US20070248839A1 - Dibenzosilol Polymers, Their Preparation and Uses - Google Patents

Dibenzosilol Polymers, Their Preparation and Uses Download PDF

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US20070248839A1
US20070248839A1 US10/578,895 US57889504A US2007248839A1 US 20070248839 A1 US20070248839 A1 US 20070248839A1 US 57889504 A US57889504 A US 57889504A US 2007248839 A1 US2007248839 A1 US 2007248839A1
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formula
polymer
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Carl Towns
Chris Mak
Khai Chan
Andrew Holmes
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Cambridge Display Technology Ltd
Cambridge Enterprise Ltd
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Cambridge University Technical Services Ltd CUTS
Cambridge Enterprise Ltd
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Definitions

  • the invention relates to polymers for electronic and optical applications and the synthesis thereof.
  • OLED organic light-emissive device
  • photovoltaic device a photovoltaic device
  • the basic structure of these devices is a semiconducting organic layer, sandwiched between a cathode for injecting or accepting negative charge carriers (electrons) and an anode for injecting or accepting positive charge carriers (holes) into or from the organic layer.
  • an OLED is typically fabricated on a glass or plastic substrate coated with a transparent first electrode such as indium-tin-oxide (“ITO”).
  • ITO indium-tin-oxide
  • a layer of a thin film of at least one electroluminescent organic material covers the first electrode.
  • a cathode covers the layer of electroluminescent organic material.
  • the cathode is typically a metal or alloy and may comprise a single layer, such as aluminium, or a plurality of layers such as calcium and aluminium.
  • Other layers can be added to the device, for example to improve charge injection from the electrodes to the electroluminescent material.
  • a hole injection layer such as poly(ethylene dioxythiophene)/polystyrene sulfonate (PEDOT-PSS) or polyaniline may be provided between the anode and the electroluminescent material.
  • one of the electrodes is transparent, to allow the photons to escape or enter the device.
  • holes are injected into the highest occupied molecular orbital (HOMO) of the electroluminescent material and electrons are injected into its lowest unoccupied molecular orbital (LUMO). Holes and electrons then combine to generate excitons which undergo radiative decay, the wavelength of emission being at least partially dependant on the HOMO-LUMO bandgap.
  • HOMO highest occupied molecular orbital
  • LUMO unoccupied molecular orbital
  • Organic materials for use as light-emissive materials include polymers such as poly(p-phenylenevinylene) (as disclosed in WO 90/13148), polyfluorenes and polyphenylenes; the class of materials known as small molecule materials such as tris-(8-hydroxyquinoline)aluminium (“Alq 3 ”) as disclosed in U.S. Pat. No. 4,539,507; and the class of materials known as dendrimers as disclosed in WO 99/21935. These materials electroluminesce by radiative decay of singlet excitons (i.e. fluorescence) however spin statistics dictate that up to 75% of excitons are triplet excitons which undergo non-radiative decay, i.e.
  • quantum efficiency may be as low as 25% for fluorescent OLEDs and so these materials or similar materials capable of transporting charge may be used as hosts for dopants comprising heavy metal complexes capable of harvesting triplet excitons for radiative decay (phosphorescence) as disclosed in, for example, Pure Appl. Chem., 1999, 71, 2095, Materials Science & Engineering, R: Reports (2002), R39(5-6), 143-222 and Polymeric Materials Science and Engineering (2000), 83, 202-203.
  • Polyfluorenes having a repeat unit of formula (A) are disclosed in for example, Adv. Mater. 2000 12(23) 1737-1750: wherein R′′ represents a solubilising group such as n-octyl.
  • polymers have attracted considerable interest as electroluminescent materials because they are solution processable and have good film forming properties. Furthermore, these polymers may be made by Yamamoto or Suzuki polymerisation, for which the appropriate monomers are accessed simply by halogenation of fluorene to form a 2,7-dihalofluorene. These polymerisation techniques enable polymerisation of fluorene monomers with a wide range of aromatic co-monomers and afford a high degree of control over regioregularity of the polymer. Thus, the physical and electronic properties of polyfluorenes may be tailored by appropriate selection of monomers.
  • Linkage of the fluorene repeat units through the 2- and 7-positions is important for maximisation of conjugation through the repeat unit.
  • a difficulty encountered with blue electroluminescent polymers to date is that their lifetime (i.e. the time taken for brightness to halve from a given starting brightness at fixed current) tends to be shorter than that of corresponding red or green materials.
  • One of the factors that has been proposed as contributing to the more rapid degradation of blue materials is that their LUMO levels, and consequently the energy level of the charged state following injection of an electron into the LUMO, tend to be less deep (i.e. relatively low electron affinity) than those of corresponding red or green materials. It is therefore possible that materials comprising these lower electron affinities are less electrochemically stable and so more prone to degradation.
  • a full colour display will preferably have a common cathode material for all three electroluminescent materials.
  • a common cathode material for all three electroluminescent materials.
  • a blue electroluminescent material having a higher electron affinity than polyfluorenes or a material capable of injecting electrons into blue electroluminescent polymers is therefore desirable, however increasing the electron affinity of a wide bandgap material will tend to result in a smaller bandgap thus making the material less suitable as a blue emitter or as an electron transporting material for a blue emitter.
  • a further drawback of polyfluorenes is that blue electroluminescent polyfluorenes have a tendency to shift over time towards longer wavelengths, i.e. towards a redder colour of emission. This effect is believed to be due to oxidative degradation and aggregation of the polymer.
  • EP 1318163 discloses a monomer of formula (B), and electroluminescent polymers derived therefrom:
  • JP 2003-206289 discloses a monomer of formula (C) and polymers derived therefrom:
  • the alkoxy groups serve to direct lithiation at the adjacent 2- and 7-positions.
  • the alkoxy groups serve to direct bromination in the same way.
  • these alkoxy groups are significant in monomer synthesis, they are likely to cause repeat units derived from such monomers to suffer from steric interference with adjacent repeat units resulting in a twist in the polymer backbone and loss of conductivity. Furthermore, the electron donating nature of these alkoxy groups decreases the electron affinity of polymers derived from these monomers.
  • a further drawback of polymers derived from monomers (B) and (C) is that the phenyl and methyl groups of these monomer do not afford solubility in common organic solvents such as xylene.
  • the present inventors have found a novel class of dibenzosiloles that solve the aforementioned drawbacks of polyfluorenes.
  • the invention provides a polymer comprising an optionally substituted first repeat unit of formula (I): wherein each R is the same or different and represents H or an electron withdrawing group; and each R 1 is the same or different and represents a substituent.
  • Preferred electron withdrawing groups are selected from: groups comprising fluorine, cyano, nitro, carboxyl, amides, ketones, phosphinoyl, phosphonates, sulfones and esters.
  • Preferred groups comprising fluorine include fluorine atoms, fluoroalkyl, fluoroaryl and fluoroheteroaryl.
  • polymers according to the first aspect of the invention are high electron affinity, wide bandgap materials.
  • polymers according to the invention do not possess electron-donating groups in the 3- and 6-positions that lessen the electron affinity of the dibenzosilole units.
  • At least one R group is hydrogen. More preferably, both R groups are hydrogen.
  • At least one R 1 is a solubilising group.
  • each R 1 is the same or different and is selected from the group consisting of optionally substituted C 1-20 alkyl, C 1-20 alkoxy, aryl and heteroaryl. More preferably, each R 1 is independently a C 4-10 alkyl, most preferably n-hexyl or n-octyl.
  • the optional substituents, where present, are preferably electron withdrawing groups, in particular fluorine. One or more such substituents may be provided on each R 1 group.
  • the polymer comprises an optionally substituted aryl or heteroaryl second repeat unit.
  • the invention provides a monomer of formula (II): wherein R and R 1 are as described in the first aspect of the invention and each X is the same or different and represents a polymerisable group.
  • each X is the same or different and is selected from the group consisting of boronic acid groups, boronic ester groups, borane groups and halide functional groups.
  • the invention provides a method of forming a polymer comprising the step of polymerising the monomer of formula (II).
  • each X is independently selected from the group consisting of boronic acid groups, boronic ester groups and borane groups and halide functional groups and the polymerisation is performed in the presence of a transition metal catalyst.
  • each X is the same or different and is a halide functional group, and the polymerisation is performed in the presence of a nickel complex catalyst.
  • the method comprises polymerising:
  • the invention provides an optical device comprising a polymer according to the first aspect of the invention.
  • the optical device comprises an anode, a cathode and a layer of the polymer according to the first aspect of the invention located between the anode and the cathode.
  • the optical device is an electroluminescent device.
  • the invention provides a switching device comprising a polymer according to the first aspect of the invention.
  • the switching device is a thin film transistor.
  • monomers of formula (II) may be formed from a class of key intermediates that do not require the presence of ortho-directing groups.
  • the invention provides an optionally substituted compound of formula (IV): wherein each X 1 and each X 2 is the same or different and represents a leaving group capable of participating in a transmetallation reaction and X 2 has an electronegativity less than that of X 1 .
  • both X 1 groups are the same and both X 2 groups are the same.
  • the electronegativity of the least electronegative X 1 group shall be greater than the electronegativity of the most electronegative X 2 group.
  • each X 1 and X 2 is independently a halogen. More preferably, X 1 and X 2 are selected from bromine, chlorine and iodine. Most preferably, X 1 is bromine and X 2 is iodine.
  • the compound of formula (IV) serves as an intermediate to a variety of monomers including but not limited to dibenzosiloles.
  • the invention provides a method of forming a monomer of formula (VI) from a compound of formula (V) according to the following scheme: wherein the method comprises reacting the compound of formula (V) with a transmetallating agent followed by reaction with a compound of formula LG-Y-LG, wherein X 1 and R are as defined in the sixth aspect of the invention; each X 3 is the same or different and represents a leaving group capable of participating in a transmetallation having an electronegativity less than or the same as that of X 1 ; Y represents a divalent residue comprising a backbone of 1-3 atoms; and each LG is the same or different and represents a leaving group.
  • transmetallating agent is meant a compound capable of reacting with the C—X 2 bond of the compound of formula (IV) to transform it into a carbon-metal bond.
  • Y comprises a single atom in its backbone selected from the group consisting of —CR 3 2 —, —SiR 3 2 —, —NR 3 —, —PR 3 —, —GeR 3 2 —, —SnR 3 2 —, O and S, wherein selected from the group consisting of optionally substituted alkyl, alkoxy, aryl and heteroaryl. More preferably, Y is selected from the group consisting of —CR 3 2 —, —SiR 3 2 —, —NR 3 —, —PR 3 —, —GeR 3 2 —, —SnR 3 2 —, O and S.
  • each R 3 is the same or different and is a C 1-20 alkyl.
  • each LG is the same or different and is a halogen, more preferably chlorine, bromine or iodine.
  • the transmetallating agent is a compound of formula R 4 -M wherein R 4 is alkyl or aryl and M is a metal.
  • M is lithium.
  • R 4 is C 1-4 alkyl or phenyl.
  • linkage of dibenzosilole repeat units according to the invention through their 2- and 7-positions maximises conjugation of polymer chains comprising these repeat units.
  • the present inventors have found that non-2,7-linked dibenzosiloles possess a wider bandgap than corresponding 2,7-linked dibenzosiloles and at the same time retain a desirable high electron affinity.
  • non-2,7-linked dibenzosiloles have been found to possess a higher triplet energy level than corresponding 2,7-linked dibenzosiloles and as such may serve as the host material for a wider range of fluorescent or phosphorescent dopants.
  • the invention provides a polymer comprising an optionally substituted first repeat unit of formula (VII): wherein each R 2 is the same or different and represents a substituent; the R 2 groups may be linked to form a ring; and bond (a) is not linked to the 2-position of the repeat unit of formula (VII).
  • Bond (b) may or may not be bound to the 7-position of the repeat unit of formula (VII), however in a preferred embodiment bond (b) is not bound to the 7-position of the repeat unit of formula (VII).
  • bond (a) is bound to the 3-position of the repeat unit of formula (VII).
  • bond (b) is bound to the 6-position of the repeat unit of formula (VII).
  • At least one R 2 is a solubilising group.
  • each R 2 is the same or different and is selected from the group consisting of optionally substituted C 1-20 alkyl, C 1-20 alkoxy, aryl and heteroaryl. More preferably, each R 2 is independently a C 4-10 alkyl, most preferably n-hexyl or n-octyl.
  • the polymer comprises an optionally substituted aryl or heteroaryl second repeat unit.
  • the invention provides an optionally substituted monomer of formula (VIII): wherein each R 2 is as defined in the eighth aspect of the invention; each X is as defined in the second aspect of the invention and at least one X is not linked to the 2-position of the repeat unit of formula (VIII).
  • the monomer of formula (VIII) may be polymerised in accordance with the method described in the third aspect of the invention.
  • polymers comprising dibenzosilole repeat units function very effectively as host materials for luminescent dopants.
  • the invention provides an electroluminescent device comprising an anode, a cathode and an electroluminescent layer located between the anode and cathode wherein the electroluminescent layer comprises a polymeric host material comprising an optionally substituted first repeat unit of formula (IX) and a luminescent dopant wherein R 1 is as described in the first aspect of the invention.
  • the repeat unit of formula (IX) is not linked through its 2-position. More preferably, the repeat unit of formula (IX) is not linked through its 2- or 7-positions. Most preferably, the repeat unit of formula (IX) is linked through its 3- and 6-positions.
  • the polymer comprises a second repeat unit.
  • the second repeat unit comprises a hole transporting material. More preferably, the second repeat unit is a carbazole, more preferably a 3,6-linked carbazole.
  • the luminescent dopant may be phosphorescent or fluorescent.
  • the luminescent dopant is phosphorescent.
  • the repeat unit of formula (IX) is unsubstituted.
  • the dibenzosiloles disclosed in this prior art do not carry any reactive groups other than at the silicon atom of the dibenzosilole where transalkylation takes place.
  • the present inventors have surprisingly found that the substituents carried at the silicon atom of dibenzosiloles may selectively be changed, e.g. by transalkylation, even when reactive substituents are present elsewhere on the dibenzosilole.
  • the invention provides a method of forming an optionally substituted compound of formula (X) according to the following process: wherein each R 8 is Independently selected from the group consisting of C 1-20 alkyl and aryl; each R 9 is different from R 8 and is independently selected from the group consisting of C 1-20 alkyl, aryl and heteroaryl; M 1 is a metal; and Z is a reactive group capable of undergoing reaction with M 1 -R 9 .
  • M 1 is lithium
  • R 8 is methyl
  • Z is trialkylsilyl, more preferably trimethylsilyl.
  • R 9 —R 9 are C 4-20 alkylene or optionally substituted biaryl or bi-heteroaryl, in particular biphenyl.
  • a particularly preferred compound of formula M 1 -R 9 —R 9 -M 1 has the structure shown below, which may optionally be substituted:
  • FIG. 1 shows a prior art electroluminescent device
  • FIG. 2 ( a ) shows a plot of photoluminescent wavelength over time for a prior art polyfluorene
  • FIG. 2 ( b ) shows a plot of photoluminescent wavelength over time for a co-polymer according to the invention
  • FIG. 2 ( c ) shows a plot of photoluminescent wavelength over time for a homopolymer according to the invention
  • FIG. 3 shows a plot of electroluminescent wavelength for polymers according to the invention as compared to a prior art polyfluorene
  • a polymer according to the present invention may comprise a homopolymer or copolymers (including terpolymers or higher order polymers).
  • Copolymers according to the present invention include regular alternating, random and block polymers where the percentage of each monomer used to prepare the polymer may vary.
  • Preferred co-repeat units include triarylamines, arylenes and heteroarylenes.
  • arylene repeat units are fluorene, particularly 2,7-linked 9,9 dialkyl fluorene or 2,7-linked 9,9 diaryl fluorene; spirofluorene such as 2,7-linked 9,9-spirofluorene; indenofluorene such as a 2,7-linked indenofluorene; or phenyl such as alkyl or alkoxy substituted 1,4-phenylene. Each of these groups may optionally be substituted.
  • Particularly preferred triarylamine repeat units derived from triarylamine monomers include units of formulae 1-6:
  • a and B may be the same or different and are substituent groups. It is preferred that one or both of A and B is independently selected from the group consisting of alkyl, aryl, perfluoroalkyl, cyano, alkoxy, heteroaryl, alkylaryl and arylalkyl groups. One or more of A and B also may be hydrogen. It is preferred that one or more of A and B is independently an unsubstituted, isobutyl group, an n-alkyl, an n-alkoxy or a trifluoromethyl group because they are suitable for helping to select the HOMO level and/or for improving solubility of the polymer.
  • heteroaryl repeat units include units of formulae 7-21: wherein R 6 and R 7 are the same or different and are each independently hydrogen or a substituent group, preferably alkyl, aryl, perfluoroalkyl, thioalkyl, cyano, alkoxy, heteroaryl, alkylaryl or arylalkyl.
  • R 6 and R 7 are preferably the same. More preferably, they are the same and are each a phenyl group.
  • Ar groups are known in this art, for example as disclosed in WO 00/55927 and WO 00/46321, the contents of which are incorporated herein by reference.
  • the polymer is soluble.
  • Substituents such as C 1-10 alkyl or C 1-10 alkoxy may usefully be selected to confer on the polymer solubility in a particular solvent system.
  • Typical solvents include mono- or poly-alkylated benzenes such as toluene and xylene or tetrahydrofuran.
  • Techniques for solution deposition of the polymer according to the invention include inkjet printing as disclosed in EP 0880303, spin-coating, dip-coating, doctor blade coating and screen printing.
  • the polymers according to the invention may carry cross-linkable groups such as oxetanes, azides, acrylates, vinyl and ethynyl groups in order that the polymer may be deposited in a soluble form followed by cross-linking to render the polymer insoluble.
  • Cross-linking may be achieved through thermal treatment or exposure of the polymer to radiation, in particular UV radiation.
  • Cross-linking may be employed to allow deposition of multiple layers from solution as disclosed in WO 96/20253.
  • photo-initiated cross-linking may be used by exposure of a polymer layer through a mask to form a pattern of insoluble material from which unexposed, soluble polymer may be removed by solvent treatment as disclosed in Nature 421, 829-833, 2003.
  • Suzuki polymerisation as disclosed in, for example, WO 00/53656 and Yamamoto polymerisation as disclosed in, for example, “Macromolecules”, 31, 1099-1103 (1998).
  • Suzuki polymerisation entails the coupling of halide and boron derivative functional groups;
  • Yamamoto polymerisation entails the coupling of halide functional groups.
  • each monomer is provided with two reactive functional groups wherein each functional group is independently selected from the group consisting of (a) boron derivative functional groups selected from boronic acid groups, boronic ester groups and borane groups and (b) halide functional groups.
  • the transmetallating agents used to prepare monomers of the invention include alkyl- and aryl-lithium compounds such as methyllithium, n-butyllithium, t-butyllithium, phenyllithium and lithium di-isopropyl amine.
  • Examples of monomers of formula (VI) preparable according to the method of the invention include the following:
  • the standard architecture of an optical device according to the invention in particular an electroluminescent device, comprises a transparent glass or plastic substrate 1 , an anode of indium tin oxide 2 and a cathode 4 .
  • the polymer according to the invention is located in layer 3 between anode 2 and cathode 4 .
  • Layer 3 may comprise the polymer according to the invention alone or a plurality of polymers. Where a plurality of polymers are deposited, they may comprise a blend of at least two of a hole transporting polymer, an electron transporting polymer and, where the device is a PLED, an emissive polymer as disclosed in WO 99/48160.
  • layer 3 may be formed from a single polymer that comprises regions selected from two or more of hole transporting regions, electron transporting regions and emissive regions as disclosed in, for example, WO 00/55927 and U.S. Pat. No. 6,353,083.
  • Each of the functions of hole transport, electron transport and emission may be provided by separate polymers or separate regions of a single polymer. Alternatively, more than one function may be performed by a single region or polymer.
  • a single polymer or region may be capable of both charge transport and emission.
  • Each region may comprise a single repeat unit, e.g. a triarylamine repeat unit may be a hole transporting region.
  • each region may be a chain of repeat units, such as a chain of polyfluorene or dibenzosilole units as an electron transporting region.
  • the different regions within such a polymer may be provided along the polymer backbone, as per U.S. Pat. No. 6,353,083, or as groups pendant from the polymer backbone as per WO 01/62869.
  • a separate hole transporting layer and/or an electron transporting layer may be provided.
  • the polymers according to the invention may be used as the host for a fluorescent dopant as disclosed in, for example, J. Appl. Phys. 65, 3610, 1989 or as the host for a phosphorescent dopant as disclosed in, for example, Nature (London), 1998, 395, 151.
  • Preferred metal complexes comprise optionally substituted complexes of formula (XI): M 1 L 1 q L 2 r L 3 s (XI) wherein M 1 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 coordination sites on L 3 .
  • Heavy elements M induce strong spin-orbit coupling to allow rapid intersystem crossing and emission from triplet states (phosphorescence).
  • Suitable heavy metals M include:
  • Suitable coordinating groups for the f-block metals include oxygen or nitrogen donor systems such as carboxylic acids, 1,3-diketonates, hydroxy carboxylic acids, Schiff bases including acyl phenols and iminoacyl groups.
  • oxygen or nitrogen donor systems such as carboxylic acids, 1,3-diketonates, hydroxy carboxylic acids, Schiff bases including acyl phenols and iminoacyl groups.
  • luminescent lanthanide metal complexes require sensitsing 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 form organometallic complexes with carbon or nitrogen donors such as porphyrin or bidentate ligands of formula (XII): wherein Ar 1 and Ar2 may be the same or different and are independently selected from optionally substituted aryl or heteroaryl; Z 1 and Z 2 may be the same or different and are independently selected from carbon or nitrogen; and Ar 1 and Ar 2 may be fused together.
  • Ligands wherein Z 1 is carbon and Z 2 is nitrogen are particularly preferred.
  • Each of Ar 1 and Ar2 may carry one or more substituents.
  • 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 02/68435 and EP 1245659; and dendrons which may be used to obtain or enhance solution processability of the metal complex as disclosed in WO 02/66552.
  • 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. For these complexes, the emission colour is determined by the choice of ligand as well as the metal.
  • a wide range of fluorescent low molecular weight metal complexes are known and have been demonstrated in organic light emitting devices [see, e. g., Macromol. Sym. 125 (1997) 1-48, U.S. Pat. No. 5,150,006, U.S. Pat. No. 6,083,634 and U.S. Pat. No. 5,432,014], in particular tris-(8-hydroxyquinoline)aluminium.
  • 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 salicylato 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 metal complex may be incorporated into the host polymer of the invention, either as a substituent on the main chain of the polymer or incorporated into the main chain of the polymer, as disclosed in, for example, EP 1245659, WO 02/31896, WO 03/18653 and WO 03/22908.
  • the polymer may provide the functions of emission and at least one of hole transport and electron transport.
  • the host polymer of the invention may be a homopolymer or a copolymer.
  • suitable co-repeat units include carbazoles, such as 2,7-linked carbazole repeat units.
  • 3,6-linked carbazole repeat units as disclosed in J. Am. Chem. Soc. 2004, 126, 6035-6042 may also be used.
  • a preferred host material has formula (XIII): wherein R 1 is as defined in the first aspect of the invention.
  • Polymers of this type may comprise blocks of the illustrated dibenzosilole and carbazole units, however in a particularly preferred embodiment the polymer (XIII) is a 1:1 copolymer of alternating dibenzosilole and carbazole units.
  • Suitable co-repeat units for host co-polymers according to the invention include triarylamine repeat units of formulae 1-6 described above. Accordingly, another preferred host polymer has formula (XIV): wherein R 1 is as defined in the first aspect of the invention and A is as defined above. Polymers of this type may comprise blocks of the Illustrated dibenzosilole and triarylamine units, however in a particularly preferred embodiment the polymer (XIV) is a 1:1 copolymer of alternating dibenzosilole and carbazole units.
  • a layer of organic hole injection material (not shown) between the anode 2 and the polymer layer 3 is desirable because it assists hole injection from the anode into the layer or layers of semiconducting polymer.
  • organic hole injection materials include poly(ethylene dioxythiophene) (PEDT/PSS) as disclosed in EP 0901176 and EP 0947123, or polyaniline as disclosed in U.S. Pat. No. 5,723,873 and U.S. Pat. No. 5,798,170.
  • Cathode 4 is selected from materials that have a workfunction allowing injection of electrons into the electroluminescent layer. Other factors influence the selection of the cathode such as the possibility of the adverse interactions between the cathode and the electroluminescent 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 calcium and aluminium as disclosed in WO 98/10621, elemental barium disclosed in WO 98/57381, Appl. Phys. Lett.
  • a typical electroluminescent device comprises an anode having a workfunction of 4.8 eV. Accordingly, the HOMO level of the hole transporting region is preferably around 4.8-5.5 eV. Similarly, the cathode of a typical device will have a workfunction of around 3 eV. Accordingly, the LUMO level of the electron transporting region is preferably around 3-3.5 eV.
  • the polymers according to the invention may also be used in current switching devices for an integrated circuit as disclosed in, for example, WO 99/54936.
  • the polymer may be a component of a field effect transistor comprising an insulator with a gate electrode located on one side of the insulator; a polymer according to the invention located on the other side of the insulator; and a drain electrode and a source electrode located on the polymer.
  • Electroluminescent devices may be monochrome devices or full colour devices (i.e. formed from red, green and blue electroluminescent materials).
  • 4,4′-Dibromo-biphenyl-2,2′-diamine (5.0 g, 14.6 mmol) was suspended in 16% w/w aqueous.
  • HCl (16 cm 3 ) at 0° C.
  • Sodium nitrite (2.2 g, 31.9 mmol) was added dropwise whilst maintaining the temperature at 0° C.
  • KI solution (5.0 g, 30.1 mmol in 5 cm 3 H 2 O) was added dropwise to the reaction mixture at ⁇ 10° C. The reaction mixture was allowed to warm to room temperature, and then to 50° C. for 2 h.
  • Monomers according to the second aspect of the invention may alternatively be prepared according to the process set out below wherein the intermediate compound 2,2′-dibromo-4,4′-di(trimethylsilyl)-1,1′-biphenyl is firstly prepared according to the reaction scheme shown below:
  • the monomer according to the second aspect of the invention may be derived from this biphenyl intermediate by one of two routes:
  • a homopolymer according to the first aspect of the invention was prepared by Suzuki polymerisation of Monomer 1 and Monomer 2 followed by end-capping with bromobenzene and phenylboronic acid according to the following scheme to afford dibenzosilole polymer PS6:
  • a copolymer according to the invention was prepared by Suzuki polymerisation as disclosed in WO 00/53656 with a diboronic acid of di(n-hexyl)fluorene followed by end-capping with bromobenzene and phenyl boronic acid to afford Polymer PS6F6 as shown below:
  • a device- was made according to the above method comprising a layer of poly-9,9-di(n-hexyl)-2,7-fluorene (hereinafter referred to as Polymer PF6).
  • the PS6 homopolymer according to the invention has a deeper LUMO level, i.e. it has a higher electron affinity, than the corresponding polyfluorene homopolymer PF6.
  • a wide HOMO-LUMO bandgap similar to that of PF6 is preserved.
  • data for the PF6S6 polymer shows that a deep LUMO level is preserved when the dibenzosilole units of the invention are conjugated with units having a shallower LUMO level.
  • devices comprising PS6 or PS6F6 give sustained blue emission with emission maxima being identical to that of photoluminescence at 426 nm.
  • the PF6 device on the other hand degraded very rapidly under current and showed a green emission upon operation, displaying a broad peak at about 540 nm.
  • a monomer according to the ninth aspect of the invention was synthesised according to the following reaction scheme. Again, as with the 2,7-linked dibenzosiloles described above, transalkylation of the dimethylsilyl group (step a) does not affect the trimethylsilyl end groups and so this route again provides a means for introducing a wide range of substituents on the silicon atom.
  • Poly(9,9-dihexyl-2,7-fluorenyl-alt-9,9-dihexyl-3,6-dibenzosilyl) was prepared according to the following method:
  • the table below shows the absorption maxima and optical band gaps of the copolymers.
  • Band gaps of the polymers measured from the UV absorption onsets.
  • Polymer A comprising a 3,7-linked dibenzosilole according to the eighth aspect of the invention is significantly blue shifted and has a wider bandgap as compared to the 2,7-linked poly-dibenzosilole Polymer B and the 2,7-linked polyfluorene PF6.
  • the films of the copolymers were prepared by spin-coating the samples (1.0 wt % solution in toluene) on the gold working electrode. Measurements were then taken in a solution of Bu 4 N + ClO 4 ⁇ (0.10 M) in acetonitrile at a scan rate of 50 mV/s at room temperature, using a platinum wire as the counter electrode and a Ag/AgCl electrode as the reference electrode. Both measurements were calibrated against ferrocene which has an ionization potential of 4.8 eV.
  • the 3,6-linked poly-dibenzosilole of Polymer A according to the eighth aspect of the invention has a wider HOMO-LUMO bandgap as compared to 2,7-linked Polymer A.
  • b Optical band gap energy determined by the onset absorption (UV-Vis).
  • c Determined from E onset(ox) (taking energy level of ferrocene to be ⁇ 4.8 eV under vacuum).
  • d Determined from adding E g opt to the HOMO energy level.

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US20140187716A1 (en) * 2011-07-15 2014-07-03 The University Of Melbourne Process for the synthesis of conjugated polymers
US9134239B2 (en) 2011-03-21 2015-09-15 The Regents Of The University Of California Thin layer high explosive fluorescent polymer sensing methods, sensors and kits
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