass, however alternative substrates may be used, in particular where flexibility of the device is desirable.
• the substrate may comprise a plastic as in US 6268695 which discloses a substrate of alternating plastic and barrier layers or a laminate of thin glass and plastic as disclosed in EP 0949850.
• the device may be encapsulated with an encapsulant (not shown) to prevent ingress of moisture and oxygen.
• encapsulants include a sheet of glass, films having suitable barrier properties such as silicon dioxide, silicon monoxide, silicon nitride or alternating stacks of polymer and dielectric as disclosed in, for example, WO 01/81649 or an airtight container as disclosed in, for example, WO 01/19142.
• a transparent encapsulating layer such as silicon monoxide or silicon dioxide may be deposited to micron levels of thickness, although in one preferred embodiment the thickness of such a layer is in the range of 20-300 nm.
• a getter material for absorption of any atmospheric moisture and / or oxygen that may permeate through the substrate or encapsulant may be disposed between the substrate and the encapsulant.
• Suitable solvents for forming compositions of the polymer for solution processing include many common organic solvents, such as mono- or poly-alkylbenzenes such as toluene and xylene.
• Particularly preferred solution deposition techniques including printing and coating techniques such spin-coating and inkjet printing.
• electroluminescent material is unnecessary - for example for lighting applications or simple monochrome segmented displays.
• Inkjet printing is particularly suitable for high information content displays, in particular full colour displays.
• a device may be inkjet printed by providing a patterned layer over the first electrode and defining wells for printing of one colour (in the case of a monochrome device) or multiple colours (in the case of a multicolour, in particular full colour device).
• the patterned layer is typically a layer of photoresist that is patterned to define wells as described in, for example, EP 0880303.
• the ink may be printed into channels defined within a patterned layer.
• the photoresist may be patterned to form channels which, unlike wells, extend over a plurality of pixels and which may be closed or open at the channel ends.
• solution deposition techniques include dip-coating, roll printing and screen printing.
• Monomer2 stagel was prepared after a similiar procedure described for Monomerl stage 1 starting from l-Bromo-3,5-di-n-hexylbenzene (292.0 g, 0.8976 mol) and 2,7- dibromofluorenone (275.8 g, 0.8160 mol). This yielded crude monomer2 stage 1
• the dark brown mixture was stirred for 1 hr, transferred to a separating funnel and the two phases were separated.
• the aqueous phase was extracted with hexane (2 x 400 ml), the organic phases were combined, washed with water (3 x 400 ml, pH7) and brine (400 ml).
• the solvent was removed under reduced pressure to yield an orange oil.
• the oil was dissolved in hexane (500 ml), filtered through a silica plug(09 cm x 6 cm, packed with hexane), eluted with hexane (1.5 L) followed by hexane/dichloro methane (80:20,1.0 L).
• a blue light-emitting polymer was formed by Suzuki polymerization as described in WO 00/53656 of Monomer Example 1 and the following further monomers:
• Monomer 7 was prepared according to the method described in WO 2010/001982.
• Monomer 9 was prepared according to the following method: nerme ae Thionyl chloride (100 ml) was added to 3,5-dibromobenzoic acid (50.0g, 178 mmoles) and heated at reflux for 6 hours. The excess thionyl chloride was then removed by distillation and the remaining brown solid was dissolved in dry tetrahydrofuran (1 L) and cooled to below -70°C under nitrogen in an acetone/dry ice bath. Phenyl magnesium bromide solution (179 ml, 1M in tetrahydrofuran, 179 mmoles) was added dropwise to the cold reaction mixture and the temperature was then allowed to rise to room temperature while stirring for 4 hours.
• Polymers were synthesized as described in WO 00/53656 from 50% dipinacoldiesters and 50% dibromides: PdCI 2 (PPh 3 ) 2 -f- onomerl ,2,.
• Monomerl,2 ??. ccaann bbee ( one or more different esters or bromides to result in random copolymers.
• HIL is a hole-injecting layer comprising a hole-injecting material
• HTL is a hole- transporting layer formed by spin-coating a light-emitting polymer comprising fluorene repeat units of formula (IV) and amine repeat units of formula (V)
• LE is a light-emitting layer formed by spin-coating Polymer A, B, C or D
• the cathode comprises a trilayer structure of a metal fluoride, aluminium and silver. Stability of the polymer was determined by measuring the time taken for brightness of the device to fall to 50% of an initial luminance. As shown in Figure 2, the comparative device containing polymer A in the light-emitting layer has a substantially shorter lifetime than the device containing polymer B, which contains asymmetrically substituted fluorene monomers.
• the comparative device containing polymer C in the light-emitting layer has a substantially shorter lifetime than the device containing polymer B, which contains asymmetrically substituted fluorene monomers.
• the comparative lifetime data of the device examples illustrate the increased stability obtained by incorporation of a repeat unit of formula (la), (lla) or (III).
• Modelling was performed at density functional level of theory using the B3LYP functional and 6-31g* basis set as implemented in Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Electroluminescent Light Sources (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

Family

ID=43824867

Family Applications (1)

Country Status (7)

Cited By (3)

Families Citing this family (4)

Citations (38)

Family Cites Families (12)

• 2011
  • 2011-01-31 GB GB1101641.7A patent/GB2494096B/en not_active Expired - Fee Related
• 2012
  • 2012-01-26 JP JP2013550943A patent/JP5886879B2/ja active Active
  • 2012-01-26 KR KR1020137022504A patent/KR101856276B1/ko active IP Right Grant
  • 2012-01-26 US US13/982,728 patent/US9293709B2/en active Active
  • 2012-01-26 CN CN201280006948.7A patent/CN103339168B/zh active Active
  • 2012-01-26 DE DE112012000614T patent/DE112012000614T5/de active Pending
  • 2012-01-26 CN CN201610563043.XA patent/CN106188503B/zh active Active
  • 2012-01-26 WO PCT/GB2012/000080 patent/WO2012104579A1/en active Application Filing
• 2016
  • 2016-02-17 JP JP2016027511A patent/JP2016138275A/ja active Pending

Patent Citations (38)

Non-Patent Citations (6)

Also Published As

Similar Documents

Legal Events