WO2013159862A1 - Conjugated polymers - Google Patents

Conjugated polymers Download PDF

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Publication number
WO2013159862A1
WO2013159862A1 PCT/EP2013/000977 EP2013000977W WO2013159862A1 WO 2013159862 A1 WO2013159862 A1 WO 2013159862A1 EP 2013000977 W EP2013000977 W EP 2013000977W WO 2013159862 A1 WO2013159862 A1 WO 2013159862A1
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WIPO (PCT)
Prior art keywords
polymer
formula
group
atoms
aryl
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PCT/EP2013/000977
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French (fr)
Inventor
Mansoor D'lavari
William Mitchell
Changsheng Wang
Steven Tierney
David Sparrowe
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Merck Patent Gmbh
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Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to JP2015507402A priority Critical patent/JP6345649B2/en
Priority to KR1020147032827A priority patent/KR20150016255A/en
Priority to GB1420608.0A priority patent/GB2516207A/en
Priority to EP13717167.4A priority patent/EP2841485A1/en
Priority to US14/396,786 priority patent/US9676901B2/en
Priority to CN201380021008.XA priority patent/CN104245786B/en
Publication of WO2013159862A1 publication Critical patent/WO2013159862A1/en

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Definitions

  • the invention relates to novel conjugated polymers containing one or more repeating units derived from indacenodibenzothiophene or dithia- dicyclopenta-dibenzothiophene, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations.
  • OE organic electronic
  • OPD organic photovoltaic
  • OPD organic photodetectors
  • OSC Organic semiconducting
  • OLED organic photovoltaics
  • Conjugated polymers have found use in OPVs as they allow devices to be manufactured by solution-processing techniques such as spin casting, dip coating or ink jet printing. Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices.
  • solution-processing techniques such as spin casting, dip coating or ink jet printing.
  • Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices.
  • polymer based photovoltaic devices are achieving efficiencies above 8%.
  • ⁇ - ⁇ overlaps defines the primary energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), enables both charge injection and transport, and facilitates optical absorption.
  • HOMO and LUMO the primary energy levels of the highest occupied and lowest unoccupied molecular orbitals
  • the latter further fine-tunes the energy leverls and enables solubility and hence processability of the materials as well as ⁇ - ⁇ interactions of the molecular backbones in the solid state.
  • a high degree of molecular planarity reduces the energetic disorder of OSC backbones and accordingly enhances charge carrier mobilities.
  • OSC organic semiconducting
  • IDDBT fused indacenodibenzothiophene
  • TTDBT dithia-dicyclopenta-dibenzothiophene
  • the invention relates to conjugated polymers comprising one or more divalent units of formula I
  • thiophene ring may also be substituted in 3-position by a group R 1 ,
  • thiophene ring may also be substituted in 3-position by a group R ,
  • O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, CI, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, preferably by halogen or by one or more of the aforementioned alkyl or cyclic alkyl groups,
  • Y 1 and Y 2 independently of each other denote H, F, CI or CN, R° and R 00 independently of each other denote H or optionally
  • substituted C - 0 carbyl or hydrocarbyl and preferably denote H or alkyl with 1 to 12 C-atoms.
  • the invention further relates to a formulation comprising one or more polymers comprising a unit of formula I and one or more solvents, preferably selected from organic solvents.
  • the invention further relates to the use of units of formula I as electron donor units in semiconducting polymers.
  • the invention further relates to conjugated polymers comprising one or more repeating units of formula I and/or one or more groups selected from aryl and heteroaryl groups that are optionally substituted, and wherein at least one repeating unit in the polymer is a unit of formula I.
  • the invention further relates to monomers containing a unit of formula I and further containing one or more reactive groups which can be reacted to form a conjugated polymer as described above and below.
  • the invention further relates to semiconducting polymers comprising one or more units of formula I as electron donor units, and preferably further comprising one or more units having electron acceptor properties.
  • the invention further relates to the use of the polymers according to the present invention as electron donor or p-type semiconductor.
  • the invention further relates to the use of the polymers according to the present invention as electron donor component in a semiconducting material, formulation, polymer blend, device or component of a device.
  • the invention further relates to a semiconducting material, formulation, polymer blend, device or component of a device comprising a polymer according to the present invention as electron donor component, and preferably further comprising one or more compounds or polymers having electron acceptor properties.
  • the invention further relates to a mixture or polymer blend comprising one or more polymers according to the present invention and one or more additional compounds which are preferably selected from compounds having one or more of semiconducting, charge transport, hole or electron transport, hole or electron blocking, electrically conducting,
  • the invention further relates to a mixture or polymer blend as described above and below, which comprises one or more polymers of the present invention and one or more n-type organic semiconductor compounds, preferably selected from fullerenes or substituted fullerenes.
  • the invention further relates to a formulation comprising one or more polymers, formulations, mixtures or polymer blends according to the present invention and optionally one or more solvents, preferably selected from organic solvents.
  • the invention further relates to the use of a polymer, formulation, mixture or polymer blend of the present invention as charge transport,
  • the invention further relates to a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer, formulation, mixture or polymer blend according to the present invention.
  • the invention further relates to an optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a polymer, formulation, mixture or polymer blend, or comprises a charge transport,
  • photoluminescent devices include, without limitation, organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, and photoconductors.
  • OFET organic field effect transistors
  • OFT organic thin film transistors
  • OLED organic light emitting diodes
  • OLET organic light emitting transistors
  • OLED organic light emitting transistors
  • OLET organic light emitting transistors
  • OLED organic light emitting transistors
  • OLED organic light emitting transistors
  • OLET organic photovoltaic devices
  • OPD organic photodetectors
  • organic solar cells laser diodes, Schottky diodes, and photoconductors.
  • the components of the above devices include, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
  • charge injection layers charge transport layers
  • interlayers interlayers
  • planarising layers antistatic films
  • PEM polymer electrolyte membranes
  • conducting substrates conducting patterns.
  • the assemblies comprising such devices or components include, without limitation, integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containg them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.
  • IC integrated circuits
  • RFID radio frequency identification
  • electrophotographic devices electrophotographic recording devices
  • organic memory devices organic memory devices
  • sensor devices biosensors and biochips
  • the compounds, polymers, formulations, mixtures or polymer blends of the present invention can be used as electrode materials in batteries and in components or devices for detecting and discriminating DNA sequences.
  • the polymers of the present invention are easy to synthesize and exhibit advantageous properties. They show good processability for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods.
  • the co-polymers derived from monomers of the present invention and electron donor monomers show low bandgaps, high charge carrier mobilities, high external quantum efficiencies in BHJ solar cells, good morphology when used in p/n-type blends e.g. with fullerenes, high oxidative stability, and a long lifetime in electronic devices, and are promising materials for organic electronic OE devices, especially for OPV devices with high power conversion efficiency.
  • the units of formula I are especially suitable as (electron) donor unit in both n-type and p-type semiconducting compounds, polymers or copolymers, in particular copolymers containing both donor and acceptor units, and for the preparation of blends of p-type and n-type
  • the repeating units of formula I contain an enlarged system of fused aromatic rings, which creates numerous benefits in developing novel high performance OSC materials.
  • a large number of fused aromatic rings along the long axis of the core structure increases the overall planarity and reduces the number of the potential twists of the conjugated molecular backbone. Elongation of the ⁇ - ⁇ structure or monomer increases the extent of conjugation which facilitates charge transport along the polymer backbone.
  • the high proportion of sulphur atoms in the molecular backbone through the presence of fused thiophene rings promotes more intermolecular short contacts, which benefits charge hopping between molecules.
  • the large number of fused rings leads to an increased proportion of ladder structure in the OSC polymer main chain. This forms a broader and more intense absorption band resulting in improved solar light harvesting compared with prior art materials.
  • fusing aromatic rings can more efficiently modify the HOMO and LUMO energy levels and bandgaps of the target monomer structures compared with periphery substitutions.
  • the polymers of the present invention show the following advantageous properties: i) The indacenodibenzothiophene (IDDBT) and dithia-dicyclopenta- dibenzothiophene (TTDBT) units are expected to exhibit a co-planar structure. Adopting a highly co-planar structure in the solid-state is beneficial for charge transport. ii) The IDDBT and TTDBT core structures can be solubilised by both four alkyl groups or two alkylidene groups. Compared with the tetra-alkyl analogues, the dialkylidene substituted IDDBT-based molecules and polymers are expected to possess a higher degree of planarity.
  • indacenodibenzothiophene (IDDBT) and dithia-dicyclopenta- dibenzothiophene (TTDBT) cores or co-polymerisation with appropriate co-monomer(s) can afford conjugated polymers that are suitable as organic semiconductors for organic electronic applications.
  • polymer will be understood to mean a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass (Pure Appl. Chem., 1996, 68, 2291).
  • oligomer will be understood to mean a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass (Pure Appl. Chem., 1996, 68, 2291).
  • a polymer will be understood to mean a compound having > 1 , i.e. at least 2 repeat units, preferably ⁇ 5 repeat units, and an oligomer will be understood to mean a compound with > 1 and ⁇ 10, preferably ⁇ 5, repeat units.
  • polymer will be understood to mean a molecule that encompasses a backbone (also referred to as “main chain”) of one or more distinct types of repeat units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms “oligomer”, “copolymer”, “homopolymer” and the like.
  • polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto. Further, such residues and other elements, while normally removed during post polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media.
  • an asterisk ( * ) will be understood to mean a chemical linkage to an adjacent unit or to a terminal group in the polymer backbone.
  • an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring.
  • the terms “repeat unit”, “repeating unit” and “monomeric unit” are used interchangeably and will be understood to mean the constitutional repeating unit (CRU), which is the smallest constitutional unit the repetition of which constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain ⁇ Pure Appl. Chem., 1996, 68, 2291).
  • the term “unit” will be understood to mean a structural unit which can be a repeating unit on its own, or can together with other units form a constitutional repeating unit.
  • terminal group will be understood to mean a group that terminates a polymer backbone.
  • the expression "in terminal position in the backbone” will be understood to mean a divalent unit or repeat unit that is linked at one side to such a terminal group and at the other side to another repeat unit.
  • Such terminal groups include endcap groups, or reactive groups that are attached to a monomer forming the polymer backbone which did not participate in the polymerisation reaction, like for example a group having the meaning of R 5 or R 6 as defined below.
  • endcap group will be understood to mean a group that is attached to, or replacing, a terminal group of the polymer backbone.
  • the endcap group can be introduced into the polymer by an endcapping process. Endcapping can be carried out for example by reacting the terminal groups of the polymer backbone with a
  • endcapper like for example an alkyl- or arylhalide, an alkyl- or arylstannane or an alkyl- or arylboronate.
  • the endcapper can be added for example after the polymerisation reaction. Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerisation reaction. In situ addition of an endcapper can also be used to terminate the polymerisation reaction and thus control the molecular weight of the forming polymer.
  • Typical endcap groups are for example H, phenyl and lower alkyl.
  • small molecule will be understood to mean a monomeric compound which typically does not contain a reactive group by which it can be reacted to form a polymer, and which is designated to be used in monomeric form.
  • monomer unless stated otherwise will be understood to mean a monomeric compound that carries one or more reactive functional groups by which it can be reacted to form a polymer.
  • the terms "donor” or “donating” and “acceptor” or “accepting” will be understood to mean an electron donor or electron acceptor, respectively.
  • Electrical donor will be understood to mean a chemical entity that donates electrons to another compound or another group of atoms of a compound.
  • Electrical acceptor will be understood to mean a chemical entity that accepts electrons transferred to it from another compound or another group of atoms of a compound, (see also U.S. Environmental Protection Agency, 2009, Glossary of technical terms, httD://www.epa.qov/oust/cat/TUMGLOSS.HTM
  • n-type or n-type semoiconductor will be understood to mean an extrinsic semiconductor in which the conduction electron density is in excess of the mobile hole density
  • p- type or p-type semiconductor will be understood to mean an extrinsic semiconductor in which mobile hole density is in excess of the conduction electron density
  • leaving group will be understood to mean an atom or group (which may be charged or uncharged) that becomes detached from an atom in what is considered to be the residual or main part of the molecule taking part in a specified reaction (see also Pure AppI. Chem., 1994, 66, 1134).
  • conjugated will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp 2 - hybridisation (or optionally also sp-hybridisation), and wherein these C atoms may also be replaced by hetero atoms. In the simplest case this is for example a compound with alternating C-C single and double (or triple) bonds, but is also inclusive of compounds with aromatic units like for example 1 ,4-phenylene.
  • the term "mainly” in this connection will be understood to mean that a compound with naturally (spontaneously) occurring defects, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
  • the molecular weight is given as the number average molecular weight M n or weight average molecular weight Mw, which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene or 1 , 2, 4-trichloro- benzene. Unless stated otherwise, 1 ,2,4-trichlorobenzene is used as solvent.
  • GPC gel permeation chromatography
  • the term "carbyl group” will be understood to mean denotes any monovalent or multivalent organic radical moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example -C ⁇ C-), or optionally combined with at least one non- carbon atom such as N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
  • the term "hydrocarbyl group” will be understood to mean a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example N, O, S, P, Si, Se, As, Te or Ge.
  • hetero atom will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean N, O, S, P, Si, Se, As, Te or Ge.
  • a carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, including spiro and/or fused rings.
  • Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy,
  • alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore
  • alkylaryloxy arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and
  • aryloxycarbonyloxy each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, wherein all these groups do optionally contain one or more hetero atoms, preferably selected from N, O, S, P, Si, Se, As, Te and Ge.
  • the carbyl or hydrocarbyl group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially aryl, alkenyl and alkynyl groups (especially ethynyl). Where the Ci-C 40 carbyl or hydrocarbyl group is acyclic, the group may be straight-chain or branched.
  • the C1-C40 carbyl or hydrocarbyl group includes for example: a Ci-C 40 alkyl group, a Ci-C 4 o fluoroalkyl group, a Ci-C 40 alkoxy or oxaalkyl group, a C2-C40 alkenyl group, a C 2 -C 4 o alkynyl group, a C 3 -C 40 allyl group, a C 4 -C 4 o alkyldienyl group, a C4-C40 polyenyl group, a C 2 -C 4 o ketone group, a C 2 -C 40 ester group, a C 6 -Ci 8 aryl group, a C 6 -C 4 o alkylaryl group, a C 6 -C 4 o arylalkyl group, a C -C 4 o cycloalkyl group, a C -C 40 cycloalkenyl group, and the like.
  • Ci-C 20 alkyl group a Ci-C 20 fluoroalkyl group, a C 2 -C 2 o alkenyl group, a C 2 -C 2 o alkynyl group, a C3- C 2 o allyl group, a C 4 -C 2 o alkyldienyl group, , a C 2 -C 20 ketone group, a C 2 - C 20 ester group, a C 6 -Ci 2 aryl group, and a C 4 -C 2 o polyenyl group, respectively.
  • groups having carbon atoms and groups having hetero atoms like e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.
  • Very preferred substituents L are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoroalkoxy with 1 to 12 C atoms or alkenyl, alkynyl with 2 to 12 C atoms.
  • aryl and heteroaryl groups are phenyl in which, in addition, one or more CH groups may be replaced by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above.
  • Very preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2- selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2- b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, seleno[2,3- bjselenophene, thieno[3,2-b]selenophene, thieno[3,2-b]furan,
  • aryl and heteroaryl groups are those selected from the groups shown hereinafter.
  • An alkyl or alkoxy radical i.e. where the terminal CH 2 group is replaced by -0-, can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
  • alkenyl groups are C2-C7-I E-alkenyl, C 4 -C 7 -3E- alkenyl, C 5 -C7-4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C2-C7-I E-alkenyl, C 4 -C 7 -3E-alkenyl and C 5 -C 7 -4-alkenyl.
  • alkenyl groups examples are vinyl, 1E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl,
  • radicals together form a carbonyloxy group -C(O)-O- or an oxycarbonyl group -O-C(O)-.
  • this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxy- ethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl,
  • An alkyl group wherein two or more CH2 groups are replaced by -O- and/or -C(O)O- can be straight-chain or branched. It is preferably straight- chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy- methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy- butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy- heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy- decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4 ) 4-bis-(
  • a fluoroalkyl group is preferably peril uoroalkyl CjF2i+i , wherein i is an integer from 1 to 15, in particular CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 Fn, C 6 F 13 ,
  • C 7 Fi5 or C 8 F 17 very preferably CeFi3, or partially fluor ' inated alkyl, in particular 1 ,1-difluoroalkyl, all of which are straight-chain or branched.
  • R 1 ,2 are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.
  • Very preferred groups of this type are selected from the group consisting of the following formulae wherein "ALK” denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached.
  • ALK optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached.
  • ALK denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to
  • halogen includes F, CI, Br or I, preferably F, CI or Br.
  • X 1 and X 2 have the meanings of formula I as given above and below, wherein the terminal thiophene rings may also be substituted in 3- position by a group R 1 . In a preferred embodiment one or both terminal thiophene rings are substituted in 3-position by a group R
  • R and R 2 preferably denote straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubstituted or substituted by one or more F atoms.
  • R 1 and R 2 is H and the other is different from H, and is preferably straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubsituted or substituted by one or more F atoms.
  • R 1 and/or R 2 are independently of each other selected from the group consisting of aryl and heteroaryl, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms.
  • Preferred polymers according to the present invention comprise one or more repeating units of formula II:
  • Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and
  • aryl or heteroaryl that is different from U preferably has 5 to 30 ring atoms, and is optionally substituted, preferably by one or more groups R s ,
  • R s is on each occurrence identically or differently F, Br, CI, -CN, ⁇
  • R° and R 00 are independently of each other H or optionally substituted
  • C-1-40 carbyl or hydrocarbyl, and preferably denote H or alkyl with 1 to 12 C-atoms,
  • X° is halogen, preferably F, CI or Br, a, b and c are on each occurrence identically or differently 0, 1 or 2, d is on each occurrence identically or differently 0 or an integer from 1 to 10, wherein the polymer comprises at least one repeating unit of formula II wherein b is at least 1.
  • polymers according to the present invention comprise, in addition to the units of formula I or II, one or more repeating units selected from monocyclic or polycyclic aryl or heteroaryl groups that are optionally substituted.
  • Additional repeating units are preferably selected of formula III -[(Ar 1 ) a -(A c )b-(ArV(Ar 3 )d]- HI wherein Ar 1 , Ar 2 , Ar 3 , a, b, c and d are as defined in formula II, and A c is an aryl or heteroaryl group that is different from U and Ar 1"3 , preferably has 5 to 30 ring atoms, is optionally substituted by one or more groups R s as defined above and below, and is preferably selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula III wherein b is at least 1.
  • R s preferably has one of the meanings given for R 1 .
  • the conjugated polymers according to the present invention are preferably selected of formula IV:
  • A is a unit of formula I or II or its preferred subformulae
  • B is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted, and is preferably selected of formula III, x is > 0 and ⁇ 1 , y is > 0 and ⁇ 1 , x + y is 1 , and n is an integer >1.
  • Preferred polymers of formula IV are selected of the following formulae * -[(Ar 1 -U-ArV(Ar 3 ) v ]n-* IVa
  • the total number of repeating units n is preferably from 2 to 10,000.
  • the total number of repeating units n is preferably > 5, very preferably > 10, most preferably > 50, and preferably ⁇ 500, very preferably ⁇ 1 ,000, most preferably ⁇ 2,000, including any combination of the aforementioned lower and upper limits of n.
  • the polymers of the present invention include homopolymers and
  • copolymers like statistical or random copolymers, alternating copolymers and block copolymers, as well as combinations thereof.
  • polymers selected from the following groups:
  • Group B consisting of random or alternating copolymers formed by
  • Group D consisting of random or alternating copolymers formed by
  • Preferred polymers of formula IV and IVa to IVe are selected of formula V R 5 -chain-R 6 V wherein "chain” denotes a polymer chain of formulae IV or IVa to IVe, and R 5 and R 6 have independently of each other one of the meanings of R 1 as defined above, or denote, independently of each other, H, F, Br, CI, I, - CH 2 CI, -CHO, -CR ⁇ CR ⁇ , -SHWR"', -SiR'X'X", -SiR'R' , -SnR' ⁇ 'R'", - BR'R", -B(OR')(OR"), -B(OH) 2 , -0-S0 2 -R', -C ⁇ CH, -C ⁇ C-SiR' 3 , -ZnX' or an endcap group, X' and X" denote halogen, R', R" and R'" have
  • R 5 and R 6 are H, Ci -20 alkyl, or optionally substituted C6-12 aryl or C 2- i 0 heteroaryl, very preferably H or phenyl.
  • R 7 -Ar 1 -U-R' VI3 R ⁇ U-Ar ⁇ R' VI4 wherein U, Ar ⁇ Ar 2 , R 7 and R 8 are as defined in formula VI.
  • R 11 and R 12 independently of each other denote H or have one of the meanings of R 1 as defined above and below.
  • - X 1 and X 2 are Si(R 1 R 2 ),
  • - n is at least 5, preferably at least 10, very preferably at least 50, and up to 2,000, preferably up to 500.
  • - M w is at least 5,000, preferably at least 8,000, very preferably at least 0,000, and preferably up to 300,000, very preferably up to 100,000,
  • R 1 and R 2 are H and the other is different from H
  • R 1 and/or R 2 are independently of each other selected from the group consisting of primary alkyl with 1 to 30 C atoms, secondary alkyl with 3 to 30 C atoms, and tertiary alkyl with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F,
  • R and/or R 2 are independently of each other selected from the group consisting of aryl and heteroaryl, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms,
  • R 1 and/or R 2 are independently of each other selected from the group consisting of primary alkoxy or sulfanylalkyi with 1 to 30 C atoms, secondary alkoxy or sulfanylalkyi with 3 to 30 C atoms, and tertiary alkoxy or sulfanylalkyi with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F,
  • R 1 and/or R 2 are independently of each other selected from the group consisting of aryloxy and heteroa ry loxy, each of which is optionally alkylated or alkoxylated and has 4 to 30 ring atoms,
  • R 1 and/or R 2 are independently of each other selected from the group consisting of alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, all of which are straight-chain or branched, are optionally fluorinated, and have from 1 to 30 C atoms
  • - R 1 and/or R 2 denote independently of each other F, CI, Br, I, CN, R 9 , - C(0)-R 9 , -C(O)-O-R 9 or -0-C(0)-R 9 , -S0 2 -R 9 , -SO3-R 9 , wherein R 9 is straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by -0-, -S-, - C(O)-, -C(0)-O-, -O-C(O)-, -0-C(0)-0-, -SO2-, -SO
  • R 9 is aryl or heteroaryl having 4 to 30 ring atoms which is unsubstituted or which is substituted by one or more halogen atoms or by one or more groups R as defined above,
  • R° and R 00 are selected from H or d-C ⁇ -alkyl
  • two groups Z 2 may also form a cyclic group.
  • the compounds of the present invention can be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature. Other methods of preparation can be taken from the examples.
  • the polymers can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling and Yamamoto coupling are especially preferred.
  • the monomers which are polymerised to form the repeat units of the polymers can be prepared according to methods which are known to the person skilled in the art.
  • polymers are prepared from monomers of formula VI or their preferred subformulae as described above and below.
  • Another aspect of the invention is a process for preparing a polymer by coupling one or more identical or different monomeric units of formula I or monomers of formula VI with each other and/or with one or more comonomers in a polymerisation reaction, preferably in an aryl-aryl coupling reaction.
  • Suitable and preferred comonomers are selected from the following formulae
  • R 7 -Ar 3 -R 8 E wherein Ar 1 , Ar 2 , Ar 3 , a and c have one of the meanings of formula II or one of the preferred meanings given above and below, A c has one of the meanings of formula III or one of the preferred meanings given above and below, and R 7 and R 8 have one of meanings of formula VI or one of the preferred meanings given above and below.
  • Very preferred is a process for preparing a polymer by coupling one or more monomers selected from formula VI or formulae VI1-VI4 with one or more monomers of formula C, and optionally with one or more monomers selected from formula D and E, in an aryl-aryl coupling reaction, wherein preferably R 7 and R 8 are selected from CI, Br, I, -B(OZ 2 ) 2 and -Sn(Z ) 3 .
  • preferred embodiments of the present invention relate to a) a process of preparing a polymer by coupling a monomer of formula V11
  • R 7 , R 8 , U, A c , Ar 1 ,2 are as defined in formula II, III and VI, and R 7 and R 8 are preferably selected from CI, Br, I, -B(OZ 2 ) 2 and -Sn(Z 4 ) 3 as defined in formula VI.
  • aryl-aryl coupling methods used in the processes described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C-H activation coupling, Ullmann coupling or Buchwald coupling.
  • Suzuki coupling is described for example in WO 00/53656 A1.
  • Negishi coupling is described for example in J. Chem. Soc, Chem. Commun., 1977, 683-684.
  • Yamamoto coupling is described in for example in T. Yamamoto er a/., Prog. Polym.
  • Suzuki and Stille polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers.
  • Statistical or block copolymers can be prepared for example from the above monomers wherein one of the reactive groups is halogen and the other reactive group is a boronic acid, boronic acid derivative group or and alkylstannane. The synthesis of statistical, alternating and block
  • copolymers is described in detail for example in WO 03/048225 A2 or WO 2005/014688 A2.
  • Preferred catalysts are selected from Pd(0) complexes or Pd(ll) salts.
  • Preferred Pd(0) complexes are those bearing at least one phosphine ligand such as Pd( h3P) .
  • Another preferred phosphine ligand is tris(o/f/70-tolyl)phosphine, i.e. Pd(o-Tol3P) .
  • Preferred Pd(ll) salts include palladium acetate, i.e. Pd(OAc) 2 .
  • the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dibenzyl-ideneacetone)dipalladium(0),
  • phosphine ligand for example triphenylphosphine, tris(orf/70- tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki coupling is performed in the presence of a base, for example sodium carbonate, potassium
  • Yamamoto coupling employs a Ni(0) complex, for example bis(1,5- cyclooctadienyl) nickel(O).
  • leaving groups of formula -0-S0 2 Z 1 can be used wherein Z 1 is as described above.
  • Particular examples of such leaving groups are tosylate, mesylate and triflate.
  • R 1,2 have the meanings given above.
  • the synthesis of two bromo benzothiophene isomers is exemplarily shown in Scheme 1.
  • the compounds and polymers according to the present invention can also be used in mixtures or polymer blends, for example together with monomeric compounds or together with other polymers having charge- transport, semiconducting, electrically conducting, photoconducting and/or light emitting semiconducting properties, or for example with polymers having hole blocking or electron blocking properties for use as interlayers or charge blocking layers in OLED devices.
  • another aspect of the invention relates to a polymer blend comprising one or more polymers according to the present invention and one or more further polymers having one or more of the above-mentioned properties.
  • These blends can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the polymers are mixed with each other or dissolved in suitable solvents and the solutions combined.
  • Another aspect of the invention relates to a formulation comprising one or more small molecules, polymers, mixtures or polymer blends as described above and below and one or more organic solvents.
  • Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Additional solvents which can be used include 1 ,2,4-trimethylbenzene, 1 ,2,3,4-tetra- methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2,6-lutidine, 2-fluoro- m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, N,N- dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3- dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro- methylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3-
  • solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p- xylene, 1,4-dioxane, acetone, methylethylketone, 1,2-dichloroethane, 1 ,1 ,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, ⁇ , ⁇ -dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetraline, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene and/or mixtures thereof.
  • the concentration of the compounds or polymers in the solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
  • the solution also comprises one or more binders to adjust the rheological properties, as described for example in WO 2005/055248 A1.
  • solutions are evaluated as one of the following categories: complete solution, borderline solution or
  • the compounds and polymers according to the present invention can also be used in patterned OSC layers in the devices as described above and below. For applications in modern microelectronics it is generally desirable to generate small structures or patterns to reduce cost (more devices/unit area), and power consumption. Patterning of thin layers comprising a polymer according to the present invention can be carried out for example by photolithography, electron beam lithography or laser patterning.
  • the compounds, polymers, polymer blends or formulations of the present invention may be deposited by any suitable method.
  • Liquid coating of devices is more desirable than vacuum deposition techniques.
  • Solution deposition methods are especially preferred.
  • the formulations of the present invention enable the use of a number of liquid coating techniques.
  • Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.
  • Ink jet printing is particularly preferred when high resolution layers and devices needs to be prepared.
  • Selected formulations of the present invention may be applied to prefabricated device substrates by ink jet printing or microdispensing.
  • industrial piezoelectric print heads such as but not limited to those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar may be used to apply the organic semiconductor layer to a substrate.
  • semi-industrial heads such as those manufactured by Brother, Epson,
  • Konica, Seiko Instruments Toshiba TEC or single nozzle microdispensers such as those produced by Microdrop and Microfab may be used.
  • Solvents must fulfil the requirements stated above and must not have any detrimental effect on the chosen print head. Additionally, solvents should have boiling points >100°C, preferably >140°C and more preferably >150°C in order to prevent operability problems caused by the solution drying out inside the print head.
  • suitable solvents include substituted and non-substituted xylene
  • di-Ci-2-alkyl formamide substituted and non-substituted anisoles and other phenol-ether derivatives
  • substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and non-substituted /V,A -di-C . 2 -alkylanilines and other fluorinated or chlorinated aromatics.
  • a preferred solvent for depositing a compound or polymer according to the present invention by ink jet printing comprises a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three.
  • the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total.
  • Such a solvent enables an ink jet fluid to be formed comprising the solvent with the compound or polymer, which reduces or prevents clogging of the jets and separation of the components during spraying.
  • the solvent(s) may include those selected from the following list of examples: dodecylbenzene, 1 -methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, diethylbenzene.
  • the solvent may be a solvent mixture, that is a combination of two or more solvents, each solvent preferably having a boiling point >100°C, more preferably >140°C. Such solvent(s) also enhance film formation in the layer deposited and reduce defects in the layer.
  • the ink jet fluid (that is mixture of solvent, binder and semiconducting compound) preferably has a viscosity at 20°C of 1-100 mPa s, more preferably 1-50 mPa s and most preferably 1-30 mPa s.
  • the polymer blends and formulations according to the present invention can additionally comprise one or more further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, nanoparticles, colourants, dyes or pigments, furthermore, especially in case crosslinkable binders are used, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents or co- reacting monomers.
  • further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, nanoparticles, colourants, dyes or pigments, furthermore, especially in case crosslinkable binders
  • the compounds and polymers to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices.
  • the polymers of the present invention are typically applied as thin layers or films.
  • the present invention also provides the use of the semiconducting compound, polymer, polymers blend, formulation or layer in an electronic device.
  • the formulation may be used as a high mobility semiconducting material in various devices and apparatus.
  • the formulation may be used, for example, in the form of a semiconducting layer or film.
  • the present invention provides a semiconducting layer for use in an electronic device, the layer comprising a compound, polymer, polymer blend or formulation according to the invention.
  • the layer or film may be less than about 30 microns.
  • the thickness may be less than about 1 micron thick.
  • the layer may be deposited, for example on a part of an electronic device, by any of the aforementioned solution coating or printing techniques.
  • the invention additionally provides an electronic device comprising a compound, polymer, polymer blend, formulation or organic
  • Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices,
  • electrophotographic recording devices organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates and conducting patterns.
  • Especially preferred electronic device are OFETs, OLEDs and OPV devices, in particular bulk heterojunction (BHJ) OPV devices and OPD devices.
  • the active semiconductor channel between the drain and source may comprise the layer of the invention.
  • the charge (hole or electron) injection or transport layer may comprise the layer of the invention.
  • the polymer according to the present invention is preferably used in a formulation that comprises or contains, more preferably consists essentially of, very preferably exclusively of, a p- type (electron donor) semiconductor and an n-type (electron acceptor) semiconductor.
  • the p-type semiconductor is constituted by a polymer according to the present invention.
  • the n-type semiconductor can be an inorganic material such as zinc oxide (ZnO x ), zinc tin oxide (ZTO), titan oxide (TiO x ), molybdenum oxide (MoO x ), nickel oxide (NiO x ), or cadmium selenide (CdSe), or an organic material such as graphene or a fullerene or substituted fullerene, for example an indene-C 60 -fullerene bisaduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C 6 o fullerene, also known as "PCBM-C60" or "C 6 oPCBM", as disclosed for example in G.
  • inorganic material such as zinc oxide (ZnO x ), zinc tin oxide (ZTO), titan oxide (TiO x ), molybdenum oxide (MoO x ), nickel oxide (NiO x ), or c
  • CeoPCBM Preferably the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene, like for example PCBM-C 60 , PCBM-C 70 , PCBM-C 6 i , PCB -C71, bis-PCBM-C 6 i, bis-PCBM-C 7 i, ICBA ⁇ V,V 4 4"- tetrahydro-di[1 ,4]methanonaphthaleno [1 ,2:2 , ,3';56,60:2",3 ,, ][5 l 6]fullerene-C60-lh), graphene, or a metal oxide, like for example, ZnO x , TiO x , ZTO, MoO x , NiO x , to form the active layer in an OPV or OPD device.
  • the device preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi- transparent substrate
  • the OPV or OPD device comprises, between the active layer and the first or second electrode, one or more additional buffer layers acting as hole transporting layer and/or electron blocking layer, which comprise a material such as metal oxide, like for example, ZTO, MoO x , ⁇ , a conjugated polymer electrolyte, like for example PEDOT.PSS, a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example N,N'-diphenyl-N,N'-bis(1-naphthyl)(1 ,1'- biphenyl)-4,4'diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1 , r- biphenyl-4,4'-diamine (TPD), or alternatively as hole blocking layer and/or electron transporting layer, which comprise a material such as metal oxide, like for example, ZnO x , TiO x , a salt
  • the ratio polymenfullerene is preferably from 5:1 to 1 :5 by weight, more preferably from 1:1 to 1:3 by weight, most preferably 1:1 to 1 :2 by weight.
  • a polymeric binder may also be included, from 5 to 95% by weight. Examples of binder include polystyrene (PS), polypropylene (PP) and polymethylmethacrylate (PMMA).
  • PS polystyrene
  • PP polypropylene
  • PMMA polymethylmethacrylate
  • the compounds, polymers, polymer blends or formulations of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred.
  • the formulations of the present invention enable the use of a number of liquid coating techniques.
  • Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, dip coating, curtain coating, brush coating, slot dye coating or pad printing.
  • area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like.
  • Suitable solutions or formulations containing the blend or mixture of a polymer according to the present invention with a C 6 o or C 70 fullerene or modified fullerene like PCBM must be prepared.
  • suitable solvent must be selected to ensure full dissolution of both component, p-type and n-type and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.
  • Organic solvent are generally used for this purpose.
  • Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents. Examples include, but are not limited to chlorobenzene, 1 ,2-dichlorobenzene, chloroform, 1 ,2- dichloroethane, dichloromethane, carbon tetrachloride, toluene, cyclohexanone, ethylacetate, tetrahydrofuran, anisole, morpholine, o- xylene, m-xylene, p-xylene, 1 ,4-dioxane, acetone, methylethylketone, 1 ,2- dichloroethane, 1 ,1,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, dimethylacet
  • the OPV device can for example be of any type known from the literature (see e.g. Waldauf ef a/., Appl. Phys. Lett., 2006, 89, 233517).
  • a first preferred OPV device comprises the following layers (in the sequence from bottom to top):
  • a high work function electrode preferably comprising a metal oxide, like for example ITO, serving as anode
  • an optional conducting polymer layer or hole transport layer preferably comprising an organic poymer or polymer blend, for example of
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene): poly(styrene- sulfonate), or TBD (N,N'-dyphenyl-N-N'-bis(3-methylphenyl)-
  • NBD N,N'-dyphenyl-N-N'-bis(1- napthylphenyl)-1 , 1 'biphenyl-4,4'-diamine
  • active layer comprising a p-type and an n- type organic semiconductor, which can exist for example as a p-type/n- type bilayer or as distinct p-type and n-type layers, or as blend or p-type and n-type semiconductor, forming a BHJ,
  • a layer having electron transport properties for example comprising LiF
  • a low work function electrode preferably comprising a metal like for example aluminum, serving as cathode
  • At least one of the electrodes preferably the anode, is transparent to visible light
  • a second preferred OPV device according to the invention is an inverted OPV device and comprises the following layers (in the sequence from bottom to top):
  • a high work function metal or metal oxide electrode comprising for example ITO, serving as cathode
  • a layer having hole blocking properties preferably comprising a metal oxide like TiO x or Zn x ,
  • an active layer comprising a p-type and an n-type organic
  • BHJ BHJ
  • an optional conducting polymer layer or hole transport layer preferably comprising an organic poymer or polymer blend, for example of
  • an electrode comprising a high work function metal like for example silver, serving as anode
  • At least one of the electrodes preferably the cathode, is transparent to visible light
  • the p-type semiconductor is a polymer according to the present invention.
  • the p-type and n-type semiconductor materials are preferably selected from the materials, like the polymer/fullerene systems, as described above.
  • the active layer When the active layer is deposited on the substrate, it forms a BHJ that phase separates at nanoscale level.
  • phase separation see Dennler et al, Proceedings of the IEEE, 2005, 93 (8), 1429 or Hoppe et al, Adv. Func. Mater, 2004, 14(10), 1005.
  • An optional annealing step may be then necessary to optimize blend morpohology and consequently OPV device performance.
  • Another method to optimize device performance is to prepare formulations for the fabrication of OPV(BHJ) devices that may include high boiling point additives to promote phase separation in the right way.
  • 1 ,8-Octanedithiol, 1 ,8-diiodooctane, nitrobenzene, chloronaphthalene, and other additives have been used to obtain high-efficiency solar cells. Examples are disclosed in J. Peet, ef al, Nat. Mater., 2007, 6, 497 or Frechet ef al. J. Am. Chem. Soc, 2010, 132, 7595-7597.
  • the compounds, polymers, formulations and layers of the present invention are also suitable for use in an OFET as the semiconducting channel. Accordingly, the invention also provides an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a compound, polymer, polymer blend, formulation or organic semiconducting layer according to the present invention.
  • an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a compound, polymer, polymer blend, formulation or organic semiconducting layer according to the present invention.
  • Other features of the OFET are well known to those skilled in the art.
  • OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode are generally known, and are described for example in US 5,892,244, US 5,998,804, US 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT displays and security applications.
  • semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
  • An OFET device preferably comprises:
  • the semiconductor layer preferably comprises a compound, polymer, polymer blend or formulation as described above and below.
  • the OFET device can be a top gate device or a bottom gate device.
  • the gate insulator layer preferably comprises a fluoropolymer, like e.g. the commercially available Cytop 809M® or Cytop 107M® (from Asahi Glass).
  • a fluoropolymer like e.g. the commercially available Cytop 809M® or Cytop 107M® (from Asahi Glass).
  • the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent.
  • a suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380).
  • FC75® available from Acros, catalogue number 12380.
  • Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the
  • organic dielectric materials having a low
  • OFETs and other devices with semiconducting materials according to the present invention can be used for RFID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with monetry value, like stamps, tickets, shares, cheques etc.
  • the materials according to the invention can be used in OLEDs, e.g. as the active display material in a flat panel display
  • OLEDs are realized using multilayer structures.
  • An emission layer is generally sandwiched between one or more electron- transport and/or hole-transport layers.
  • the inventive compounds, materials and films may be employed in one or more of the charge transport layers and/or in the emission layer, corresponding to their electrical and/or optical properties.
  • their use within the emission layer is especially advantageous, if the compounds, materials and films according to the invention show electroluminescent properties themselves or comprise electroluminescent groups or compounds. The selection, characterization as well as the processing of suitable
  • the materials according to this invention may be employed as materials of light sources, e.g. in display devices, as described in EP 0 889 350 A1 or by C. Weder et a/., Science, 1998, 279, 835-837.
  • a further aspect of the invention relates to both the oxidised and reduced form of the compounds according to this invention. Either loss or gain of electrons results in formation of a highly delocatised ionic form, which is of high conductivity. This can occur on exposure to common dopants.
  • Suitable dopants and methods of doping are known to those skilled in the art, e.g. from EP 0 528 662, US 5, 98, 153 or WO 96/21659.
  • the doping process typically implies treatment of the semiconductor material with an oxidating or reducing agent in a redox reaction to form delocalised ionic centres in the material, with the corresponding
  • Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion-implantantion of the dopant into the semiconductor material.
  • suitable dopants are for example halogens (e.g., I 2 , Cl 2 , Br 2 , ICI, ICI 3 , IBr and IF), Lewis acids (e.g., PF 5 , AsF 5 , SbF 5 , BF3, BCI3, SbCle, BBr 3 and S0 3 ), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HN0 3 , H 2 S0 4 , HCI0 4 , FS0 3 H and CISO3H), transition metal compounds (e.g., FeCI 3 , FeOCI, Fe(CI0 4 ) 3 , Fe(4-CH 3 C 6 H 4 S0 3 )3, TiCI 4 , ZrCI 4 , HfCI 4 , NbF 5 , NbCI 5 , TaCI 5 , MoF 5 , MoCI 5 , WF5, WCI 6 , UF 6 and LnCI 3 (
  • examples of dopants are cations (e.g., H + , Li + , Na ⁇ K + , Rb + and Cs + ), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline- earth metals (e.g., Ca, Sr, and Ba), 0 2 , XeOF 4 , (N0 2 + ) (SbF 6 ⁇ ), (N0 2 + ) (SbCle * ), (N0 2 + ) (BF 4 ), AgCI0 4 , H 2 lrCI 6 , La(N0 3 ) 3 6H 2 0, FS0 2 OOS0 2 F, Eu, acetylcholine, R 4 N + , (R is an alkyl group), R P + (R is an alkyl group), R 6 As + (R is an alkyl group), and R 3 S + (R is an alkyl group).
  • dopants are cations (e.g.
  • the conducting form of the compounds of the present invention can be used as an organic "metal” in applications including, but not limited to, charge injection layers and ITO planarising layers in OLED applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers.
  • the compounds and formulations according to the present invention may also be suitable for use in organic plasmon-emitting diodes (OPEDs), as described for example in Koller et al., Nat. Photonics, 2008, 2, 684.
  • the materials according to the present invention can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US 2003/0021913.
  • the use of charge transport compounds according to the present invention can increase the electrical conductivity of the alignment layer.
  • this increased electrical conductivity can reduce adverse residual dc effects in the switchable LCD cell and suppress image sticking or, for example in ferroelectric LCDs, reduce the residual charge produced by the switching of the spontaneous polarisation charge of the ferroelectric LCs.
  • this increased electrical conductivity can enhance the electroluminescence of the light emitting material.
  • the compounds or materials according to the present invention having mesogenic or liquid crystalline properties can form oriented anisotropic films as described above, which are especially useful as alignment layers to induce or enhance alignment in a liquid crystal medium provided onto said anisotropic film.
  • the materials according to the present invention may also be combined with photoisomerisable
  • the materials according to the present invention can be employed as chemical sensors or materials for detecting and discriminating DNA sequences.
  • Such uses are described for example in L. Chen, D. W. McBranch, H. Wang, R. Helgeson, F. Wudl and D. G. Whitten, Proc. Natl. Acad. Sci. U.S.A., 1999, 96, 12287; D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan and A. J. Heeger, Proc. Natl. Acad. Sci.
  • Lithium diisopropylamide (2.0 M in THF, 31.0 cm 3 , 62 mmol) is added dropwise to a solution of 6-bromo-benzo[b]thiophene (12.0 g, 56 mmol) in anhydrous tetrahydrofuran ( 50 cm 3 ) under a nitrogen atmosphere at -30 ° C over 30 minutes.
  • the resulting solution is stirred at -20 ° C for 2 hours and then quenched with chlorotrimethylsilane (6.7 g, 62 mmol).
  • the ice bath is removed and the reaction mixture is warmed to 23 ° C and stirred for 17 hours.
  • the reaction mixture is diluted with water (75 cm 3 ) and extracted with diethyl ether (5 x 50 cm 3 ).
  • Nitrogen gas is bubbled through a suspension of (6-bromo- benzo[b]thiophen-2-yl)-trimethylsilane (2.0 g, 7.0 mmol),
  • Nitrogen gas is bubbled through a solution of 2,5-dibromo-terephthalic acid diethyl ester (4.0 g, 1 1 mmol) and trimethyl(6-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)benzo[b]thiophen-2-yl)silane (7.7 g, 23 mmol) in anhydrous toluene (40 cm 3 ) for 1 hour. Potassium carbonate (6.1 g, 44 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) are then added to the reaction mixture.
  • 2,5-dibromo-terephthalic acid diethyl ester 4.0 g, 1 1 mmol
  • reaction mixture is stirred at 120 °C for 17 hours.
  • the reaction mixture is concentrated in vacuo and purified using silica gel column chromatography (gradient of 40- 60 petroleum to diethyl ether) to give 2,5-bis-(2-trimethylsilanyl- benzo[b]thiophen-6-yl)-terephthalic acid diethyl ester (3.5 g 53%) as a white solid.
  • Nitrogen gas is bubbled through a mixture of 2,20-dibromo-(6,12-dihydro- 6,6, 2, 2-tetrakis(4-dodecylphenyl)- 1 ,7-dithia-dicyclopenta[a, h]- indeno[1 ,2-b]fluorene) (200 mg, 0.133 mmol) and 5,5'-bis- trimethylstannanyl-[2,2']bithiophenyl (65.5 mg, 0.133 mmol) in anhydrous toluene (2 cm 3 ) and anhydrous ⁇ /,/V-dimethylformamide (0.5 cm 3 ) for 1 hour.
  • Tris(dibenzylideneacetone)dipalladium(0) (4.9 mg, 0.005 mmol) and tri-o-tolyl-phosphine (6.5 mg, 0.02 mmol) are added to the reaction mixture followed by heating at 120 °C for 65 hours.
  • the reaction mixture is poured into methanol (100 cm 3 ) and the polymer precipitate collected by filtration.
  • the crude polymer is subjected to sequential Soxhiet extraction; methanol, acetone, 40-60 petroleum, 80-100 petroleum, cyclohexanes, chloroform and chlorobenzene.
  • Nitrogen gas is bubbled through a mixture of 2,7-di([1 ,3,2]dioxaborolane)- 9,10-dioctyl-phenanthrene (65.1 mg, 0.120 mmol), 2,20-dibromo-(6,12- dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]- indeno[ ,2-b]fluorene) (180 mg, 0.120 mmol) and potassium phosphate monohydrate (0.2 g, 1.1 mmol) in a mixture of toluene (3 cm 3 ), 1,4-dioxane (3 cm 3 ) and water (3 cm 3 ) for 1 hour.
  • Tris(dibenzylideneacetone)dipalladium(0) (2.7 mg, 0.003 mmol) and tri-o- tolyl-phosphine (5.8 mg, 0.019 mmol) are added to the reaction mixture followed by heating at 100 °C for 3 hours.
  • the reaction mixture is poured into methanol (100 cm 3 ) and the polymer precipitate collected by filtration.
  • the crude polymer is subjected to sequential Soxhiet extraction; methanol, acetone, 40-60 petroleum, 80-100 petroleum, cyclohexanes and
  • the resulting mixture is heated to 90 °C and the prepared (4- tributylstannanyl-benzo[b]thiophen-2-yl) is added.
  • the reaction mixture is stirred at 90 °C for 17 hours.
  • the reaction mixture is concentrated in vacuo and purified using silica gel column chromatography (gradient of 40-60 petroleum to diethyl ether) to give diethyl 2,5-di(benzo[b]thiophen-4- yl)terephthalate (0.9 g, 31 %) as a white solid.
  • reaction mixture is then quenched with water (125 cm 3 ) and extracted with diethyl ether (3 x 50 cm 3 ).
  • the combined organic layer is washed with water (50 cm 3 ), brine (50 cm 3 ), dried over anhydrous magnesium sulphate and then filtered.
  • the filtrate is concentrated in vacuo, triturated with methanol (50 cm 3 ) and the solid collected by filtration to give crude ⁇ 2,5-bis-benzo[b]thiophen-6-yl-4- [hydroxy-bis-(4- dodecyl -phenyl)-methyl]-phenyl ⁇ -bis-(4-octyl-phenyl)- methanol.
  • reaction mixture is concentrated in vacuo and purified using silica gel chromatography (gradient of 40-60 petroleum to dichloromethane) to yield 6,12-dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-3,9-dithia- dicyclopenta[c,f]-indeno[1 ,2-b]fluorene (760 mg, 51 %) as a white solid.
  • reaction mixture is concentrated in vacuo and the crude product crystallized from n-heptane and diethyl ether (40 cm 3 , 1 :1) to give 2,18-dibromo-(6,12-dihydro-6,6,12,12-tetrakis(4- dodecylphenyl)-3,9-dithia-dicyclopenta[c,f]-indeno[1 ,2-b]fluorene) (98 mg 18%) as a white crystalline solid.
  • Nitrogen gas is bubbled through a mixture of 2,18-dibromo-(6,12-dihydro- e.e. ⁇ .l -tetrakisi ⁇ dodecylpheny -S.Q-dithia-dicyclopentatcfl-indenofl ⁇ - b]fluorene) (200.0 mg, 0.133 mmol), 5,5'-bis-trimethylstannanyl- [2,2']bithiophenyl (62.0 mg, 0.133 mmol),
  • the crude polymer is subjected to sequential Soxhiet extraction; acetone, 40-60 petrol, cyclohexane and chloroform.
  • the chloroform extract is concentrated in vacuo and poured into methanol (300 cm 3 ) and the solid collected by filtration to give poly[2,18-[(6,12-dihydro- 6,6,12,12-tetrakis(4-dodecylphenyl)-3,9-dithia-dicyclopenta[c,f]-indeno[1 ,2- b]fluorene)]]-a/f-[2,5-thieno[3,2-b]thiophene) (180 mg, 83%) as a dark red solid.
  • GPC chlorobenzene, 50 °C
  • M n 29,000 g/mol
  • M w 54,000 g/mol.
  • Top-gate thiri-film organic field-effect transistors were fabricated on glass substrates with photolithographically defined Au source-drain electrodes.
  • a 7 mg/cm 3 solution of the organic semiconductor in dichlorobenzene was spin-coated on top followed by a spin-coated fluoropolymer dielectric material (Lisicon® D139 from Merck, Germany).
  • a photolithographically defined Au gate electrode was deposited. The electrical characterization of the transistor devices was carried out in ambient air atmosphere using computer controlled Agilent 4155C
  • Vo Turn-on voltage
  • the mobility ( ⁇ 53 for example polymer 1 in top-gate OFETs is 0.06 cm 2 /Vs.
  • Figure 1 shows the transfer characteristics and the charge carrier mobility of a top-gate OFET prepared as described above, wherein polymer 1 is used as the organic semiconductor.

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Abstract

The invention relates to novel conjugated polymers containing one or more repearting units derived from indacenodibenzothiophene or dithia-dicyclopenta-dibenzothiophene, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations.

Description

Conjugated Polymers
Technical Field The invention relates to novel conjugated polymers containing one or more repeating units derived from indacenodibenzothiophene or dithia- dicyclopenta-dibenzothiophene, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations. Background
Organic semiconducting (OSC) materials are receiving growing interest mostly due to their rapid development in the recent years and the lucrative commercial prospects of organic electronics.
One particular area of importance is organic photovoltaics (OPV).
Conjugated polymers have found use in OPVs as they allow devices to be manufactured by solution-processing techniques such as spin casting, dip coating or ink jet printing. Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices. Currently, polymer based photovoltaic devices are achieving efficiencies above 8%.
In order to obtain ideal solution-processible OSC molecules two basic features are essential, firstly a rigid π-conjugated core unit to form the backbone, and secondly a suitable functionality attached to the aromatic core unit in the OSC backbone. The former extends π-π overlaps, defines the primary energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), enables both charge injection and transport, and facilitates optical absorption. The latter further fine-tunes the energy leverls and enables solubility and hence processability of the materials as well as π-π interactions of the molecular backbones in the solid state.
A high degree of molecular planarity reduces the energetic disorder of OSC backbones and accordingly enhances charge carrier mobilities.
Linearly fusing aromatic rings is an efficient way of achieving maximum planarity with extended π-π conjugation of OSC molecules. Accordingly, most of the known polymeric OSCs with high charge carrier mobilities are generally composed of fused ring aromatic systems and are
semicrystalline in their solid states. On the other hand, such fused aromatic ring systems are often difficult to synthesize, and do also often show poor solubility in organic solvents, which renders their processing as thin films for use in OE devices more difficult. Also, the OSC materials disclosed in prior art still leave room for further improvement regarding their electronic properties.
Thus there is still a need for organic semiconducting (OSC) polymers which are easy to synthesize, especially by methods suitable for mass production, show good structural organization and film-forming properties, exhibit good electronic properties, especially a high charge carrier mobility, a good processibility, especially a high solubility in organic solvents, and high stability in air. Especially for use in OPV cells, there is a need for OSC materials having a low bandgap, which enable improved light harvesting by the photoactive layer and can lead to higher cell efficiencies, compared to the polymers from prior art.
It was an aim of the present invention to provide compounds for use as organic semiconducting materials that are easy to synthesize, especially by methods suitable for mass production, and do especially show good processibility, high stability, good solubility in organic solvents, high charge carrier mobility, and a low bandgap. Another aim of the invention was to extend the pool of OSC materials available to the expert. Other aims of the present invention are immediately evident to the expert from the following detailed description.
The inventors of the present invention have found that one or more of the above aims can be achieved by providing conjugated polymers containing one or more repeating units based on a fused indacenodibenzothiophene (IDDBT) unit of structure (I) or dithia-dicyclopenta-dibenzothiophene (TTDBT) of structure (II) as shown below, wherein X is for example CRR or C=CRR, and R is for example alkyl, or derivatives thereof.
Figure imgf000004_0001
(II)
Suprisingly it was found that these enlarged fused ring systems, and the polymers containing them, still show sufficient solubility in organic solvents, which can also be further improved by introducing alkyl or alkylidene substituents onto the indacene unit. Both the homo- and copolymers can be prepared through known transition metal catalysed polycondensation reactions. As a result the polymers of the present invention were found to be attractive candidates for solution processable organic semiconductors both for use in transistor applications and photovoltaic applications. By further variation of the substituents on the fused aromatic ring system, the solubility and electronic properties of the monomers and polymers can be further optimised.
Summary
The invention relates to conjugated polymers comprising one or more divalent units of formula I
Figure imgf000005_0001
independently of each other denote C(R1R2), C=C(R1R2), Si(R1R2) or C=0,
Figure imgf000005_0002
wherein the thiophene ring may also be substituted in 3-position by a group R1,
Figure imgf000005_0003
wherein the thiophene ring may also be substituted in 3-position by a group R ,
B
Figure imgf000005_0004
R1 and R2 independently of each other denote H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH2 groups are optionally replaced by -0-, -S-, - C(0)~, -C(S)-, -C(0)-0-, -O-C(O)-, -NR°- -SiR°R00-, -CF2-, -CHR°=CR00-, -CY1=CY2- or -C≡C- in such a manner that
O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, CI, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, preferably by halogen or by one or more of the aforementioned alkyl or cyclic alkyl groups,
Y1 and Y2 independently of each other denote H, F, CI or CN, R° and R00 independently of each other denote H or optionally
substituted C - 0 carbyl or hydrocarbyl, and preferably denote H or alkyl with 1 to 12 C-atoms.
The invention further relates to a formulation comprising one or more polymers comprising a unit of formula I and one or more solvents, preferably selected from organic solvents.
The invention further relates to the use of units of formula I as electron donor units in semiconducting polymers.
The invention further relates to conjugated polymers comprising one or more repeating units of formula I and/or one or more groups selected from aryl and heteroaryl groups that are optionally substituted, and wherein at least one repeating unit in the polymer is a unit of formula I.
The invention further relates to monomers containing a unit of formula I and further containing one or more reactive groups which can be reacted to form a conjugated polymer as described above and below. The invention further relates to semiconducting polymers comprising one or more units of formula I as electron donor units, and preferably further comprising one or more units having electron acceptor properties.
The invention further relates to the use of the polymers according to the present invention as electron donor or p-type semiconductor.
The invention further relates to the use of the polymers according to the present invention as electron donor component in a semiconducting material, formulation, polymer blend, device or component of a device. The invention further relates to a semiconducting material, formulation, polymer blend, device or component of a device comprising a polymer according to the present invention as electron donor component, and preferably further comprising one or more compounds or polymers having electron acceptor properties.
The invention further relates to a mixture or polymer blend comprising one or more polymers according to the present invention and one or more additional compounds which are preferably selected from compounds having one or more of semiconducting, charge transport, hole or electron transport, hole or electron blocking, electrically conducting,
photoconducting or light emitting properties.
The invention further relates to a mixture or polymer blend as described above and below, which comprises one or more polymers of the present invention and one or more n-type organic semiconductor compounds, preferably selected from fullerenes or substituted fullerenes.
The invention further relates to a formulation comprising one or more polymers, formulations, mixtures or polymer blends according to the present invention and optionally one or more solvents, preferably selected from organic solvents.
The invention further relates to the use of a polymer, formulation, mixture or polymer blend of the present invention as charge transport,
semiconducting, electrically conducting, photoconducting or light emitting material, or in an optical, electrooptical, electronic, electroluminescent or photoluminescent device, or in a component of such a device or in an assembly comprising such a device or component.
The invention further relates to a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer, formulation, mixture or polymer blend according to the present invention.
The invention further relates to an optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a polymer, formulation, mixture or polymer blend, or comprises a charge transport,
semiconducting, electrically conducting, photoconducting or light emitting material, according to the present invention.
The optical, electrooptical, electronic, electroluminescent and
photoluminescent devices include, without limitation, organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, and photoconductors.
The components of the above devices include, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
The assemblies comprising such devices or components include, without limitation, integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containg them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips. In addition the compounds, polymers, formulations, mixtures or polymer blends of the present invention can be used as electrode materials in batteries and in components or devices for detecting and discriminating DNA sequences.
Detailed Description
The polymers of the present invention are easy to synthesize and exhibit advantageous properties. They show good processability for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods. At the same time, the co-polymers derived from monomers of the present invention and electron donor monomers show low bandgaps, high charge carrier mobilities, high external quantum efficiencies in BHJ solar cells, good morphology when used in p/n-type blends e.g. with fullerenes, high oxidative stability, and a long lifetime in electronic devices, and are promising materials for organic electronic OE devices, especially for OPV devices with high power conversion efficiency.
The units of formula I are especially suitable as (electron) donor unit in both n-type and p-type semiconducting compounds, polymers or copolymers, in particular copolymers containing both donor and acceptor units, and for the preparation of blends of p-type and n-type
semiconductors which are suitable for use in BHJ photovoltaic devices.
The repeating units of formula I contain an enlarged system of fused aromatic rings, which creates numerous benefits in developing novel high performance OSC materials. Firstly, a large number of fused aromatic rings along the long axis of the core structure increases the overall planarity and reduces the number of the potential twists of the conjugated molecular backbone. Elongation of the π-π structure or monomer increases the extent of conjugation which facilitates charge transport along the polymer backbone. Secondly, the high proportion of sulphur atoms in the molecular backbone through the presence of fused thiophene rings promotes more intermolecular short contacts, which benefits charge hopping between molecules. Thirdly, the large number of fused rings leads to an increased proportion of ladder structure in the OSC polymer main chain. This forms a broader and more intense absorption band resulting in improved solar light harvesting compared with prior art materials.
Additionally but not lastly, fusing aromatic rings can more efficiently modify the HOMO and LUMO energy levels and bandgaps of the target monomer structures compared with periphery substitutions.
Besides, the polymers of the present invention show the following advantageous properties: i) The indacenodibenzothiophene (IDDBT) and dithia-dicyclopenta- dibenzothiophene (TTDBT) units are expected to exhibit a co-planar structure. Adopting a highly co-planar structure in the solid-state is beneficial for charge transport. ii) The IDDBT and TTDBT core structures can be solubilised by both four alkyl groups or two alkylidene groups. Compared with the tetra-alkyl analogues, the dialkylidene substituted IDDBT-based molecules and polymers are expected to possess a higher degree of planarity. This is due to the sp2 carbon atoms in the alkylidenes which allow the alkyl chains to take an in-plane configuration. This configuration reduces the inter-planar separation of the π-π backbones, and improves the degree of inter-molecular π-π interactions. tii) The optoelectronic properties of conjugated polymers vary significantly based upon the degree of extended conjugation between the
consecutive repeating units and the inherent electron densities within the polymer backbones. By fusing additional aromatic rings along the long axis, the π-conjugation of the resultant molecules and
consequently the polymers can be extended and the number of the inter-unit twists in the backbone can be reduced iv) Additional fine-tuning and further modification of the
indacenodibenzothiophene (IDDBT) and dithia-dicyclopenta- dibenzothiophene (TTDBT) cores or co-polymerisation with appropriate co-monomer(s) can afford conjugated polymers that are suitable as organic semiconductors for organic electronic applications. The synthesis of the unit of formula I, its functional derivatives,
compounds, homopolymers, and co-polymers can be achieved based on methods that are known to the skilled person and described in the literature, as will be further illustrated herein.
As used herein, the term "polymer" will be understood to mean a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass (Pure Appl. Chem., 1996, 68, 2291). The term "oligomer" will be understood to mean a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass (Pure Appl. Chem., 1996, 68, 2291). In a preferred meaning as used herein present invention a polymer will be understood to mean a compound having > 1 , i.e. at least 2 repeat units, preferably≥ 5 repeat units, and an oligomer will be understood to mean a compound with > 1 and < 10, preferably < 5, repeat units.
Further, as used herein, the term "polymer" will be understood to mean a molecule that encompasses a backbone (also referred to as "main chain") of one or more distinct types of repeat units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms "oligomer", "copolymer", "homopolymer" and the like. Further, it will be understood that the term polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto. Further, such residues and other elements, while normally removed during post polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media.
As used herein, in a formula showing a polymer or a repeat unit, like for example a unit of formula I or a polymer of formula III or IV, or their subformulae, an asterisk (*) will be understood to mean a chemical linkage to an adjacent unit or to a terminal group in the polymer backbone. In a ring, like for example a benzene or thiophene ring in formula I, an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring.
As used herein, the terms "repeat unit", "repeating unit" and "monomeric unit" are used interchangeably and will be understood to mean the constitutional repeating unit (CRU), which is the smallest constitutional unit the repetition of which constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain {Pure Appl. Chem., 1996, 68, 2291). As further used herein, the term "unit" will be understood to mean a structural unit which can be a repeating unit on its own, or can together with other units form a constitutional repeating unit.
As used herein, a "terminal group" will be understood to mean a group that terminates a polymer backbone. The expression "in terminal position in the backbone" will be understood to mean a divalent unit or repeat unit that is linked at one side to such a terminal group and at the other side to another repeat unit. Such terminal groups include endcap groups, or reactive groups that are attached to a monomer forming the polymer backbone which did not participate in the polymerisation reaction, like for example a group having the meaning of R5 or R6 as defined below.
As used herein, the term "endcap group" will be understood to mean a group that is attached to, or replacing, a terminal group of the polymer backbone. The endcap group can be introduced into the polymer by an endcapping process. Endcapping can be carried out for example by reacting the terminal groups of the polymer backbone with a
monofunctional compound ("endcapper") like for example an alkyl- or arylhalide, an alkyl- or arylstannane or an alkyl- or arylboronate. The endcapper can be added for example after the polymerisation reaction. Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerisation reaction. In situ addition of an endcapper can also be used to terminate the polymerisation reaction and thus control the molecular weight of the forming polymer. Typical endcap groups are for example H, phenyl and lower alkyl. As used herein, the term "small molecule" will be understood to mean a monomeric compound which typically does not contain a reactive group by which it can be reacted to form a polymer, and which is designated to be used in monomeric form. In contrast thereto, the term "monomer" unless stated otherwise will be understood to mean a monomeric compound that carries one or more reactive functional groups by which it can be reacted to form a polymer.
As used herein, the the terms "donor" or "donating" and "acceptor" or "accepting" will be understood to mean an electron donor or electron acceptor, respectively. "Electron donor" will be understood to mean a chemical entity that donates electrons to another compound or another group of atoms of a compound. "Electron acceptor" will be understood to mean a chemical entity that accepts electrons transferred to it from another compound or another group of atoms of a compound, (see also U.S. Environmental Protection Agency, 2009, Glossary of technical terms, httD://www.epa.qov/oust/cat/TUMGLOSS.HTM
As used herein, the term "n-type" or "n-type semoiconductor" will be understood to mean an extrinsic semiconductor in which the conduction electron density is in excess of the mobile hole density, and the term "p- type" or "p-type semiconductor" will be understood to mean an extrinsic semiconductor in which mobile hole density is in excess of the conduction electron density (see also, J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).
As used herein, the term "leaving group" will be understood to mean an atom or group (which may be charged or uncharged) that becomes detached from an atom in what is considered to be the residual or main part of the molecule taking part in a specified reaction (see also Pure AppI. Chem., 1994, 66, 1134).
As used herein, the term "conjugated" will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp2- hybridisation (or optionally also sp-hybridisation), and wherein these C atoms may also be replaced by hetero atoms. In the simplest case this is for example a compound with alternating C-C single and double (or triple) bonds, but is also inclusive of compounds with aromatic units like for example 1 ,4-phenylene. The term "mainly" in this connection will be understood to mean that a compound with naturally (spontaneously) occurring defects, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
As used herein, unless stated otherwise the molecular weight is given as the number average molecular weight Mn or weight average molecular weight Mw, which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene or 1 , 2, 4-trichloro- benzene. Unless stated otherwise, 1 ,2,4-trichlorobenzene is used as solvent. The degree of polymerization, also referred to as total number of repeat units, n, will be understood to mean the number average degree of polymerization given as n = Mn/Mu, wherein Mn is the number average molecular weight and Mu is the molecular weight of the single repeat unit, see J. M. G. Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991.
As used herein, the term "carbyl group" will be understood to mean denotes any monovalent or multivalent organic radical moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example -C≡C-), or optionally combined with at least one non- carbon atom such as N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.). The term "hydrocarbyl group" will be understood to mean a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example N, O, S, P, Si, Se, As, Te or Ge.
As used herein, the term "hetero atom" will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean N, O, S, P, Si, Se, As, Te or Ge. A carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, including spiro and/or fused rings. Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy,
alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore
alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and
aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, wherein all these groups do optionally contain one or more hetero atoms, preferably selected from N, O, S, P, Si, Se, As, Te and Ge.
The carbyl or hydrocarbyl group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially aryl, alkenyl and alkynyl groups (especially ethynyl). Where the Ci-C40 carbyl or hydrocarbyl group is acyclic, the group may be straight-chain or branched. The C1-C40 carbyl or hydrocarbyl group includes for example: a Ci-C40 alkyl group, a Ci-C4o fluoroalkyl group, a Ci-C40 alkoxy or oxaalkyl group, a C2-C40 alkenyl group, a C2-C4o alkynyl group, a C3-C40 allyl group, a C4-C4o alkyldienyl group, a C4-C40 polyenyl group, a C2-C4o ketone group, a C2-C40 ester group, a C6-Ci8 aryl group, a C6-C4o alkylaryl group, a C6-C4o arylalkyl group, a C -C4o cycloalkyl group, a C -C40 cycloalkenyl group, and the like. Preferred among the foregoing groups are a Ci-C20 alkyl group, a Ci-C20 fluoroalkyl group, a C2-C2o alkenyl group, a C2 -C2o alkynyl group, a C3- C2o allyl group, a C4-C2o alkyldienyl group, , a C2-C20 ketone group, a C2- C20 ester group, a C6-Ci2 aryl group, and a C4-C2o polyenyl group, respectively. Also included are combinations of groups having carbon atoms and groups having hetero atoms, like e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.
The terms "aryl" and "heteroaryl" as used herein preferably mean a mono-, bi- or tricyclic aromatic or heteroaromatic group with 4 to 30 ring C atoms that may also comprise condensed rings and is optionally substituted with one or more groups L, wherein L is selected from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=0)NR°R°°, -C(=0)X°, -C(=0)R°, -NH2, -NR°R00, -SH, -SR°, -S03H, - S02R°, -OH, -NO2, -CF3, -SF5, Ρ-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, and is preferably alkyl, alkoxy, thiaalkyi, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy with 1 to 20 C atoms that is optionally fluorinated, and R°, R00, X°, P and Sp have the meanings given above and below.
Very preferred substituents L are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoroalkoxy with 1 to 12 C atoms or alkenyl, alkynyl with 2 to 12 C atoms. Especially preferred aryl and heteroaryl groups are phenyl in which, in addition, one or more CH groups may be replaced by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above. Very preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2- selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2- b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, seleno[2,3- bjselenophene, thieno[3,2-b]selenophene, thieno[3,2-b]furan, indole, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1 ,2-b;4,5- b']dithiophene, benzo[2,1-b;3,4-b']dithiophene, quinole, 2- methylquinole, isoquinole, quinoxaline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzothiadiazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above. Further examples of aryl and heteroaryl groups are those selected from the groups shown hereinafter. An alkyl or alkoxy radical, i.e. where the terminal CH2 group is replaced by -0-, can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
An alkenyl group, wherein one or more CH2 groups are replaced by - CH=CH- can be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop- 2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-,
4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-,
5- , 6-, 7-, 8- or dec-9-enyl. Especially preferred alkenyl groups are C2-C7-I E-alkenyl, C4-C7-3E- alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-I E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl,
3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl,
4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
An oxaalkyl group, i.e. where one CH2 group is replaced by -0-, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-
(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7- oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9- oxadecyl, for example.Oxaalkyl, i.e. where one CH2 group is replaced by - 0-, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-
(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7- oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9- oxadecyl, for example. ln an alkyl group wherein one CH2 group is replaced by -O- and one by - C(O)-, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group -C(O)-O- or an oxycarbonyl group -O-C(O)-. Preferably this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxy- ethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl,
4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy- carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl,
2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy- carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)-butyl.
An alkyl group wherein two or more CH2 groups are replaced by -O- and/or -C(O)O- can be straight-chain or branched. It is preferably straight- chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy- methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy- butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy- heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy- decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4)4-bis-(methoxycarbonyl)-butyl, 5,5-bis- (methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis- (methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis- (ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis- (ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis- (ethoxycarbonyl)-hexyl. A thioalkyl group, i.e where one CH2 group is replaced by -S-, is preferably straight-chain thiomethyl (-SCH3), 1-thioethyl (-SCH2CH3), 1- thiopropyl (= -SCH2CH2CH3), 1- (thiobutyl), -(thiopentyl), l-(thiohexyl), 1- (thioheptyl), l-(thiooctyl), l-(thiononyl), l-(thiodecyl), l-(thioundecyl) or 1- (thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridised vinyl carbon atom is replaced. A fluoroalkyl group is preferably peril uoroalkyl CjF2i+i , wherein i is an integer from 1 to 15, in particular CF3, C2F5, C3F7, C4F9, C5Fn, C6F13,
C7Fi5 or C8F17, very preferably CeFi3, or partially fluor'inated alkyl, in particular 1 ,1-difluoroalkyl, all of which are straight-chain or branched.
Alkyl, alkoxy, alkenyl, oxaalkyi, thioalkyi, carbonyl and carbonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are 2- butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2- ethylhexyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2- methylpentoxy, 3-methylpentoxy, 2-ethyl-hexoxy, -methylhexoxy, 2- octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2- hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-meth-oxyoctoxy, 6- methy!octoxy, 6-methyloctanoyloxy, 5-methylheptyloxy-carbonyl, 2- methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2- chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methyl-valeryl- oxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa- hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2- oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1 ,1 ,1-trifluoro- 2-octyloxy, 1,1 ,1 -trifluoro-2-octyl, 2-fluoromethyloctyloxy for example. Very preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1 ,1 ,1-trifluoro-2-hexyl, 1 ,1 ,1- trifluoro-2-octyl and 1 ,1,1-trifluoro-2-octyloxy.
Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tert. butyl, isopropoxy, 2-methyl-propoxy and 3- methylbutoxy.
In a preferred embodiment, R1 ,2 are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms. Very preferred groups of this type are selected from the group consisting of the following formulae
Figure imgf000020_0001
wherein "ALK" denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached. Especially preferred among these groups are those wherein all ALK subgroups are identical.
-CY 1=CY12- is preferably -CH=CH-, -CF=CF- or -CH=C(CN)-
As used herein, "halogen" includes F, CI, Br or I, preferably F, CI or Br.
A used herein, -CO-, -C(=0)- and -C(O)- will be understood to
O
I I
carbonyl group, i.e. a group having the structure
Preferably X1 and X2 in formula I denote C(R R2), C=(R1R2), Si(R R2) or C=0 very preferably C(R1 R2) or C=(R1 R2).
Preferably the units of formula I are selected from the following formulae:
la
Figure imgf000020_0002
Figure imgf000021_0001
wherein X1 and X2 have the meanings of formula I as given above and below, wherein the terminal thiophene rings may also be substituted in 3- position by a group R1. In a preferred embodiment one or both terminal thiophene rings are substituted in 3-position by a group R
In the units of formula I and its preferred subformulae, R and R2 preferably denote straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubstituted or substituted by one or more F atoms.
Further preferably one of R1 and R2 is H and the other is different from H, and is preferably straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubsituted or substituted by one or more F atoms.
Further preferably R1 and/or R2 are independently of each other selected from the group consisting of aryl and heteroaryl, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms.
If R and/or R2 in formula I denote substituted aryl or heteroaryl, it is preferably substituted by one or more groups L, wherein L is selected from P-Sp-, F, CI, Br, I, -OH, -CN, -NO2 , -NCO, -NCS, -OCN, -SCN, - C(=O)NR°R00, -C(=O)X°, -C(=O)R°, -NR°R00, C(=O)OH, optionally substituted aryl or heteroaryl having 4 to 20 ring atoms, or straight chain, branched or cyclic alkyl with 1 to 20, preferably 1 to 12 C atoms wherein one or more non-adjacent CH2 groups are optionally replaced, in each case independently from one another, by -0-, -S-, -NR0-, -SiR°R00-, - C(=0)-, -C(=0)0-, -CY =CY2- or -C≡C- in such a manner that O and/or S atoms are not linked directly to one another and which is unsubstituted or substituted with one or more F or CI atoms or OH groups, X° is halogen, preferably F, CI or Br, and Y1, Y2, R° and R00 have the meanings given above and below.
Further preferably R and/or R2 in formula I denote aryl or heteroaryl that is substituted by one or more straight-chain, branched or cyclic alkyl groups with 1 to 30 C atoms, in which one or more non-adjacent CH2 groups are optionally replaced by one or more non-adjacent CH2 groups are optionally replaced by -O-, -S-, -C(O)-, -C(O)-O-, -O-C(O)-, -O-C(O)-O- , -NR0-, -SiR°R00-, -CF2-, -CHR°=CR00-, -CY1=CY2- or -C≡C- in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, CI, Br, I or CN.
Preferred polymers according to the present invention comprise one or more repeating units of formula II:
-[(Ar1)a-(U)b-(Ar2)c-(Ar3)d]- II wherein
U is a unit of formula I,
Ar1, Ar2, Ar3 are, on each occurrence identically or differently, and
independently of each other, aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms, and is optionally substituted, preferably by one or more groups Rs,
Rs is on each occurrence identically or differently F, Br, CI, -CN,■
NC, -NCO, -NCS, -OCN, -SCN, -C(O)NR°R00, -C(O)X°, - C(O)R°, -C(O)OR°, -NH2, -NR°R00, -SH, -SR°, -SO3H, -SO2R° -OH, -NO2, -CF3, -SF5, optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
R° and R00 are independently of each other H or optionally substituted
C-1-40 carbyl or hydrocarbyl, and preferably denote H or alkyl with 1 to 12 C-atoms,
X° is halogen, preferably F, CI or Br, a, b and c are on each occurrence identically or differently 0, 1 or 2, d is on each occurrence identically or differently 0 or an integer from 1 to 10, wherein the polymer comprises at least one repeating unit of formula II wherein b is at least 1.
Further preferred polymers according to the present invention comprise, in addition to the units of formula I or II, one or more repeating units selected from monocyclic or polycyclic aryl or heteroaryl groups that are optionally substituted.
These additional repeating units are preferably selected of formula III -[(Ar1)a-(Ac)b-(ArV(Ar3)d]- HI wherein Ar1, Ar2, Ar3, a, b, c and d are as defined in formula II, and Ac is an aryl or heteroaryl group that is different from U and Ar1"3, preferably has 5 to 30 ring atoms, is optionally substituted by one or more groups Rs as defined above and below, and is preferably selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula III wherein b is at least 1.
Rs preferably has one of the meanings given for R1. The conjugated polymers according to the present invention are preferably selected of formula IV:
*-†-(A)x— (B> y Jn IV wherein
A is a unit of formula I or II or its preferred subformulae,
B is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted, and is preferably selected of formula III, x is > 0 and < 1 , y is > 0 and < 1 , x + y is 1 , and n is an integer >1.
Preferred polymers of formula IV are selected of the following formulae *-[(Ar1-U-ArV(Ar3)v]n-* IVa
Figure imgf000024_0001
*_[(Ar1-U-A^)x-(Ar3-A^-Ar3)v]n-* IVc
*-[(Ar1)a-(U)b-(Ai^)c-(Ar3)d]n-* IVd
*-([(Ar1 )a-(U)b-(Ar2)c-(Ar3)d]x-[(Ar1)a-(Ac)b-(Ar2)c-(Ar3)d)y)n-* IVe wherein U, Ar1, Ar2, Ar3, a, b, c and d have in each occurrence identically or differently one of the meanings given in formula II, A° has on each occurrence identically or differently one of the meanings given in formula III, and x, y and n are as defined in formula IV, wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units
Figure imgf000025_0001
and in at least one of the repeating units [(Ar1)a-(Ac)b-(Ar2)c-(Ar3)d] b is at least 1.
In the polymers according to the present invention, the total number of repeating units n is preferably from 2 to 10,000. The total number of repeating units n is preferably > 5, very preferably > 10, most preferably > 50, and preferably < 500, very preferably < 1 ,000, most preferably < 2,000, including any combination of the aforementioned lower and upper limits of n.
The polymers of the present invention include homopolymers and
copolymers, like statistical or random copolymers, alternating copolymers and block copolymers, as well as combinations thereof.
Especially preferred are polymers selected from the following groups:
- Group A consisting of homopolymers of the unit U or (Ar1-U) or (Ar1-U- Ar2) or (Ar -U-Ar3) or (U-Ai^-Ar3) or (Ar^U-Ai^-Ar3), i.e. where all repeating units are identical, ,
- Group B consisting of random or alternating copolymers formed by
identical units (A^-U-Ar2) and identical units (Ar3),
- Group C consisting of random or alternating copolymers formed by
identical units (A^-U-Ar2) and identical units (A1),
- Group D consisting of random or alternating copolymers formed by
identical units (Ar^U-Ar2) and identical units (Ar^A^Ar2), wherein in all these groups U, Ac, Ar1, Ar2 and Ar3 are as defined above and below, in groups A, B and C Ar1, Ar2 and Ar3 are different from a single bond, and in group D one of Ar1 and Ar2 may also denote a single bond . Preferred polymers of formula IV and IVa to IVe are selected of formula V R5-chain-R6 V wherein "chain" denotes a polymer chain of formulae IV or IVa to IVe, and R5 and R6 have independently of each other one of the meanings of R1 as defined above, or denote, independently of each other, H, F, Br, CI, I, - CH2CI, -CHO, -CR^CR^, -SHWR"', -SiR'X'X", -SiR'R' , -SnR'^'R'", - BR'R", -B(OR')(OR"), -B(OH)2, -0-S02-R', -C≡CH, -C≡C-SiR'3, -ZnX' or an endcap group, X' and X" denote halogen, R', R" and R'" have
independently of each other one of the meanings of R° given in formula I, and two of R', R" and R"' may also form a ring together with the hetero atom to which they are attached. Preferred endcap groups R5 and R6 are H, Ci-20 alkyl, or optionally substituted C6-12 aryl or C2-i0 heteroaryl, very preferably H or phenyl.
In the polymers represented by formula IV, IVa to IVe and V, x denotes the mole fraction of units A, y denotes the mole fraction of units B, and n denotes the degree of polymerisation or total number of units A and B. These formulae includes block copolymers, random or statistical copolymers and alternating copoymers of A and B, as well as
homopolymers of A for the case when x is > 0 and y is 0. Another aspect of the invention relates to monomers of formula VI
Figure imgf000026_0001
wherein U, Ar1, Ar2, a and b have the meanings of formula II, or one of the preferred meanings as described above and below, and R7 and R8 are, preferably independently of each other, selected from the group consisting of CI, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, -SiMe2F, - SiMeF2, -0-S02Z1, -B(OZ2)2 , -CZ3=C(Z3)2, -CsCH, - C≡CSi(Z1)3, -ZnX0 and -Sn(Z4)3, wherein X° is halogen, preferably CI, Br or I, Z1"4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z2 may also together form a cyclic group. Especially preferred are monomers of the following formulae
R^Ar^U-Ar2-^ V11
R7-U-R' VI2
R7-Ar1-U-R' VI3 R^U-Ar^R' VI4 wherein U, Ar\ Ar2, R7 and R8 are as defined in formula VI.
Especially preferred are repeating units, monomers and polymers of formulae I, II, III, IV, IVa-IVe, V, VI and their subformulae wherein one or more of Ar1, Ar2 and Ar3 denote aryl or heteroaryl, preferably having electron donor properties, selected from the group consisting of the following formulae
Figure imgf000027_0001
(D1) (D2) (D3) (D4)
Figure imgf000027_0002
(D10)
Figure imgf000028_0001
Figure imgf000029_0001
(D39) (D40) (D41)
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0003
Figure imgf000033_0004
(D71) wherein one of X11 and X12 is S and the other is Se, and R11 , R12, R13, R14, R15, R16, R17 and R18 independently of each other denote H or have one of the meanings of R as defined above and below.
Further preferred are repeating units, monomers and polymers of formulae I, II, III, IV. IVa to IVe, V, VI and their subformulae wherein Ac and/or Ar3 denotes aryl or heteroaryl, preferably having electron acceptor properties, selected from the group consisting of the following formulae
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001

Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000040_0002
(A89) (A90) (A91)
wherein one of X11 and X12 is S and the other is Se, and R11, R12, R13, R14, R15 and R 6 independently of each other denote H or have one of the meanings of R1 as defined above and below.
Especially preferred copolymers of the following formulae: -(U)x- IVa
-(U)x-(Ar)x- IVb
-(U-Ar)n- IVc wherein U and Ar1 are as defined in formula II, and n, x and y are as defined in formula IV.
Further preferred are repeating units, monomers and polymers of formulae l-VI and their subformulae selected from the following list of preferred embodiments: - y is > 0 and < 1 ,
- X1 and X2 are C(R1R2)„
- X1 and X2 are C=(R1R2),
- X1 and X2 are Si(R1R2),
- X1 and X2 are C=0,
- n is at least 5, preferably at least 10, very preferably at least 50, and up to 2,000, preferably up to 500.
- Mw is at least 5,000, preferably at least 8,000, very preferably at least 0,000, and preferably up to 300,000, very preferably up to 100,000,
- one of R1 and R2 is H and the other is different from H,
- R and R2 are different from H,
- R1 and/or R2 are independently of each other selected from the group consisting of primary alkyl with 1 to 30 C atoms, secondary alkyl with 3 to 30 C atoms, and tertiary alkyl with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F,
- R and/or R2 are independently of each other selected from the group consisting of aryl and heteroaryl, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms,
- R1 and/or R2 are independently of each other selected from the group consisting of primary alkoxy or sulfanylalkyi with 1 to 30 C atoms, secondary alkoxy or sulfanylalkyi with 3 to 30 C atoms, and tertiary alkoxy or sulfanylalkyi with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F,
- R1 and/or R2 are independently of each other selected from the group consisting of aryloxy and heteroa ry loxy, each of which is optionally alkylated or alkoxylated and has 4 to 30 ring atoms,
- R1 and/or R2 are independently of each other selected from the group consisting of alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, all of which are straight-chain or branched, are optionally fluorinated, and have from 1 to 30 C atoms, - R1 and/or R2 denote independently of each other F, CI, Br, I, CN, R9, - C(0)-R9, -C(O)-O-R9 or -0-C(0)-R9, -S02-R9, -SO3-R9, wherein R9 is straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by -0-, -S-, - C(O)-, -C(0)-O-, -O-C(O)-, -0-C(0)-0-, -SO2-, -SO3-, -CR°=CR00- or -
C≡C- and in which one or more H atoms are optionally replaced by F, CI, Br, I or CN, or R9 is aryl or heteroaryl having 4 to 30 ring atoms which is unsubstituted or which is substituted by one or more halogen atoms or by one or more groups R as defined above,
- R° and R00 are selected from H or d-C^-alkyl,
- R5 and R6 are selected from H, halogen, -CH2CI, -CHO, -CH=CH2 - SiR'R"R"', -SnR'R"R'", -BR'R", -B(OR')(OR"), -B(OH)2, P-Sp, Ci-C20- alkyl, Ci-C2o-alkoxy, C2-C2o-alkenyl, Ci-C2o-fluoroalkyl and optionally substituted aryl or heteroaryl, preferably phenyl,
- R7 and R8 are, preferably independently of each other, selected from the group consisting of CI, Br, I, O-tosylate, O-triflate, O-mesylate, O- nonaflate, -SiMe2F, -SiMeF2, -0-S02Z1, -B(OZ2)2 , -CZ3=C(Z4)2, -C≡CH, C≡CSi(Z1)3, -ZnX° and -Sn(Z4)3) wherein X° is halogen, Z1"4 are selected from the group consisting of alkyl and aryl, each being optionally
substituted, and two groups Z2 may also form a cyclic group.
The compounds of the present invention can be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature. Other methods of preparation can be taken from the examples. For example, the polymers can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling and Yamamoto coupling are especially preferred. The monomers which are polymerised to form the repeat units of the polymers can be prepared according to methods which are known to the person skilled in the art.
Preferably the polymers are prepared from monomers of formula VI or their preferred subformulae as described above and below.
Another aspect of the invention is a process for preparing a polymer by coupling one or more identical or different monomeric units of formula I or monomers of formula VI with each other and/or with one or more comonomers in a polymerisation reaction, preferably in an aryl-aryl coupling reaction.
Suitable and preferred comonomers are selected from the following formulae
Figure imgf000043_0001
R7-Ar1-R8 D
R7-Ar3-R8 E wherein Ar1, Ar2, Ar3, a and c have one of the meanings of formula II or one of the preferred meanings given above and below, Ac has one of the meanings of formula III or one of the preferred meanings given above and below, and R7 and R8 have one of meanings of formula VI or one of the preferred meanings given above and below.
Very preferred is a process for preparing a polymer by coupling one or more monomers selected from formula VI or formulae VI1-VI4 with one or more monomers of formula C, and optionally with one or more monomers selected from formula D and E, in an aryl-aryl coupling reaction, wherein preferably R7 and R8 are selected from CI, Br, I, -B(OZ2)2 and -Sn(Z )3.
For example, preferred embodiments of the present invention relate to a) a process of preparing a polymer by coupling a monomer of formula V11
R7-Ar1-U-Ar*-R8 V11 with a monomer of formula D1 R7-Ar -Rj D1 in an aryl-aryl coupling reaction,
or
b) a process of preparing a polymer by coupling a monomer of formula VI2 R7-U-R8 VI2
with a monomer of formula C1
R^Ar^-Ai^-R8 C1
in an aryl-aryl coupling reaction,
or
c) a process of preparing a polymer by coupling a monomer of formula VI2 R7-U-R8 VI2
with a monomer of formula C2
R7-Ac-R8 C2
in an aryl-aryl coupling reaction, or
d) a process of preparing a polymer by coupling a monomer of formula VI2 R7-U-R8 VI2
with a monomer of formula C2
R7-Ac-R8 C1
and a monomer of formula D1 R7-Ar -R8 D1 in an aryl-aryl coupling reaction, wherein R7, R8, U, Ac, Ar1 ,2 are as defined in formula II, III and VI, and R7 and R8 are preferably selected from CI, Br, I, -B(OZ2)2 and -Sn(Z4)3 as defined in formula VI.
Preferred aryl-aryl coupling methods used in the processes described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C-H activation coupling, Ullmann coupling or Buchwald coupling. Especially preferred are Suzuki coupling, Negishi coupling, Stille coupling and Yamamoto coupling. Suzuki coupling is described for example in WO 00/53656 A1. Negishi coupling is described for example in J. Chem. Soc, Chem. Commun., 1977, 683-684. Yamamoto coupling is described in for example in T. Yamamoto er a/., Prog. Polym. Sci., 1993, 17, 1153-1205, or WO 2004/022626 A1. For example, when using Yamamoto coupling, monomers having two reactive halide groups are preferably used. When using Suzuki coupling, monomers having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, monomers having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, monomers having two reactive organozinc groups or two reactive halide groups are preferably used.
Suzuki and Stille polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers. Statistical or block copolymers can be prepared for example from the above monomers wherein one of the reactive groups is halogen and the other reactive group is a boronic acid, boronic acid derivative group or and alkylstannane. The synthesis of statistical, alternating and block
copolymers is described in detail for example in WO 03/048225 A2 or WO 2005/014688 A2.
Preferred catalysts, especially for Suzuki, Negishi or Stille coupling, are selected from Pd(0) complexes or Pd(ll) salts. Preferred Pd(0) complexes are those bearing at least one phosphine ligand such as Pd( h3P) . Another preferred phosphine ligand is tris(o/f/70-tolyl)phosphine, i.e. Pd(o-Tol3P) . Preferred Pd(ll) salts include palladium acetate, i.e. Pd(OAc)2. Alternatively the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dibenzyl-ideneacetone)dipalladium(0),
bis(dibenzylideneacetone)palladium(0), or Pd(ll) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(orf/70- tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki coupling is performed in the presence of a base, for example sodium carbonate, potassium
carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide.
Yamamoto coupling employs a Ni(0) complex, for example bis(1,5- cyclooctadienyl) nickel(O).
As alternatives to halogens as described above, leaving groups of formula -0-S02Z1 can be used wherein Z1 is as described above. Particular examples of such leaving groups are tosylate, mesylate and triflate. Especially suitable and preferred synthesis methods of the repeating units, monomers and polymers of formulae l-VI and their subformulae are illustrated in the synthesis schemes shown hereinafter, wherein R1,2 have the meanings given above. The synthesis of two bromo benzothiophene isomers is exemplarily shown in Scheme 1.
Scheme 1
Figure imgf000047_0001
Figure imgf000047_0002
The synthesis of indacenodibenzothiophenes is exemplarily shown Schemes 2 to 5.
Scheme 2
Figure imgf000047_0003
Figure imgf000048_0001

Figure imgf000049_0001
Scheme 4
Figure imgf000049_0002
Figure imgf000050_0001

Figure imgf000051_0001
The synthesis of dithia-dicyclopenta-dibenzothiophenes is exemplarily shown in Schemes 6 and 7. Scheme 6
Figure imgf000051_0002
Figure imgf000051_0003
-51 -
Figure imgf000052_0001
The homopolymerisation of the indacenodibenzothiophenes is exemplarily shown in Scheme 8. Scheme 8
Figure imgf000053_0001
wherein X1 , X2, A1, A2 and B are as defined in formula I, and either Y1=Br and Y2=(B(OR)2> or Y =Br and Y2=SnR3.
The co-polymerisation of the indacenodibenzothiophenes is exemplarily shown in Scheme 9
Scheme 9
Figure imgf000053_0002
Figure imgf000054_0001
The novel methods of preparing monomers and polymers as described above and below are another aspect of the invention.
The compounds and polymers according to the present invention can also be used in mixtures or polymer blends, for example together with monomeric compounds or together with other polymers having charge- transport, semiconducting, electrically conducting, photoconducting and/or light emitting semiconducting properties, or for example with polymers having hole blocking or electron blocking properties for use as interlayers or charge blocking layers in OLED devices. Thus, another aspect of the invention relates to a polymer blend comprising one or more polymers according to the present invention and one or more further polymers having one or more of the above-mentioned properties. These blends can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the polymers are mixed with each other or dissolved in suitable solvents and the solutions combined.
Another aspect of the invention relates to a formulation comprising one or more small molecules, polymers, mixtures or polymer blends as described above and below and one or more organic solvents.
Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Additional solvents which can be used include 1 ,2,4-trimethylbenzene, 1 ,2,3,4-tetra- methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2,6-lutidine, 2-fluoro- m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, N,N- dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3- dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro- methylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3- methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4- fluoroveratrol, 2,6-dimethylanisole, 3-fluorobenzo-nitrile, 2,5- dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethyl-anisole, Ν,Ν-dimethylaniline, ethyl benzoate, 1-fluoro-3,5-dimethoxy-benzene, 1- methylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzo-trifluoride, benzotrifluoride, dioxane, trifluoromethoxy-benzene, 4- fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluoro-toluene, 2- fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4- difluorobenzene, 2-fluoropyridine, 3-chlorofluorobenzene, 1-chloro-2,5- difluorobenzene, 4-chlorofluorobenzene, chloro-benzene, o- dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylene, o-xylene or mixture of o-, m-, and p-isomers. Solvents with relatively low polarity are generally preferred. For inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred. For spin coating alkylated benzenes like xylene and toluene are preferred.
Examples of especially preferred solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p- xylene, 1,4-dioxane, acetone, methylethylketone, 1,2-dichloroethane, 1 ,1 ,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, Ν,Ν-dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetraline, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene and/or mixtures thereof.
The concentration of the compounds or polymers in the solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Optionally, the solution also comprises one or more binders to adjust the rheological properties, as described for example in WO 2005/055248 A1.
After the appropriate mixing and ageing, solutions are evaluated as one of the following categories: complete solution, borderline solution or
insoluble. The contour line is drawn to outline the solubility parameter- hydrogen bonding limits dividing solubility and insolubility. 'Complete' solvents falling within the solubility area can be chosen from literature values such as published in "Crowley, J.D., Teague, G.S. Jr and Lowe, J.W. Jr., Journal of Paint Technology, 1966, 38 (496), 296 ". Solvent blends may also be used and can be identified as described in "Solvents, W.H.Ellis, Federation of Societies for Coatings Technology, p9-10, 1986". Such a procedure may lead to a blend of 'non' solvents that will dissolve both the polymers of the present invention, although it is desirable to have at least one true solvent in a blend.
The compounds and polymers according to the present invention can also be used in patterned OSC layers in the devices as described above and below. For applications in modern microelectronics it is generally desirable to generate small structures or patterns to reduce cost (more devices/unit area), and power consumption. Patterning of thin layers comprising a polymer according to the present invention can be carried out for example by photolithography, electron beam lithography or laser patterning.
For use as thin layers in electronic or electrooptical devices the compounds, polymers, polymer blends or formulations of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.
Ink jet printing is particularly preferred when high resolution layers and devices needs to be prepared. Selected formulations of the present invention may be applied to prefabricated device substrates by ink jet printing or microdispensing. Preferably industrial piezoelectric print heads such as but not limited to those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar may be used to apply the organic semiconductor layer to a substrate. Additionally semi-industrial heads such as those manufactured by Brother, Epson,
Konica, Seiko Instruments Toshiba TEC or single nozzle microdispensers such as those produced by Microdrop and Microfab may be used.
In order to be applied by ink jet printing or microdispensing, the
compounds or polymers should be first dissolved in a suitable solvent.
Solvents must fulfil the requirements stated above and must not have any detrimental effect on the chosen print head. Additionally, solvents should have boiling points >100°C, preferably >140°C and more preferably >150°C in order to prevent operability problems caused by the solution drying out inside the print head. Apart from the solvents mentioned above, suitable solvents include substituted and non-substituted xylene
derivatives, di-Ci-2-alkyl formamide, substituted and non-substituted anisoles and other phenol-ether derivatives, substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and non-substituted /V,A -di-C .2-alkylanilines and other fluorinated or chlorinated aromatics.
A preferred solvent for depositing a compound or polymer according to the present invention by ink jet printing comprises a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three. For example, the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total. Such a solvent enables an ink jet fluid to be formed comprising the solvent with the compound or polymer, which reduces or prevents clogging of the jets and separation of the components during spraying. The solvent(s) may include those selected from the following list of examples: dodecylbenzene, 1 -methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, diethylbenzene. The solvent may be a solvent mixture, that is a combination of two or more solvents, each solvent preferably having a boiling point >100°C, more preferably >140°C. Such solvent(s) also enhance film formation in the layer deposited and reduce defects in the layer.
The ink jet fluid (that is mixture of solvent, binder and semiconducting compound) preferably has a viscosity at 20°C of 1-100 mPa s, more preferably 1-50 mPa s and most preferably 1-30 mPa s.
The polymer blends and formulations according to the present invention can additionally comprise one or more further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, nanoparticles, colourants, dyes or pigments, furthermore, especially in case crosslinkable binders are used, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents or co- reacting monomers.
The compounds and polymers to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices. In these devices, the polymers of the present invention are typically applied as thin layers or films.
Thus, the present invention also provides the use of the semiconducting compound, polymer, polymers blend, formulation or layer in an electronic device. The formulation may be used as a high mobility semiconducting material in various devices and apparatus. The formulation may be used, for example, in the form of a semiconducting layer or film. Accordingly, in another aspect, the present invention provides a semiconducting layer for use in an electronic device, the layer comprising a compound, polymer, polymer blend or formulation according to the invention. The layer or film may be less than about 30 microns. For various electronic device
applications, the thickness may be less than about 1 micron thick. The layer may be deposited, for example on a part of an electronic device, by any of the aforementioned solution coating or printing techniques. The invention additionally provides an electronic device comprising a compound, polymer, polymer blend, formulation or organic
semiconducting layer according to the present invention. Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices,
electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates and conducting patterns.
Especially preferred electronic device are OFETs, OLEDs and OPV devices, in particular bulk heterojunction (BHJ) OPV devices and OPD devices. In an OFET, for example, the active semiconductor channel between the drain and source may comprise the layer of the invention. As another example, in an OLED device, the charge (hole or electron) injection or transport layer may comprise the layer of the invention.
For use in OPV or OPD devices the polymer according to the present invention is preferably used in a formulation that comprises or contains, more preferably consists essentially of, very preferably exclusively of, a p- type (electron donor) semiconductor and an n-type (electron acceptor) semiconductor. The p-type semiconductor is constituted by a polymer according to the present invention. The n-type semiconductor can be an inorganic material such as zinc oxide (ZnOx), zinc tin oxide (ZTO), titan oxide (TiOx), molybdenum oxide (MoOx), nickel oxide (NiOx), or cadmium selenide (CdSe), or an organic material such as graphene or a fullerene or substituted fullerene, for example an indene-C60-fullerene bisaduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C6o fullerene, also known as "PCBM-C60" or "C6oPCBM", as disclosed for example in G. Yu, J. Gao, J.C. Hummelen, F. WudI, A.J. Heeger, Science 1995, Vol. 270, p. 1789 ff and having the structure shown below, or structural analogous compounds with e.g. a C6i fullerene group, a C70 fullerene group, or a C7i fullerene group, or an organic polymer (see for example Coakley, K. M. and McGehee, M. D. Chem. Mater. 2004, 16, 4533).
Figure imgf000060_0001
CeoPCBM Preferably the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene, like for example PCBM-C60, PCBM-C70, PCBM-C6i , PCB -C71, bis-PCBM-C6i, bis-PCBM-C7i, ICBA {V,V 4 4"- tetrahydro-di[1 ,4]methanonaphthaleno [1 ,2:2,,3';56,60:2",3,,][5l6]fullerene-C60-lh), graphene, or a metal oxide, like for example, ZnOx, TiOx, ZTO, MoOx, NiOx, to form the active layer in an OPV or OPD device. The device preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi- transparent substrate on one side of the active layer, and a second metallic or semi-transparent electrode on the other side of the active layer.
Further preferably the OPV or OPD device comprises, between the active layer and the first or second electrode, one or more additional buffer layers acting as hole transporting layer and/or electron blocking layer, which comprise a material such as metal oxide, like for example, ZTO, MoOx, ΝιΌχ, a conjugated polymer electrolyte, like for example PEDOT.PSS, a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example N,N'-diphenyl-N,N'-bis(1-naphthyl)(1 ,1'- biphenyl)-4,4'diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1 , r- biphenyl-4,4'-diamine (TPD), or alternatively as hole blocking layer and/or electron transporting layer, which comprise a material such as metal oxide, like for example, ZnOx, TiOx, a salt, like for example LiF, NaF, CsF, a conjugated polymer electrolyte, like for example poly[3-(6- trimethylammoniumhexyl)thiophene], poly(9,9-bis(2-ethylhexyl)- fluorene]-0-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly [(9,9- bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9- dioctylfluorene)] or an organic compound, like for example tris(8- quinolinolato)-aluminium(lll) (Alq3), 4,7-diphenyl-1 ,10-phenanthroline.
In a blend or mixture of a polymer according to the present invention with a fullerene or modified fullerene, the ratio polymenfullerene is preferably from 5:1 to 1 :5 by weight, more preferably from 1:1 to 1:3 by weight, most preferably 1:1 to 1 :2 by weight. A polymeric binder may also be included, from 5 to 95% by weight. Examples of binder include polystyrene (PS), polypropylene (PP) and polymethylmethacrylate (PMMA). To produce thin layers in BHJ OPV devices the compounds, polymers, polymer blends or formulations of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, dip coating, curtain coating, brush coating, slot dye coating or pad printing. For the fabrication of OPV devices and modules area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like. Suitable solutions or formulations containing the blend or mixture of a polymer according to the present invention with a C6o or C70 fullerene or modified fullerene like PCBM must be prepared. In the preparation of formulations, suitable solvent must be selected to ensure full dissolution of both component, p-type and n-type and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.
Organic solvent are generally used for this purpose. Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents. Examples include, but are not limited to chlorobenzene, 1 ,2-dichlorobenzene, chloroform, 1 ,2- dichloroethane, dichloromethane, carbon tetrachloride, toluene, cyclohexanone, ethylacetate, tetrahydrofuran, anisole, morpholine, o- xylene, m-xylene, p-xylene, 1 ,4-dioxane, acetone, methylethylketone, 1 ,2- dichloroethane, 1 ,1,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetraline, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene and combinations thereof.
The OPV device can for example be of any type known from the literature (see e.g. Waldauf ef a/., Appl. Phys. Lett., 2006, 89, 233517).
A first preferred OPV device according to the invention comprises the following layers (in the sequence from bottom to top):
- optionally a substrate,
- a high work function electrode, preferably comprising a metal oxide, like for example ITO, serving as anode,
- an optional conducting polymer layer or hole transport layer, preferably comprising an organic poymer or polymer blend, for example of
PEDOT:PSS (poly(3,4-ethylenedioxythiophene): poly(styrene- sulfonate), or TBD (N,N'-dyphenyl-N-N'-bis(3-methylphenyl)-
1 ,1 'biphenyl-4,4'-diamine) or NBD (N,N'-dyphenyl-N-N'-bis(1- napthylphenyl)-1 , 1 'biphenyl-4,4'-diamine),
- a layer, also referred to as "active layer", comprising a p-type and an n- type organic semiconductor, which can exist for example as a p-type/n- type bilayer or as distinct p-type and n-type layers, or as blend or p-type and n-type semiconductor, forming a BHJ,
- optionally a layer having electron transport properties, for example comprising LiF,
- a low work function electrode, preferably comprising a metal like for example aluminum, serving as cathode,
wherein at least one of the electrodes, preferably the anode, is transparent to visible light, and
wherein the p-type semiconductor is a polymer according to the present invention. A second preferred OPV device according to the invention is an inverted OPV device and comprises the following layers (in the sequence from bottom to top):
- optionally a substrate,
- a high work function metal or metal oxide electrode, comprising for example ITO, serving as cathode,
- a layer having hole blocking properties, preferably comprising a metal oxide like TiOx or Znx,
- an active layer comprising a p-type and an n-type organic
semiconductor, situated between the electrodes, which can exist for example as a p-type/n-type bilayer or as distinct p-type and n-type layers, or as blend or p-type and n-type semiconductor, forming a BHJ,
- an optional conducting polymer layer or hole transport layer, preferably comprising an organic poymer or polymer blend, for example of
PEDOT:PSS or TBD or NBD,
- an electrode comprising a high work function metal like for example silver, serving as anode,
wherein at least one of the electrodes, preferably the cathode, is transparent to visible light, and
wherein the p-type semiconductor is a polymer according to the present invention.
In the OPV devices of the present invention the p-type and n-type semiconductor materials are preferably selected from the materials, like the polymer/fullerene systems, as described above.
When the active layer is deposited on the substrate, it forms a BHJ that phase separates at nanoscale level. For discussion on nanoscale phase separation see Dennler et al, Proceedings of the IEEE, 2005, 93 (8), 1429 or Hoppe et al, Adv. Func. Mater, 2004, 14(10), 1005. An optional annealing step may be then necessary to optimize blend morpohology and consequently OPV device performance.
Another method to optimize device performance is to prepare formulations for the fabrication of OPV(BHJ) devices that may include high boiling point additives to promote phase separation in the right way. 1 ,8-Octanedithiol, 1 ,8-diiodooctane, nitrobenzene, chloronaphthalene, and other additives have been used to obtain high-efficiency solar cells. Examples are disclosed in J. Peet, ef al, Nat. Mater., 2007, 6, 497 or Frechet ef al. J. Am. Chem. Soc, 2010, 132, 7595-7597.
The compounds, polymers, formulations and layers of the present invention are also suitable for use in an OFET as the semiconducting channel. Accordingly, the invention also provides an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a compound, polymer, polymer blend, formulation or organic semiconducting layer according to the present invention. Other features of the OFET are well known to those skilled in the art.
OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode, are generally known, and are described for example in US 5,892,244, US 5,998,804, US 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT displays and security applications.
The gate, source and drain electrodes and the insulating and
semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
An OFET device according to the present invention preferably comprises:
- a source electrode,
- a drain electrode,
- a gate electrode, - a semiconducting layer,
- one or more gate insulator layers,
- optionally a substrate. wherein the semiconductor layer preferably comprises a compound, polymer, polymer blend or formulation as described above and below.
The OFET device can be a top gate device or a bottom gate device.
Suitable structures and manufacturing methods of an OFET device are known to the skilled in the art and are described in the literature, for example in US 2007/0102696 A1.
The gate insulator layer preferably comprises a fluoropolymer, like e.g. the commercially available Cytop 809M® or Cytop 107M® (from Asahi Glass). Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the
perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).
Especially preferred are organic dielectric materials having a low
permittivity (or dielectric contant) from 1.0 to 5.0, very preferably from 1.8 to 4.0 ("low k materials"), as disclosed for example in US 2007/0102696 A1 or US 7,095,044.
In security applications, OFETs and other devices with semiconducting materials according to the present invention, like transistors or diodes, can be used for RFID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with monetry value, like stamps, tickets, shares, cheques etc.
Alternatively, the materials according to the invention can be used in OLEDs, e.g. as the active display material in a flat panel display
applications, or as backlight of a flat panel display like e.g. a liquid crystal display. Common OLEDs are realized using multilayer structures. An emission layer is generally sandwiched between one or more electron- transport and/or hole-transport layers. By applying an electric voltage electrons and holes as charge carriers move towards the emission layer where their recombination leads to the excitation and hence luminescence of the lumophor units contained in the emission layer. The inventive compounds, materials and films may be employed in one or more of the charge transport layers and/or in the emission layer, corresponding to their electrical and/or optical properties. Furthermore their use within the emission layer is especially advantageous, if the compounds, materials and films according to the invention show electroluminescent properties themselves or comprise electroluminescent groups or compounds. The selection, characterization as well as the processing of suitable
monomeric, oligomeric and polymeric compounds or materials for the use in OLEDs is generally known by a person skilled in the art, see, e.g., Muller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128 and the literature cited therein.
According to another use, the materials according to this invention, especially those showing photoluminescent properties, may be employed as materials of light sources, e.g. in display devices, as described in EP 0 889 350 A1 or by C. Weder et a/., Science, 1998, 279, 835-837.
A further aspect of the invention relates to both the oxidised and reduced form of the compounds according to this invention. Either loss or gain of electrons results in formation of a highly delocatised ionic form, which is of high conductivity. This can occur on exposure to common dopants.
Suitable dopants and methods of doping are known to those skilled in the art, e.g. from EP 0 528 662, US 5, 98, 153 or WO 96/21659.
The doping process typically implies treatment of the semiconductor material with an oxidating or reducing agent in a redox reaction to form delocalised ionic centres in the material, with the corresponding
counterions derived from the applied dopants. Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion-implantantion of the dopant into the semiconductor material.
When electrons are used as carriers, suitable dopants are for example halogens (e.g., I2, Cl2, Br2, ICI, ICI3, IBr and IF), Lewis acids (e.g., PF5, AsF5, SbF5, BF3, BCI3, SbCle, BBr3 and S03), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HN03, H2S04, HCI04, FS03H and CISO3H), transition metal compounds (e.g., FeCI3, FeOCI, Fe(CI04)3, Fe(4-CH3C6H4S03)3, TiCI4, ZrCI4, HfCI4, NbF5, NbCI5, TaCI5, MoF5, MoCI5, WF5, WCI6, UF6 and LnCI3 (wherein Ln is a lanthanoid), anions (e.g., CI", Br", I', I3-, HS04 ", S04 2", N03 ", CI0 ", BF4 ", PF6 ", AsF6 ", SbF6 ", FeCI4 ", Fe(CN)6 3", and anions of various sulfonic acids, such as aryl-S03 "). When holes are used as carriers, examples of dopants are cations (e.g., H+, Li+, Na\ K+, Rb+ and Cs+), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline- earth metals (e.g., Ca, Sr, and Ba), 02, XeOF4, (N02 +) (SbF6 ~), (N02 +) (SbCle*), (N02 +) (BF4 ), AgCI04, H2lrCI6, La(N03)3 6H20, FS02OOS02F, Eu, acetylcholine, R4N+, (R is an alkyl group), R P+ (R is an alkyl group), R6As+ (R is an alkyl group), and R3S+ (R is an alkyl group).
The conducting form of the compounds of the present invention can be used as an organic "metal" in applications including, but not limited to, charge injection layers and ITO planarising layers in OLED applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers. The compounds and formulations according to the present invention may also be suitable for use in organic plasmon-emitting diodes (OPEDs), as described for example in Koller et al., Nat. Photonics, 2008, 2, 684.
According to another use, the materials according to the present invention can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US 2003/0021913. The use of charge transport compounds according to the present invention can increase the electrical conductivity of the alignment layer. When used in an LCD, this increased electrical conductivity can reduce adverse residual dc effects in the switchable LCD cell and suppress image sticking or, for example in ferroelectric LCDs, reduce the residual charge produced by the switching of the spontaneous polarisation charge of the ferroelectric LCs. When used in an OLED device comprising a light emitting material provided onto the alignment layer, this increased electrical conductivity can enhance the electroluminescence of the light emitting material. The compounds or materials according to the present invention having mesogenic or liquid crystalline properties can form oriented anisotropic films as described above, which are especially useful as alignment layers to induce or enhance alignment in a liquid crystal medium provided onto said anisotropic film. The materials according to the present invention may also be combined with photoisomerisable
compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913 A1.
According to another use the materials according to the present invention, especially their water-soluble derivatives (for example with polar or ionic side groups) or ionically doped forms, can be employed as chemical sensors or materials for detecting and discriminating DNA sequences. Such uses are described for example in L. Chen, D. W. McBranch, H. Wang, R. Helgeson, F. Wudl and D. G. Whitten, Proc. Natl. Acad. Sci. U.S.A., 1999, 96, 12287; D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A., 2002, 99, 49; N. DiCesare, M. R. Pinot, K. S. Schanze and J. R. Lakowicz, Langmuir, 2002, 18, 7785; D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev., 2000, 100, 2537. Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.
Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example
"comprising" and "comprises", mean "including but not limited to", and are not intended to (and do not) exclude other components.
It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention. Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).
Above and below, unless stated otherwise percentages are percent by weight and temperatures are given in degrees Celsius. The values of the dielectric constant ε ("permittivity") refer to values taken at 20°C and 1 ,000 Hz.
The invention will now be described in more detail by reference to the following examples, which are illustrative only and do not limit the scope of the invention.
Example 1
(3-Bromophenyl)-(2,2-dimethoxyethyl)sulfane
Figure imgf000069_0001
To a solution of 2-bromo-1,1-dimethoxy-ethane (49.2 g, 0.29 mol) and 3- bromo-benzenethiol (50.0 g, 0.26 mol) in dimethyl sulfoxide (400 cm3) is added a solution of potassium hydroxide (18.0 g, 0.32 mol) in water (40 cm3). The resulting solution is stirred at 23 °C for 17 hours. The reaction mixture is extracted with 40-60 petroleum (5 x 100 cm3) and the combined organic layer is washed with brine (2 x 100 cm3), dried over anhydrous magnesium sulphate and filtered. The filtrate is concentrated in vacuo to obtain (3-Bromophenyl)-(2,2-dimethoxyethyl)sulfane (65.0 g, 89%) as a colourless oil. MS (m/e): 278 (M+, 100%). 1H NMR (300 MHz, CDCI3) 7.52-7.50 (1H, m, ArH), 7.33-7.27 (2H, m, ArH), 7.15 (1H, dd, ArH, J 7.2, 7.2), 4.53 (1H, t, CH, J 5.6), 3.38 (6H, s, CH3), 3.12 (2H, d, CH2, J 5.6).
4-Bromobenzoiblthiophene and 6-bromobenzorblthiophene
Figure imgf000070_0001
To a mixture chlorobenzene (500 cm3) and polyphosphoric acid (150 cm3) is added (3-Bromophenyl)-(2,2-dimethoxyethyl)sulfane (60.0 g, 0.22 mol). The resulting reaction mixture is stirred at 130 °C for 1 hour. The reaction mixture is then cooled to 23 °C and concentrated in vacuo. The crude product is purified using silica gel column chromatography (n-heptane) to give 4-bromobenzo[b]thiophene (11.2 g, 14 %) as a white crystaline solid [MS (m/e): 214 (M+, 100%). 1H NMR (300 MHz, CDCI3) 7.81 (1H, d, ArH, J 8.0), 7.55-7.47 (3H, m, ArH), 7.20 (1 H, dd, ArH, J 7.9, 7.9)] and 6- bromobenzo[b]thiophene (11.0 g, 24%) as a white crystaline solid. MS (m/e): 214 (M+, 99.0%). 1H NMR (300 MHz, CDCI3) 8.00-8.03 (1H, m, ArH), 7.68 (1 H, d, ArH, J 8.5), 7.47 (1H, dd, ArH, J 1.8, 8.5), 7.42 (1H, d, ArH, J 5.5), 7.29 (1 H, dd, ArH, J 5.5, 0.7).
(6-bromobenzofb1thiophen-2-vl)trimethvlsilane
Figure imgf000070_0002
Lithium diisopropylamide (2.0 M in THF, 31.0 cm3, 62 mmol) is added dropwise to a solution of 6-bromo-benzo[b]thiophene (12.0 g, 56 mmol) in anhydrous tetrahydrofuran ( 50 cm3) under a nitrogen atmosphere at -30 °C over 30 minutes. The resulting solution is stirred at -20 °C for 2 hours and then quenched with chlorotrimethylsilane (6.7 g, 62 mmol). The ice bath is removed and the reaction mixture is warmed to 23 °C and stirred for 17 hours. The reaction mixture is diluted with water (75 cm3) and extracted with diethyl ether (5 x 50 cm3). The combined organic layer is washed with brine (50 cm3) and dried over anhydrous magnesium sulfate, filtered and the solvent removed in vacuo. The crude product is purified using silica gel column chromatography (40-60 petroleum) to give (6- bromobenzo[b]thiophen-2-yl)trimethylsilane (8.9 g, 55%). MS (m/e): 286 (M+, 96.5%). 1H NMR (300 MHz, CDCI3) 8.01 (1 H, s, ArH), 7.65 (1 H, d, ArH, J 8.4), 7.45-7.41 (1 H, dd, ArH, J 1.8, 8.4), 7.40 (1 H, s, ArH), 0.37 (9H, s, CH3).
Trimethyl(6-(4.4,5.5-tetramethyl-1.3,2-dioxaborolan-2-vnbenzo[blthiophen- 2-yl)silane
Figure imgf000071_0001
Nitrogen gas is bubbled through a suspension of (6-bromo- benzo[b]thiophen-2-yl)-trimethylsilane (2.0 g, 7.0 mmol),
bis(pinacolato)diboron (2.1 g, 8.4 mmol), [1 ,1 - bis(diphenylphosphino)ferrocene]dichloropalladium (II) (1.0 g, 1.3 mmol) and potassium acetate (4.1 g, 42 mmol) in anhydrous ,4-dioxane (50 cm3) for 1 hour. The reaction mixture is heated at 100 °C for 17 hours, allowed to cool to 23 °C, diluted with diethyl ether (300 cm3) and filtered. The filtrate is concentrated in vacuo and the crude product purified using silica gel column chromatography (40-60 petroleum) to give trimethyl(6- (4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)benzo[b]thiophen-2-yl)silane (2.1 g 87%) as a cream solid. MS (m/e): 332 (M+, 96.5%). 1H NMR (300 MHz, CDCI3) 8.36 (1 H, s, ArH), 7.80 (1 H, d, ArH, J 8.0), 7.73 (1 H, d, ArH, J 8.0), 7.46 (1 H, s, ArH), 1.37 (12H, s, CH3), 0.38 (9H, s, CH3). 2.5-Bis-(2-trimethylsilanyl-benzofb1thiophen-6-yl)-terephthalic acid diethyl ester
Figure imgf000072_0001
Nitrogen gas is bubbled through a solution of 2,5-dibromo-terephthalic acid diethyl ester (4.0 g, 1 1 mmol) and trimethyl(6-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)benzo[b]thiophen-2-yl)silane (7.7 g, 23 mmol) in anhydrous toluene (40 cm3) for 1 hour. Potassium carbonate (6.1 g, 44 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) are then added to the reaction mixture. After addition, the reaction mixture is stirred at 120 °C for 17 hours. The reaction mixture is concentrated in vacuo and purified using silica gel column chromatography (gradient of 40- 60 petroleum to diethyl ether) to give 2,5-bis-(2-trimethylsilanyl- benzo[b]thiophen-6-yl)-terephthalic acid diethyl ester (3.5 g 53%) as a white solid. 1H NMR (300 MHz, CDCI3) 8.05 (2H, s, ArH), 7.95 (2H, d, ArH, J 8.0), 7.49-7.44 (4H, m, ArH), 7.36 (1 H, s, ArH), 3.93 (4H, q, CH2, J 7.16), 0.72 (6H, t, CH3, J 7.1), 0.38 (18H, s, CH3).
2.20-Trimethylsilanyl-(6.12-dihvdro-6,6.12,12-tetrakis(4-dodecylphenyl)- 1.7-dithia-dicvclopenta[a,h1-indenof1 ,2-b]fluorene)
Figure imgf000072_0002
To a solution of 1-bromo-4-dodecyl-benzene (3.4 g, 10 mmol) in
anhydrous tetrahydrofuran (60 cm3) under a nitrogen atmosphere at -78 °C is added f-butyllithium (1.9 M in heptanes, 10.9 cm3, 21.0 mmol) dropwise over 30 minutes followed by stirring for one hour. A solution of 2,5-bis-(2-trimethylsilanyl-benzo[b]thiophen-6-yl)-terephthalic acid diethyl ester (1.6 g, 2.5 mmol) in anhydrous tetrahydrofuran (20 cm3) is added in one portion followed by stirring at 23 °C for 17 hours. The reaction mixture is then quenched with water (100 cm3), extracted with diethyl ether (3 x 75 cm3). The combined organic layer is washed with water (50 cm3), brine (50 cm3), dried over anhydrous magnesium sulphate and then filtered. The filtrate is concentrated in vacuo, triturated with methanol (50 cm3) and the solid collected by filtration to give crude [4-[bis-(4-dodecyl-phenyl)- hydroxy-methyl]-2,5-bis-(2-trimethylsilanyl-benzo[b]thiophen-6-yl)-phenyl]- bis-(4-dodecyl- phenyl)-methanol. To a degassed suspension of amberlyst 15 (2.0 g) and anhydrous toluene (50 cm3) at 23 °C is added the crude [4- [bis-(4-dodecyl-phenyl)-hydroxy-methyl]-2,5-bis-(2-trimethylsilanyl- benzo[b]thiophen-6-yl)-phenyl]-bis-(4-dodecyl-phenyl)-methanol. The resulting suspension is stirred at 23 °C for 17 hours under a nitrogen atmosphere. The resulting suspension is filtered and washed through with dichloromethane (100 cm3). The filtrate is concentrated in vacuo and the crude is purified using silica gel column chromatography (40-60 petroleum) to give 2,20-trimethylsilanyl-(6,12-dihydro-6,6,12,12-tetrakis(4- dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]-indeno[1 ,2-b]fluorene) (380 mg, 0%) as a pale cream solid. 1H N R (300 MHz, CDCI3) 7.82 (2H, s, ArH), 7.79 (2H, d, ArH, J 8.1), 7.72 (2H, d, ArH, J 8.1), 7.46 (2H, s, ArH), 7.21 (8H, d, ArH, J 8.3), 7.05 (8H, d, ArH, J 8.3), 2.57-2.52 (8H, m, CH2), 1.65-1.49 (8H, m, CH2), 1.38-1.15 (72H, m, CH2), 0.87 (12H, t, CH3, J 6.5), 0.30 (18H, s, CH3).
2.20-Dibromo-(6, 12-dihvdro-6.6, 12.12-tetrakis(4-dodecylphenylV 1 ,7-dithia- dicvclopentafa,h1-indenoH ,2-b]fluorene)
Figure imgf000073_0001
1-Bromo-pyrroIidine-2,5-dione (84.5 mg, 0.48 mmol) is added portion wise to a solution of 2,20-trimethylsilanyl-(6,12-dihydro-6,6,12,12-tetrakis(4- dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]-indeno[1 ,2-b]fluorene) (300 mg, 0.24 mmol) in anhydrous tetrahydrofuran (20 cm3) under a nitrogen atmosphere with absence of light at 0 °C. After addition, the reaction mixture is stirred at 23 °C for 17 hours. The reaction mixture is
concentrated in vacuo and the crude product is recrystallized from acetone:methyl ethyl ketone (20 cm3, 1:1) to give 2,20-dibromo-(6,12- dihydro-6,6, 12, 12-tetrakis(4-dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]- indeno[ ,2-b]fluorene) (200 mg, 66%) as a white crystalline solid. H NMR (300 MHz, CDCI3) 7.80 (2H, s, ArH), 7.71 (2H, d, ArH, J 8.2), 7.66 (2H, d, ArH, J 8.2), 7.32 (2H, s, ArH), 7.15 (8H, d, ArH, J 8.4), 7.06 (8H, d, ArH, J 8.4), 2.57-2.52 (8H, m, CH2), 1.61-1.50 (8H, m, CH2), 1.39-1.16 (72H, m, CH2), 0.87 (12H, t, CH3, J 6.6).
Polvi2.20-(6.12-dihvdro-6,6.12,12-tetrakis(4-dodecylphenyl)-1.7-dithia- dicvclopentafa.hl-indenoH ,2-b1fluorene)l-a/M2,2'bithiophenel (Polymer 1)
Figure imgf000074_0001
Nitrogen gas is bubbled through a mixture of 2,20-dibromo-(6,12-dihydro- 6,6, 2, 2-tetrakis(4-dodecylphenyl)- 1 ,7-dithia-dicyclopenta[a, h]- indeno[1 ,2-b]fluorene) (200 mg, 0.133 mmol) and 5,5'-bis- trimethylstannanyl-[2,2']bithiophenyl (65.5 mg, 0.133 mmol) in anhydrous toluene (2 cm3) and anhydrous Λ/,/V-dimethylformamide (0.5 cm3) for 1 hour. Tris(dibenzylideneacetone)dipalladium(0) (4.9 mg, 0.005 mmol) and tri-o-tolyl-phosphine (6.5 mg, 0.02 mmol) are added to the reaction mixture followed by heating at 120 °C for 65 hours. The reaction mixture is poured into methanol (100 cm3) and the polymer precipitate collected by filtration. The crude polymer is subjected to sequential Soxhiet extraction; methanol, acetone, 40-60 petroleum, 80-100 petroleum, cyclohexanes, chloroform and chlorobenzene. The chlorobenzene extract is poured into methanol (200 cm3) and the polymer precipitate collected by filtration to give poly[2,20-(6,12-dihydro-6,6,12l12-tetrakis(4-dodecylphenyl)-1 ,7-dithia- dicyclopenta[a,h]-indeno[1 ,2-b]fluorene)]-a/f-[2,2'bithiophene] (150 mg, 75%) as a dark red solid. GPC (chlorobenzene, 50 °C) Mn = 65,900 g/mol, Mw = 183,400 g/mol. GPC (1 ,2,4-trichlorobenzene, 140 °C) Mn = 62,600 g/mol, Mw = 128,700 g/mol.
ΡοΙνΓ2.20-(6.12-dihvdro-6,6.12.12-tetrakis(4-dodecylphenvn-1 ,7-dithia- dicvclopentara.h1-indeno[1 ,2-b1fluorene)1-atf-i2,7-(9.10-dioctyl- phenanthrene)! (Polymer 2)
Figure imgf000075_0001
Nitrogen gas is bubbled through a mixture of 2,7-di([1 ,3,2]dioxaborolane)- 9,10-dioctyl-phenanthrene (65.1 mg, 0.120 mmol), 2,20-dibromo-(6,12- dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]- indeno[ ,2-b]fluorene) (180 mg, 0.120 mmol) and potassium phosphate monohydrate (0.2 g, 1.1 mmol) in a mixture of toluene (3 cm3), 1,4-dioxane (3 cm3) and water (3 cm3) for 1 hour.
Tris(dibenzylideneacetone)dipalladium(0) (2.7 mg, 0.003 mmol) and tri-o- tolyl-phosphine (5.8 mg, 0.019 mmol) are added to the reaction mixture followed by heating at 100 °C for 3 hours. The reaction mixture is poured into methanol (100 cm3) and the polymer precipitate collected by filtration. The crude polymer is subjected to sequential Soxhiet extraction; methanol, acetone, 40-60 petroleum, 80-100 petroleum, cyclohexanes and
chloroform. The chloroform extract is poured into methanol (150 cm3) and the polymer precipitate collected by filtration to give poly[2,20-(6,12- dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-1 ,7-dithia-dicyclopenta[a,h]- indeno[1 ,2-b]fluorene)]-a/f-[2,7-(9,10-dioctyl-phenanthrene)] (170 mg 81%) as a black solid. GPC (1 ,2,4-trichlorobenzene, 140 °C) Mn = 15,200 g/mol, Mw = 26,100 g/mol. Example 2
Diethyl 2.5-di(benzoiblthiophen-4-yl)terephthalate
Figure imgf000076_0001
To a mixture of magnesium turnings (0.91 g, 36 mmol) and anhydrous tetrahydrofuran (20 cm3) is added 4-bromobenzo[b]thiophene (7.0 g, 33 mmol) and the mixture heated at 75 °C for 17 hours. The resulting suspension is syringed into a solution of tributyltinchloride (16 g, 49 mmol) in anhydrous tetrahydrofuran (20 cm3) at -78 °C. The ice bath is removed and the resulting mixture is stirred at 23 °C for 17 hours. The reaction mixture is quenched with water (100 cm3) and extracted with 40-60 petroleum (5 x 50 cm3). The combined organic phase is washed with brine (50 cm3), dried over magnesium sulphate, filtered and the solvent removed in vacuo to give crude (4-tributylstannanyl-benzo[b]thiophen-2-yl). Nitrogen gas is bubbled for an hour through a suspension of 2,5-dibromo- terephthalic acid diethyl ester (2.3 g, 6.0 mmol) in anhydrous N,N- dimethylformamide (50 cm3) and tris(dibenzylideneacetone)dipalladium(0) (0.3 g, 0.3 mmol) and tri(o-tolyl)phosphine (0.2 g, 0.6 mmol) are added. The resulting mixture is heated to 90 °C and the prepared (4- tributylstannanyl-benzo[b]thiophen-2-yl) is added. The reaction mixture is stirred at 90 °C for 17 hours. The reaction mixture is concentrated in vacuo and purified using silica gel column chromatography (gradient of 40-60 petroleum to diethyl ether) to give diethyl 2,5-di(benzo[b]thiophen-4- yl)terephthalate (0.9 g, 31 %) as a white solid. 1H NMR (300 MHz, CDCI3) 8.05 (2H, s, ArH), 7.95 (2H, d, ArH, J 8.0), 7.49-7.44 (4H, m, ArH), 7.37 (2H, d, ArH, J 5.5), 7.28 (2H, d, ArH, J 5.5), 3.92 (4H, q, CH2, J 7.2), 0.72 (6H, t, 2CH3, J 7.2). 6.12-dihvdro-6.6.12.12-tetrakis(4-dodecylphenyl)-3.9-dithia- dicvclopenta[c.†1-indenof1 ,2-b1fluorine
Figure imgf000077_0001
To a solution of 1-bromo-4-dodecyl-benzene (1.8 g, 5.5 mmol) in anhydrous tetrahydrofuran (100 cm3) under a nitrogen atmosphere at -78 °C is added f-butyllithium (1.7 M in heptane, 6.5 cm3, 1 mmol) dropwise over 30 minutes followed by stirring for 1 hour. 2,5-Bis-benzo[b]thiophen- 4-yl-terephthalic acid diethyl ester (0.54 g, 1.1 mmol) is added in one portion followed by stirring at 23 °C for 17 hours. The reaction mixture is then quenched with water (125 cm3) and extracted with diethyl ether (3 x 50 cm3). The combined organic layer is washed with water (50 cm3), brine (50 cm3), dried over anhydrous magnesium sulphate and then filtered. The filtrate is concentrated in vacuo, triturated with methanol (50 cm3) and the solid collected by filtration to give crude {2,5-bis-benzo[b]thiophen-6-yl-4- [hydroxy-bis-(4- dodecyl -phenyl)-methyl]-phenyl}-bis-(4-octyl-phenyl)- methanol. To a suspension of toluene-4-sulfonic acid (2.1 g, 12 mmol) in anhydrous dichloromethane (100 cm3) under a nitrogen atmosphere is added {2,5-bis-benzo[b]thiophen-6-yl-4-[hydroxy-bis-(4-dodecyl -phenyl)- methyl]-phenyl}-bis-(4-octyl-phenyl)-methanol in one portion. The resulting suspension is stirred at 23 °C for 17 hours under a nitrogen atmosphere. The reaction mixture is concentrated in vacuo and purified using silica gel chromatography (gradient of 40-60 petroleum to dichloromethane) to yield 6,12-dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-3,9-dithia- dicyclopenta[c,f]-indeno[1 ,2-b]fluorene (760 mg, 51 %) as a white solid. 1H NMR (300 MHz, CDCI3) 8.13 (2H, s, ArH), 7.90 (2H, d, ArH, J 5.5), 7.89 (2H, d, ArH, J 8.0), 7.62 (2H, d, ArH, J 5.5), 7.44 (2H, d, ArH, J 8.0), 7.25 (8H, d, ArH, J 8.3), 7.08 (8H, d, ArH, J 8.3), 2.59-2.53 (8H, m, CH2), 1.66- 1.55 (8H, m, CH2), 1.38-1.20 (72H, m, CH2), 0.89 (12H, t, CH3, J 7.5).
2.18-Dibromo-('6.12-dihvdro-6,6,12.12-tetrakis(4-dodecylphenvn-3.9-dithia- dicvclopentaic.f1-indenoM ,2-b1fluorene')
Figure imgf000078_0001
1-Bromo-pyrrolidine-2,5-dione (147 mg, 0.82 mmol) is added portion wise to a solution of 6,12-dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)-3,9- dithia-dicyclopenta[c,f]-indeno[1 ,2-b]fluorene (500 mg, 0.37 mmol) in chloroform (50 cm3) and acetic acid (20 cm3) under a nitrogen atmosphere with absence of light at 0 °C. After addition, the reaction mixture is stirred at 23 °C for 17 hours. The reaction mixture is concentrated in vacuo and the crude product crystallized from n-heptane and diethyl ether (40 cm3, 1 :1) to give 2,18-dibromo-(6,12-dihydro-6,6,12,12-tetrakis(4- dodecylphenyl)-3,9-dithia-dicyclopenta[c,f]-indeno[1 ,2-b]fluorene) (98 mg 18%) as a white crystalline solid.1H NMR (300 MHz, CDCI3) 8.03 (2H, s, ArH), 7.94 (2H, d, ArH, J 5.5), 7.65 (2H, d, ArH, J 5.5), 7.54 (2H, s, ArH), 7.20 (8H, d, ArH, J 8.3), 7.08 (8H, d, ArH, J 8.3), 2.57-2.52 (8H, m, CH2), 1.63-1.53 (8H, m, CH2), 1.32-1.16 (72H, m, CH2), 0.87 (12H, t, CH3, J 7.5). Polyr2.18-r(6.12-dihvdro-6.6.12.12-tetrakis(4-dodecylphenyl)-3.9-dithia- dicvclopentaic,f1-indenori ,2-blfluorene)n-a/ -[2,5-thienor3,2-b1thiophenel (Polymer 3)
Figure imgf000079_0001
Nitrogen gas is bubbled through a mixture of 2,18-dibromo-(6,12-dihydro- e.e.^.l -tetrakisi^dodecylpheny -S.Q-dithia-dicyclopentatcfl-indenofl ^- b]fluorene) (200.0 mg, 0.133 mmol), 5,5'-bis-trimethylstannanyl- [2,2']bithiophenyl (62.0 mg, 0.133 mmol),
tris(dibenzylideneacetone)dipalladium(0) (1.9 mg, 0.003 mmol), tri-o-tolyl- phosphine (3.2 mg, 0.01 mmol) and anhydrous toluene (6 cm3) for 1 hour. The reaction mixture is then heated in a pre-heated oil bath at 100 °C for 15 minutes. Bromobenzene (0.03 cm3) is added and the mixture heated at 100 °C for 10 minutes. Tributyl-phenyl-stannane (0.13 cm3) is then added and the mixture heated at 100 °C for 20 minutes. The mixture allowed to cool slightly and poured into stirred methanol (100 cm3) and the solid collected by filtration. The crude polymer is subjected to sequential Soxhiet extraction; acetone, 40-60 petrol, cyclohexane and chloroform. The chloroform extract is concentrated in vacuo and poured into methanol (300 cm3) and the solid collected by filtration to give poly[2,18-[(6,12-dihydro- 6,6,12,12-tetrakis(4-dodecylphenyl)-3,9-dithia-dicyclopenta[c,f]-indeno[1 ,2- b]fluorene)]]-a/f-[2,5-thieno[3,2-b]thiophene) (180 mg, 83%) as a dark red solid. GPC (chlorobenzene, 50 °C) Mn = 29,000 g/mol, Mw = 54,000 g/mol.
Example 3
Transistor Fabrication and Measurement
Top-gate thiri-film organic field-effect transistors (OFETs) were fabricated on glass substrates with photolithographically defined Au source-drain electrodes. A 7 mg/cm3 solution of the organic semiconductor in dichlorobenzene was spin-coated on top followed by a spin-coated fluoropolymer dielectric material (Lisicon® D139 from Merck, Germany). Finally a photolithographically defined Au gate electrode was deposited. The electrical characterization of the transistor devices was carried out in ambient air atmosphere using computer controlled Agilent 4155C
Semiconductor Parameter Analyser. Charge carrier mobility in the saturation regime (μ53 was calculated for the. Field-effect mobility was calculated in the saturation regime (Vd > (Vg-V0)) using equation (1):
WCi
M l (Vg - V0)
dV„
(1 )
where W is the channel width, L the channel length, Ci the capacitance of insulating layer, Vg the gate voltage, V0 the turn-on voltage, and μ53ί is the charge carrier mobility in the saturation regime. Turn-on voltage (Vo) was determined as the onset of source-drain current.
The mobility (μ53 for example polymer 1 in top-gate OFETs is 0.06 cm2/Vs.
Figure 1 shows the transfer characteristics and the charge carrier mobility of a top-gate OFET prepared as described above, wherein polymer 1 is used as the organic semiconductor.

Claims

Claims
1. A polymer comprising one or more units of formula I
Figure imgf000081_0001
0 wherein independently of each other denote C(R1R2),
C=C(R1R2), Si(R R2) or C=0,
Figure imgf000081_0002
wherein the thiophene ring may also be substituted in 3-position by a group R ,'
Figure imgf000081_0003
wherein the thiophene ring may also be substituted in 3-position by a group R1,
Figure imgf000081_0004
R1 and R2 independently of each other denote H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent CH2 groups are optionally replaced by -0-, -S-, -C(O)-, -C(S)-, -C(0)-0-, -O-C(O)-, -NR0-, -SiR°R00-, -CF2-, -CHR°=CR00-, -CY1=CY2- or - C≡C- in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, CI, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, preferably by halogen or by one or more of the aforementioned alkyl or cyclic alkyl groups,
Y1 and Y2 independently of each other denote H, F, CI or CN,
R° and R00 independently of each other denote H or optionally
substituted C- O carbyl or hydrocarbyl, and preferably denote H or alkyl with 1 to 12 C-atoms.
The polymer according to claim 1 , characterized in that in formula I X1 and X2 denote C(R R2) or C=(R R2).
3. The polymer according to claim 1 or 2, characterized in that the units of formula I are selected from the following formulae:
la
Figure imgf000082_0001
Figure imgf000083_0001
wherein R and R2 have the meanings given in claim 1.
4. The polymer according to one or more of claims 1 to 3, characterized in that it comprises one or more units of formula II
-[(ArV(U)b-(ArV(Ar3)d]- II wherein
U is a unit of formula I as defined in one or more of claims
1 to 3,
Ar1, Ar2, Ar3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups Rs, is on each occurrence identically or differently F, Br, CI, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(O)NR°R00, - C(0)X°, -C(0)R°, -NH2, -NR°R00, -SH, -SR°, -S03H, - S02R°, -OH, -NO2, -CF3, -SF5, optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
R° and R00 are independently of each other H or optionally
substituted Ci-40 carbyl or hydrocarbyl, is halogen, preferably F, CI or Br, are on each occurrence identically or differently 0, 1 or is on each occurrence identically or differently 0 or an integer from 1 to 10, wherein the polymer comprises at least one repeating unit of formula II wherein b is at least 1.
5. The polymer according to one or more of claims 1 to 4, characterized in that it additionally comprises one or more repeating units selected of formula II I
-[(ArV(Ac)b-(ArV(Ar3)d]- III wherein Ar1 , Ar2, Ar3, a, b, c and d are as defined in claim 4, and Ac is an aryl or heteroaryl group that is different from U and Ar1"3, has 5 to 30 ring atoms, is optionally substituted by one or more groups Rs as defined in claim 4, and is selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula III wherein b is at least 1.
The polymer according to one or more of claims 1 to 5, characterized in that it is selected of formula IV:
Figure imgf000084_0001
wherein is a unit of formula I as defined in one or more of claims 1 to 3, is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted, and is preferably selected of formula III as defined in claim 5, is > 0 and < 1 , is > 0 and < 1 , y is 1, and is an integer >1.
7. The polymer according to one or more of claims 1 to 6, characterized in that it is selected from the following formulae
Figure imgf000085_0001
(Ar1-U-Ai^)x-(Ar3-Ar3-Ar3)v]n-* IVc
Figure imgf000085_0002
*-([(Ar )a-(U)b-(Ar2)c-(Ar3)d]x-[(Ar1 )a-(Ac)b-(Ar2)c-(Ar3)d]y)n-*IVe wherein U, Ar1, Ar2, Ar3, a, b, c and d have in each occurrence identically or differently one of the meanings given in claim 6, Ac has on each occurrence identically or differently one of the meanings given in claim 5, and x, y and n are as defined in claim 6, wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units
Figure imgf000085_0003
and in at least one of the repeating units
[(Ar )a-(Ac)b-(Ar2)c-(Ar3)d] b is at least 1. The polymer according to one or more of claims 1 to 7, characterized in that it is selected of formula V
R5-chain-R6 V wherein "chain" is a polymer chain selected of formulae IV or IVa-IVe as defined in claim 6 or 7, R5 and R6 have independently of each other one of the meanings of R1 as defined in claim 1, or denote, independently of each other, H, F, Br, CI, I, -CH2CI, -CHO, - CR^CR^, -SiR'R'R"', -SiR'X'X", -SiR'R'X', -SnR'^'R", -BR'R", - B(OR')(OR"), -B(OH)2, -0-S02-R', -C≡CH, -C≡C-SiR'3) -ZnX', or an endcap group, wherein X' and X" denote halogen, R', R" and R'" have independently of each other one of the meanings of R° given in claim 1 , and two of R', R" and R'" may also form a ring together with the hetero atom to which they are attached.
The polymer according to one or more of claims 1 to 8, wherein one or more of Ar1, Ar2 and Ar3 denote aryl or heteroaryl selected from the group consisting of the following formulae
Figure imgf000086_0001
(D5) (D6) (D7) (D8) -86-
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000087_0003
Figure imgf000087_0004
Figure imgf000087_0005
-87-
Figure imgf000088_0001
Figure imgf000088_0002
Figure imgf000088_0003
Figure imgf000088_0004
Figure imgf000088_0005
-88-
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000089_0003
Figure imgf000089_0004
Figure imgf000089_0005
-89-
Figure imgf000090_0001
Figure imgf000090_0002
Figure imgf000090_0003
Figure imgf000090_0004
Figure imgf000090_0005
-90-
Figure imgf000091_0001
Figure imgf000091_0002
Figure imgf000091_0003
Figure imgf000091_0004
Figure imgf000091_0005
(D67)
Figure imgf000092_0001
wherein one of X11 and X12 is S and the other is Se, and R11, R12, R13, R14, R15, R16, R17 and R18 independently of each other denote H or have one of the meanings of R1 as defined in claim 1.
10. The polymer according to one or more of claims 1 to 9, wherein Ac and/or Ar3 denotes aryl or heteroaryl selected from the group consisting of the following formulae -92-
Figure imgf000093_0001
Figure imgf000093_0002
Figure imgf000093_0003
Figure imgf000093_0004
Figure imgf000093_0005
-93-
Figure imgf000094_0001
Figure imgf000094_0002
Figure imgf000094_0003
Figure imgf000094_0004
-94-
Figure imgf000095_0001
Figure imgf000095_0002
Figure imgf000095_0003
Figure imgf000095_0004
-95-
Figure imgf000096_0001
Figure imgf000096_0002
Figure imgf000096_0003
Figure imgf000096_0004
-96-
Figure imgf000097_0001
Figure imgf000097_0002
Figure imgf000097_0003
Figure imgf000097_0004
Figure imgf000097_0005
-97-
Figure imgf000098_0001
Figure imgf000098_0002
Figure imgf000098_0003
Figure imgf000099_0001
Figure imgf000099_0002
(A89) (A90) (A91) wherein one of X11 and X12 is S and the other is Se, and R11, R 2, R13, R14, R15 and R16 independently of each other denote H or have one of the meanings of R1 as defined in claim 1.
11. A mixture or polymer blend comprising one or more polymers
according to one or more of claims 1 to 10 and one or more compounds or polymers having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electrically
conducting, photoconducting or light emitting properties.
The mixture or polymer blend according to claim 11 , characterized in that it comprises one or more polymers according to one or more of claims 1 to 10 and one or more n-type organic semiconductor compounds.
13. The mixture or polymer blend according to claim 12, characterized in that the n-type organic semiconductor compound is a fullerene or substituted fullerene. A formulation comprising one or more polymers, mixtures or polymer blends according to one or more of claims 1 to 13, and one or more solvents, preferably selected from organic solvents. 15. Use of a polymer, mixture, polymer blend or formulation according to one or more of claims 1 to 14 as charge transport, semiconducting, electrically conducting, photoconducting or light emitting material in an optical, electrooptical, electronic, electroluminescent or
photoluminescent device, or in a component of such a device, or in an assembly comprising such a device or component.
A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer, formulation, mixture or polymer blend according to one or more of claims 1 to 15.
An optical, electrooptical, electronic, electroluminescent or
photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material, or comprises a polymer, mixture, polymer blend or formulation, according to one or more of claims 1 to 16.
A device, a component thereof, or an assembly comprising it, according to claim 17, wherein the device is selected from organic field effect transistors (OFET), thin film transistors (TFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, and
photoconductors, the component is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates, conducting patterns, and the assembly is selected from integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containg them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.
The device according to claim 18, which is an OFET, bulk
heterojunction (BHJ) OPV device or inverted BHJ OPV device.
A monomer of formula VI
Figure imgf000101_0001
wherein a and c are as defined in claim 4, U, Ar1 and Ar2 are as defined in claim 4 or 9, R7 and R8 are selected from the group consisting of CI, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, -SiMe2F, -SiMeF2l -O-SO2Z1, -B(OZ2)2 , -CZ3=C(Z3)2, -C≡CH, - C≡CSi(Z1)3, -ZnX° and -Sn(Z4)3, wherein X° is halogen, preferably CI, Br or I, Z1"4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z2 may also together form a cyclic group.
The monomer according to claim 20, which is selected from the following formulae
Figure imgf000101_0002
R7-U-R8 VI2
R7-Ar -U-R8 VI 3
R7-U-Ar2-R8 VI4 wherein U, Ar1, Ar2, R7 and R8 are as defined in claim 20.
22. A process of preparing a polymer according to one or more of claims 1 to 10, by coupling one or more monomers according to claim 20 or 21, wherein R7 and R8 are selected from CI, Br, I, -B(OZ2)2 and -
Sn(Z4)3, with each other and/or with one or more monomers selected from the following formulae
Figure imgf000102_0001
R7-Ar1-R' D
R7-Ar3-R( E wherein Ar1, Ar2, a and c are as defined in claim 20, Ar3 is as defined in claim 4, 9 or 10, Ac is as defined in claim 5 or 10, and R7 and R8 are selected from CI, Br, I, -B(OZ2)2 and -Sn(Z4)3, in an aryl-aryl coupling reaction.
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