WO2020161052A1 - Organic semiconducting polymers - Google Patents

Organic semiconducting polymers Download PDF

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WO2020161052A1
WO2020161052A1 PCT/EP2020/052571 EP2020052571W WO2020161052A1 WO 2020161052 A1 WO2020161052 A1 WO 2020161052A1 EP 2020052571 W EP2020052571 W EP 2020052571W WO 2020161052 A1 WO2020161052 A1 WO 2020161052A1
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PCT/EP2020/052571
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Changsheng Wang
William Mitchell
David Sparrowe
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Merck Patent Gmbh
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    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/122—Copolymers statistical
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
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    • C08G2261/143—Side-chains containing nitrogen
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    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/411—Suzuki reactions
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to novel photo-crosslinkable organic semiconducting (OSC) polymers, to methods for their preparation and educts or
  • OE organic electronic
  • OLED organic photovoltaic
  • PSC perovskite-based solar cell
  • OFET organic field effect transistors
  • OLED organic light emitting diodes
  • OSC Organic semiconducting materials
  • EPD electrophoretic display devices
  • OTFT organic thin film transistor
  • OLED organic liquid crystal display panels
  • Organic electronic devices in which OSCs are used as actives materials are, in general, multi-layered sandwich structures.
  • An OTFT device e.g., is composed of minimum four layers, namely, the source and drain electrodes layer, the OSC active layer, the gate insulator/dielectric layer and the gate electrode.
  • optimised devices have more layers such as surface modification and passivation layers.
  • For bulk heterojunction OPV and OPD devices although the donor and acceptor OSCs are mixed in the same layer, both electron and hole transporting layers are normally required in addition to the electrodes leading to multi layer stacks.
  • a state-of-the-art flexible OLED device however, consists of even more layer in the stack than the other devices mentioned above.
  • Multi-layered architectures of organic electronic devices are normally fabricated through a layer-by-layer deposition process.
  • Metal electrodes are in most of the cases deposited by vapour evaporation under high vacuum although printed electrodes, subjected to further improvement, may also be possible.
  • OSC layers, particularly polymeric, are mostly solution processed, which means that OSCs materials should be soluble in organic solvent to obtain uniformed solutions.
  • the solvent should ideally be nontoxic to humans and animals, noncorrosive to the manufacturing tools and benign to the environment.
  • the solvents for different functional layers need to be“orthogonal”, which means the solvent of the layer being deposited should not dissolve or ingress into the previous layer directly underneath it. Otherwise, the previous layer will be removed, or the interface between these two layers will be damaged, or the morphology of the previous layer will be altered. In whichever case, the device
  • an alternative solution is to crosslink the OSC molecules in the films through chemical bonds after deposition, so that the material of the OSC layer is insolubilised to the solvent being used for the next layer of deposition.
  • a photo-crosslinking process will enable fabrication of top-gate OTFTs with fewer restrictions on gate dielectric materials, reduce leakage, cross-talks and off-current.
  • a cross- linked active layer will minimise the migration of active molecules such as fullerenes, achieving additional thermal stability of morphology.
  • direct photo-patterning of photosensitive organic semiconducting polymers can be made possible.
  • US6107452 discloses a class of photo-crosslinkable conjugated and non- conjugated polymers where the photo active vinyl groups are the end capping terminal groups.
  • the photo active vinyl groups are the end capping terminal groups.
  • these concepts would be insufficient to render the semiconducting polymers insoluble to achieve micrometre sized patterns, particularly, when molecular weights are high.
  • W00210129A2 discloses photo-crosslinkable electroluminescent spirofluorene copolymers, using oxetane functional groups attached to the fluorene monomer units.
  • this type of unsymmetrical substitution lead to disorder and eventually poor packing of the polymer molecules, which is particularly unfavourable to OTFT applications, where packing of the OSC molecules is of crucial to achieve high charge mobilities.
  • This type of strategy was later proved to be harmful to OTFT performances by A. Charas, et al, ( Chem . Phys. Lett., 2008, 455, 189-191 ).
  • W02006043087A1 discloses a class of photo-crosslinkable polymers, where the photoreacting groups, preferably styrene groups, are attached through a spacer moiety to a nitrogen atom forming triarylamine polymers.
  • the general formula of the monomers is claimed as follows:
  • photoresists and enabling direct photo-patterning.
  • they should be easy to synthesize, especially by methods suitable for mass
  • polymers as disclosed and claimed hereinafter.
  • These polymers represent a novel class of photo-crosslinkable and photo-patternable semiconducting polymers comprising maleimide, for example 2,3-dimethylmaleimide (DMMI), as photoreactive groups, which can be directly crosslinked under UV radiation without the presence of photo-initiators or photo-crosslinkers.
  • maleimide for example 2,3-dimethylmaleimide (DMMI)
  • DMMI 2,3-dimethylmaleimide
  • polymers can be used as the active materials in organic electronic devices such as semiconducting layer in organic thin film transistors (OTFT), donor or acceptor component in organic photovoltaic cells (OPV) and organic photodetectors (OPD), and emissive or charge transporting layers in organic light emitting diodes (OLED).
  • OFT organic thin film transistors
  • OPD organic photovoltaic cells
  • OLED organic photodetectors
  • OLED organic light emitting diodes
  • the present application also provides synthetic methods to incorporate pendent maleimide or DMMI groups to conjugated polymer main chains. Summary
  • the invention relates to a conjugated polymer comprising one or more repeating units of formula I
  • Ar 1 , Ar 2 a group selected from the following formulae
  • Ar 3 , Ar 4 , Ar 5 fused aryl or heteroaryl ring which has from 5 to 20 ring
  • atoms is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
  • Ar 6 arylene or heteroarylene which has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L or R 1 ,
  • X° halogen preferably F or Cl, k 0 or an integer from 1 to 10, preferably 0, 1 , 2, 3, 4, 5, 6 or 7, very preferably 0, 1 , 2 or 3, most preferably 1
  • the conjugated polymer comprises a) at least one unit of formula I wherein at least two groups R 1 and R 2 that are attached to the same C, Si or Ge atom denote each -Sp-R c , or wherein at least one group R 1 that is attached to an N atom denotes -Sp- R c , or b) at least one unit Ar 6 which is substituted by at least one group R 1 that denotes -Sp-R c , or both a) and b).
  • the invention further relates to a polymer as described above and below wherein the groups R c are crosslinked.
  • the invention further relates to a pattern or patterned film comprising a polymer as described above and below wherein the groups R c are crosslinked.
  • the invention further relates to a monomer comprising a divalent unit of formula I or its subformulae which are at least monosubstituted by R c , optionally further comprising one or more additional arylene or
  • heteroarylene units and further comprising one or more reactive groups which can be reacted to form a polymer according to the present invention as described above and below.
  • the invention further relates to novel synthesis methods for preparing repeating units of formula I that are at least monosubstituted by R c and monomers and polymers comprising them, and novel intermediates used therein.
  • 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 acceptor or n-type semiconductor.
  • the invention further relates to the use of a polymer according to the present invention 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, and preferably further comprising one or more compounds having electron donor or electron acceptor properties.
  • the invention further relates to a composition, which may also be a polymer blend, comprising one or more polymers according to the present invention, and further comprising one or more additional compounds 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.
  • a composition which may also be a polymer blend, comprising one or more polymers according to the present invention, and further comprising one or more additional compounds 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 composition comprising an n-type semiconductor which is a polymer according to the present invention, and further comprising one or more p-type organic semiconductors, preferably selected from conjugated polymers.
  • the invention further relates to a composition comprising a p-type semiconductor which is a polymer according to the present invention, and further comprising an n-type semiconductor, which is preferably a fullerene or fullerene derivative, a non-fullerene acceptor small molecule, or an n- type conjugated polymer.
  • the invention further relates to a formulation comprising one or more polymers or a composition according to the present invention, and further comprising one or more solvents, preferably selected from organic solvents.
  • the invention further relates to an organic semiconducting formulation comprising one or more polymers according to the present invention, and further comprising one or more organic binders or precursors thereof, preferably having a permittivity e at 1 ,000 Hz and 20°C of 3.3 or less, and optionally one or more solvents preferably selected from organic solvents.
  • the invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which is prepared using a formulation according to the present invention.
  • the invention further relates to the use of a polymer or composition according to the present invention as semiconducting, charge transport, electrically conducting, photoconducting or light emitting material, or in an optical, electronic, optoelectronic, 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 semiconducting, charge transport, electrically conducting, photoconducting or light emitting material comprising a polymer or composition according to the present invention.
  • the invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a polymer, composition pattern or patterned film according to the present invention, or comprises a semiconducting, charge transport, electrically conducting, photoconducting or light emitting material according to the present invention.
  • photoluminescent deviced 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, dye-sensitized solar cells (DSSC), perovskite-based solar cells (PSC), laser diodes, Schottky diodes, photoconductors and
  • Preferred devices are OFETs, OTFTs, OPVs, PSCs, OPDs and OLEDs, in particular OTFTs, PSCs, OPDs and bulk heterojunction (BH J) OPVs or inverted BH J OPVs.
  • a polymer or composition according to the present invention as dye in a DSSC or a PSC.
  • a DSSC or PSC comprising a polymer or composition according to the present invention.
  • the component of the above devices includes, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
  • the assembly comprising such a device or component includes, 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
  • polymers, compositions and formulations of the present invention can be used as electrode materials in batteries and in
  • the invention further relates to a bulk heterojunction which comprises, or is being formed from, a composition comprising one or more polymers according to the present invention.
  • the invention further relates to a bulk heterojunction (BHJ) OPV or OPD device or inverted BHJ OPV or OPD device, comprising such a bulk heterojunction.
  • BHJ bulk heterojunction
  • Fig. 1 shows the transistor characteristics for a top gate bottom contact field effect transistor according to Use Example 1 .
  • Fig. 2 shows a microscopic image of a directly patterned polymer film according to Use Example 2.
  • indaceno-type group and “indaceno group” mean a group comprising two cyclopentadiene rings, or heterocyclic or vinylidene derivatives thereof, that are fused to a central aromatic or heteroaromatic aromatic ring Ar, and which can have cis- or trans configuration, as exemplarily shown below
  • U is e.g. C, Si or Ge and R is a carbyl or hydrocarbyl group.
  • adjacent rings Ar 1-5 are understood to be fused, i.e. having at least two atoms and one covalent bond in common.
  • the pi-electrons may also be delocalised into adjacent rings Ar 3 , Ar 4 or Ar 5 , so that for example a ring
  • 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 International Union of Pure and Applied Chemistry, Compendium of
  • the term "donor unit” will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron donating or electron pushing property towards a neighboured conjugated unit.
  • acceptor unit will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron accepting or electron withdrawing property towards a neighboured conjugated unit.
  • spacer unit will be understood to mean a unit which can be conjugated or non-conjugated and is located between a donor and an acceptor unit, and is preferably selected such that it does not have electron accepting property towards a neighboured donor unit.
  • spacer unit will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which is located between two donor units, or between two acceptor units, or between an acceptor unit and a donor unit, such that said donor and acceptor units are not connected directly with each other.
  • n-type or n-type semiconductor 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
  • conjugated will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp 2 - hybridization (or optionally also sp-hybridization), 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, or with defects included by design, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
  • polymer will be understood to mean a molecule of high relative molecular mass, the structure of which essentially comprises multiple repetitions 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, very preferably >10, 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”,“random polymer” 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, usually a single bond, 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.
  • a dashed line (— ) will be understood to mean a single bond.
  • 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.
  • 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 polymerization reaction, like for example a group having the meaning of R 31 or R 32 as defined below.
  • 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
  • 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 polymerization reaction. Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerization reaction. In situ addition of an endcapper can also be used to terminate the polymerization 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.
  • 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 Appl. Chem., 1994, 66, 1134).
  • 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, chlorobenzene 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
  • n M n /Mu, wherein M n 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.
  • the term "carbyl group” will be understood to mean any monovalent or multivalent organic moiety which comprises at least one carbon atom either without any non-carbon atoms (like for
  • example -CoC- or optionally combined with at least one non-carbon atom such as B, N, 0, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
  • non-carbon atom such as B, N, 0, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
  • 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 B, N, O, S,
  • 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 B, N, O, S, P, Si, Se, Sn, 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, and may include spiro-connected and/or fused rings.
  • Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has up to 40, preferably up to 25, very preferably up 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 1 to 40, preferably 6 to 40 C atoms, wherein each of these groups optionally contains one or more hetero atoms, preferably selected from B, N, 0, S, P, Si, Se, As, Te and Ge.
  • carbyl and hydrocarbyl group include for example: a C-i- C40 alkyl group, a C1-C40 fluoroalkyl group, a C1-C40 alkoxy or oxaalkyl group, a C 2 -C 40 alkenyl group, a C 2 -C 40 alkynyl group, a C3-C 40 allyl group, a C 4 -C 40 alkyldienyl group, a C 4 -C 40 polyenyl group, a C 2 -C 40 ketone group, a C 2 -C 40 ester group, a C6-C 18 aryl group, a C6-C 40 alkylaryl group, a C6-C 40 arylalkyl group, a C 4 -C 40 cycloalkyl group, a C 4 -C 40 cycloalkenyl group, and the like.
  • Preferred among the foregoing groups are a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group, a C3-C 20 allyl group, a C 4 -C 20 alkyldienyl group, a C 2 -C 20 ketone group, a C 2 -C 20 ester group, a C6-C 12 aryl group, and a C 4 -C 20 polyenyl group, respectively.
  • the carbyl or hydrocarbyl group may be an acyclic group or a cyclic group. Where the carbyl or hydrocarbyl group is an acyclic group, it may be straight-chain or branched. Where the carbyl or hydrocarbyl group is a cyclic group, it may be a non-aromatic carbocyclic or heterocyclic group, or an aryl or heteroaryl group.
  • a non-aromatic carbocyclic group as referred to above and below is saturated or unsaturated and preferably has 4 to 30 ring C atoms.
  • a non aromatic heterocyclic group as referred to above and below preferably has 4 to 30 ring C atoms, wherein one or more of the C ring atoms are each optionally replaced by a hetero atom, preferably selected from N, O, P, S, Si and Se, or by a -S(O)- or -S(0) 2 - group.
  • the non-aromatic carbo- and heterocyclic groups are mono- or polycyclic, may also contain fused rings, preferably contain 1 , 2, 3 or 4 fused or unfused rings, and are optionally substituted with one or more groups L.
  • R 00 each independently denote H or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12 C atoms that is optionally fluorinated.
  • L is selected from F or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl, fluoroalkoxy, alkylcarbonyl, alkoxycarbonyl, with 1 to 16 C atoms, or alkenyl or alkynyl with 2 to 16 C atoms.
  • Preferred non-aromatic carbocyclic or heterocyclic groups are
  • An aryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, is mono- or polycyclic and may also contain fused rings, preferably contains 1 , 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
  • a heteroaryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, wherein one or more of the ring C atoms are replaced by a hetero atom, preferably selected from N, O, S, Si and Se, is mono- or polycyclic and may also contain fused rings, preferably contains 1 , 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
  • An arylalkyl or heteroarylalkyl group as referred to above and below preferably denotes -(CH2) a -aryl or -(CH2) a -heteroaryl, wherein a is an integer from 1 to 6, preferably 1 , and "aryl" and “heteroaryl” have the meanings given above and below.
  • a preferred arylalkyl group is benzyl which is optionally substituted by L.
  • arylene will be understood to mean a divalent aryl group
  • heteroarylene will be understood to mean a divalent heteroaryl group, including all preferred meanings of aryl and heteroaryl as given above and below.
  • Preferred aryl and heteroaryl groups are phenyl in which, in addition, one or more CH groups may each 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 aryl and heteroaryl groups are selected from phenyl, pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole,
  • thiophene preferably 2-thiophene, selenophene, preferably 2- selenophene, 2,5-dithiophene-2',5'-diyl, 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-b]selenophene, 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, is
  • aryl and heteroaryl groups are those selected from the groups shown hereinafter.
  • An alkyl group or an alkoxy group i.e., where the terminal CFh group is replaced by -0-, can be straight-chain or branched. Particularly preferred straight-chains have 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms and accordingly denote preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl or hexadecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, dodecoxy or hexadecoxy, furthermore methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, tridecoxy or tetradecoxy, for example.
  • alkenyl groups are C2-C7-I E-alkenyl, C4-C7-3E- alkenyl, Cs-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-I E-alkenyl, C 4 -C 7 -3E-alkenyl and C 5 -C 7 -4-alkenyl.
  • Examples for particularly preferred alkenyl groups are vinyl, 1 E-propenyl, 1 E-butenyl,
  • An oxaalkyl group i.e., where one CH2 group is replaced by -0-, can be straight-chain.
  • these radicals are preferably neighboured. Accordingly, these radicals together form a carbonyloxy group -C(0)-0- 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, acetyloxym ethyl,
  • An alkyl group wherein two or more Chh groups are replaced by -0- and/or -C(0)0- 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-(methoxycarbon
  • a fluoroalkyl group can be perfluoroalkyl CjF2i +i , wherein i is an integer from 1 to 15, in particular CF3, C2F5, C3F7, C4F9, C5F11 , C6F13, C7F15 or C8F17, very preferably C6F13, or partially fluorinated alkyl, preferably with 1 to 15 C atoms, in particular 1 ,1-difluoroalkyl, all of the aforementioned being straight-chain or branched.
  • fluoroalkyl means a partially fluorinated (i.e. not
  • the substituents on an aryl or heteroaryl ring are independently of each other selected from primary, secondary or tertiary alkyl, alkoxy, oxaalkyl, thioalkyl, alkylcarbonyl or alkoxycarbonyl with 1 to 30 C atoms, wherein one or more H atoms are each optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated, alkoxylated, alkylthiolated or esterified and has 4 to 30, preferably 5 to 20, ring atoms.
  • Further preferred substituents are selected from the group consisting of the following formulae RSub 1 RSub
  • RSubi-3 each denote L as defined above and below and where at least, preferably all, of RSubi-3 is alkyl, alkoxy, oxaalkyl, thioalkyl, alkyl- carbonyl or alkoxycarbonyl with up to 24 C atoms, preferably up to 20 C atoms, that is optionally fluorinated, and wherein the dashed line denotes the link to the ring to which these groups are attached. Very preferred among these substituents are those wherein all RSubi-3 subgroups are identical.
  • an aryl(oxy) or heteroaryl(oxy) group is "alkylated or alkoxylated", this means that it is substituted with one or more alkyl or alkoxy groups having from 1 to 24 C-atoms and being straight-chain or branched and wherein one or more H atoms are each optionally
  • Y 1 and Y 2 are independently of each other H, F, Cl or CN.
  • halogen includes F, Cl, Br or I, preferably F, Cl or Br.
  • a halogen atom that represents a substituent on a ring or chain is preferably F or Cl, very preferably F.
  • a halogen atom that represents a reactive group in a monomer or an intermediate is preferably Br or I.
  • mirror image means a moiety that can be obtained from another moiety by flipping it vertically or horizontally across an external symmetry plane or a symmetry plane extending through the moiety.
  • the moiety
  • the polymers according to the present invention are easy to synthesize and exhibit advantageous properties. They show good processibility for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods.
  • the polymers according to the present invention comprise maleimide groups as photo-active pendent group and can thus be advantageously used as photo-crosslinkable semiconducting polymers. They do not require additives like photo-initiators or photo-crosslinkers which can generally induce side-reactions and form side-products which, as a result, become additional trapping states and hence impact negatively on the charge mobilities.
  • the maleimide groups in the polymers according to the present invention are introduced in a symmetrical pattern, which is of great benefit to the ordering of the polymer main chains and hence facilitates charge carrier mobilities in OTFT, OPV and OPD devices.
  • the semiconducting polymers can be directly patterned like a conventional negative photoresist.
  • the conjugated polymer comprises at least one unit of formula I wherein at least two groups R 1 and R 2 that are attached to the same C, Si or Ge atom denote each -Sp-R c , or wherein at least one group R 1 that is attached to an N atom denotes -Sp-R c , and optionally comprises at least one unit Ar 6 which is substituted by at least one group R 1 that denotes - Sp-R c .
  • the conjugated polymer comprises at least one unit of formula I wherein U 1 and U 2 denote CR 1 R 2 and at least two groups R 1 and R 2 that are attached to the same C atom denote each -Sp-R c .
  • Preferred groups Ar 1 and Ar 2 in formula I are on each occurrence identically or differently selected from the following formulae and their mirror images
  • Ar 1 and Ar 2 are selected from formulae A1 a and A2a.
  • Preferred units of formula I according to this first preferred embodiment are selected from the following subformula
  • Preferred units of formula 11 are those wherein U 1 denotes CR 1 R 2 .
  • the groups Ar 1 and Ar 2 can be selected such that the resulting indaceno-type groups have trans- or cis- configuration.
  • a second preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1 , 2 or 3, and the indaceno-type groups have an all-trans-configuration, i.e. one of the two groups Ar 1 and Ar 2 that are fused to the same group Ar 3 is of formula A1 and the other is of formula A2, as exemplarily illustrated below.
  • Preferred units of formula I2-I4 are those wherein all of the groups U 1 and U 2 denote CR 1 R 2
  • a third preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1 , 2 or 3, and at least one, preferably all, indaceno-type groups have cis-configuration, i.e. the groups Ar 1 and Ar 2 that are fused to the same group Ar 3 are both of formula A1 or both of formula A2, as exemplarily illustrated below.
  • This third preferred embodiment includes units of formula I having an "all- cis" configuration as exemplarily shown in formula I5 and I6 below, and units of formula I including both trans-configuration and cis-configuration, as exemplarily shown in formula I7 below.
  • Preferred units of formula I according to this third preferred embodiment are selected from the following subformulae wherein U 1 , U 2 , Ar 3 , Ar 4 and Ar 5 , independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
  • Preferred units of formula I5-I7 are those wherein all groups U 1 and U 2 denote CR 1 R 2 .
  • Q 1 and Q 2 are each independently from one another H, or CnHhn+i wherein n is an integer from 1 to 16, more preferably Chh, C2H5, C3H7 or C4H9, very preferably H or CH3, most preferably CH3.
  • Preferred groups R c in formula I are selected from formula M1
  • Very preferred spacer groups Sp are selected from alkylene with 1 to 20, preferably 5 to 20, more preferably 5 to 16 C atoms.
  • Preferred groups -Sp-R c in formula I are selected from formula SM
  • n is an integer from 1 to 20, preferably 5 to 20, very preferably 8 to 16, and Q 1 and Q 2 are each independently from one another H, CFh, C 2 H5, C3FI7 or C 4 H9, very preferably FI or CFI3, most preferably CFI3.
  • Preferred groups -Sp-R c in formula I are selected from formula SM1
  • n is an integer from 1 to 20, preferably 5 to 20, very preferably 8 to 16.
  • Preferred groups Ar 3 in formula I, I2-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
  • R 5 8 one of the meanings given for R 1 above and below.
  • Preferred groups Ar 3 are selected from formulae A3b, A3d, A3f and A3t, very preferably from formulae A3b and A3d.
  • Ar 3 are selected from formula A3d wherein R 5 and R 6 denote F.
  • A4v A4w A4x wherein W 1 , W 2 , W 3 and R 5-8 have the meanings given above, V 1 denotes CR 5 or N, and R 9 has one of the meanings given for R 5 .
  • Preferred groups Ar 4 are selected from formulae A4a, A4b, A4c, A4d, A4f, A4g, A4h, A4i, A4k, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v, very preferably from formula A4a, A4b, A4c, A4d, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v.
  • Ar 4 are selected from formulae A4r and A4s wherein R 5 and R 6 are different from H.
  • Preferred groups Ar 5 in formula I, 11 -17 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
  • Preferred groups Ar 5 are selected from formulae A5a, A5b, A5c, A5d, A5f, A5g, A5h, A5i, A5k, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v, very preferably from formula A5a, A5b, A5c, A5d, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v.
  • Further preferred groups Ar 5 are selected from formulae A5r and A5s wherein R 5 and R 6 are different from H.
  • Very preferred groups Ar 3 are selected from formulae A3b1 , A3d1 , A3f1 and A3t1 , very preferably from formulae A3b1 and A3d1 .
  • Ar 3 are selected from formula A3d1 wherein R 5 and R 6 denote F.
  • Ar 3 are selected from formulae A3e1 and A3f1 wherein R 5 and R 6 are different from H.
  • A4v1 A4w1 A4x1 wherein R 5-9 have the meanings given above and below.
  • Very preferred groups Ar 4 are selected from formulae A4a1 , A4b1 , A4c1 , A4d1 , A4f1 , A4g1 , A4h1 , A4i1 , A4k1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u and A4v1 , very preferably from formula A4a1 , A4b1 , A4c1 , A4d1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u1 and A4v1.
  • Further preferred groups Ar 4 are selected from formula A4r1 and A4s1 wherein R 5 and R 6 are different from H.
  • A5g1 A5h1 A5i1 A5v1 A5w1 A5x1 wherein R 5-9 have the meanings given above and below.
  • Very preferred groups Ar 5 are selected from formulae A5a1 , A5b1 , A5c1 , A5d1 , A5f1 , A5g1 , A5h1 , A5i1 , A5k1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u and A5v1 , very preferably from formula A5a1 , A5b1 , A5c1 , A5d1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u1 and A5v1.
  • Further preferred groups Ar 5 are selected from formula A5r1 and A5s1 wherein R 5 and R 6 are different from
  • Preferred units of formula I and 11-17 are selected from the group consisting of the following subformulae
  • R 1 , R 2 , R 5 and R 6 have the meanings given above and below
  • R 3 and R 4 have one of the meanings given for R 1 and R 2 above and below
  • the benzene and thiophene rings are optionally substituted in free positions by one or more groups R 5 , and wherein preferably in at least two groups R 1 and R 2 and/or at least two groups of R 3 and R 4 , which are attached to the same C atom, denote each -Sp-R c , and very preferably all groups R 1 , R 2 , R 3 and R 4 denote -Sp-R c .
  • R 1 and R 2 when being different from - Sp-R c , are selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1 -SUB6 above.
  • R 1 and R 2 when being different from -Sp-R c , are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4- position, 2,4-positions, 2,4,6-positions or 3,5-positions, or thiophene that is optionally substituted, preferably in 5-position, 4,5-positions or 3,5- positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, most preferably from formulae SUB7-SUB18 above.
  • R 1 and R 2 when being different from -Sp-R c , are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula
  • R 5-9 are H.
  • R 5-9 when being different from H, are each independently selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1 -SUB6 above.
  • R 5-9 when being different from FI, are each independently selected are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6-positions or 3,5- positions, or thiophene that is optionally substituted, preferably in 5- position, 4,5-positions or 3,5-positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, more preferably from formulae SUB7-SUB18 above, most preferably from formulae SUB14-SUB18 above.
  • Preferred aryl and heteroaryl groups R 1-9 when being different from H, are each independently selected from the following formulae
  • Very preferred aryl and heteroaryl groups R 1-9 when being different from H, are each independently selected from formulae S1 , S4, S5, S7 and S10.
  • aryl and heteroaryl groups R 1-9 are each independently selected from formulae SUB7-SUB16 as defined above.
  • R 1-9 denote a straight- chain, branched or cyclic alkyl group with 1 to 50, preferably 2 to 50, very preferably 2 to 30, more preferably 2 to 24, most preferably 2 to 16 C atoms, in which one or more CFh or CFh groups are replaced by a cationic or anionic group.
  • the cationic group is preferably selected from the group consisting of phosphonium, sulfonium, ammonium, uronium, thiouronium, guanidinium or heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.
  • Preferred cationic groups are selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N- dialkylpyrrolidinium, 1 ,3-dialkylimidazolium, wherein "alkyl” preferably denotes a straight-chain or branched alkyl group with 1 to 12 C atoms and very preferably is selected from formulae SUB1 -6 .
  • cationic groups are selected from the group consisting of the following formulae imidazolium 1H-pyrazohum 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium
  • R 1 ', R 2 ', R 3 ' and R 4 ' denote, independently of each other, H, a straight-chain or branched alkyl group with 1 to 12 C atoms or non
  • any one of the groups R 1 ', R 2 ', R 3 ' and R 4 ' can denote a link to the respective group R 1 10
  • two neighbored groups R 1 ', R 2 ', R 3 ' or R 4 ' can denote a link to the respective group R 1 .
  • the anionic group is preferably selected from the group consisting of borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, very preferably from phosphate, sulfonate or carboxylate.
  • Si or Ge atom denote each -Sp-R c
  • at least one group R 1 in the same unit that is attached to an N atom denotes -Sp-R c ,
  • k is 0, 1 , 2 or 3, preferably 0, 1 or 2, very preferably 1 ,
  • U 1 and U 2 denote independently of each other CR 1 R 2 ,
  • W 1 , W 2 and W 3 are S or Se, preferably S,
  • W 4 is S or NR°, preferably S,
  • V 1 is CR 5 ,
  • V 1 is N
  • Ar 1 and Ar 2 are selected from formulae A1 a and A2a,
  • Ar 3 is selected from formulae A3b, A3d, A3f and A3t, very preferably from formulae A3b and A3d,
  • Ar 3 is selected from formulae A3b1 , A3d1 , A3f1 and A3t1 , very preferably from formulae A3b1 and A3d1 ,
  • Ar 3 at least one, preferably one or two of R 5-8 are different from H,
  • Ar 3 is selected from formula A3d1 wherein R 3 and R 4 denote F,
  • Ar 3 is selected from formulae A3e1 and A3f1 wherein R 5 and R 6 are different from H,
  • Ar 4 is selected from formulae A4a, A4b, A4c, A4d, A4f, A4g, A4h, A4i, A4k, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v, very preferably from formula A4a, A4b, A4c, A4d, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v,
  • Ar 4 is selected from formulae A4a1 , A4b1 , A4c1 , A4d1 , A4f1 , A4g1 , A4h1 , A4i1 , A4k1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u and A4v1 , very preferably from formula A4a1 , A4b1 , A4c1 , A4d1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u1 and A4v1 ,
  • Ar 5 is selected from formulae A5a, A5b, A5c, A5d, A5f, A5g, A5h, A5i, A5k, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v, very preferably from formula A5a, A5b, A5c, A5d, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v,
  • Ar 5 is selected from formulae A5a1 , A5b1 , A5c1 , A5d1 , A5f1 , A5g1 , A5h1 , A5i1 , A5k1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u and A5v1 , very preferably from formula A5a1 , A5b1 , A5c1 , A5d1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u1 and A5v1 ,
  • R 1 and R 2 are different from H
  • R 1 and R 2 when being different from H and -Sp-R c , are each independently selected from F, Cl or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted by one or more F atoms, or alkyl or alkoxy having 1 to 12 C atoms that is optionally fluorinated, more preferably from formulae SUB1 -SUB6 above,
  • R 1 and R 2 when being different from FI and -Sp-R c , are each independently selected from phenyl that is substituted, preferably in 4- position, or in 2,4-positions, or in 2,4,6-positions or in 3,5-positions, with alkyl or alkoxy having 1 to 20 C atoms, preferably 1 to 16 C atoms, very preferably 4-alkylphenyl wherein alkyl is C1 -16 alkyl, most preferably 4-methylphenyl, 4-hexylphenyl, 4-octylphenyl or 4- dodecylphenyl, or 4-alkoxyphenyl wherein alkoxy is C1 -16 alkoxy, most preferably 4-hexyloxyphenyl, 4-octyloxyphenyl or 4-dodecyloxyphenyl or 2,4-dialkylphenyl wherein alkyl is C1 -16 alkyl, most preferably 2,4- dihexylphenyl or 2,4-dial
  • R 5 9 are H
  • R 5-9 denotes -Sp-R c ,
  • At least one of R 5-9 is different from H
  • R 5-9 when being different from H and -Sp-R c , are each independently selected from F, Cl, CN or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and
  • alkylcarbonyloxy each having up to 20 C atoms and being
  • F atoms unsubstituted or substituted by one or more F atoms, preferably from F, or alkyl or alkoxy having up to 16 C atoms that is optionally fluorinated, more preferably from formulae SUB1 -SUB6 above,
  • R 5-9 when being different from FI and -Sp-R c , are each independently selected from aryl or heteroaryl, preferably phenyl or thiophene, each of which is optionally substituted with one or more groups L as defined in formula IA and has 4 to 30 ring atoms, preferably from phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6- positions or 3,5-positions, with alkyl or alkoxy having 1 to 20 C atoms, preferably 1 to 16 C atoms, more preferably from formulae SUB7- SUB18 above,
  • Ar 6 is selected from thiophene, thiazole, thieno[3,2-b]thiophene, thiazolo[5,4-d]thiazole, benzene, 2,1 ,3-benzothiadiazole, 1 ,2,3- benzothiadiazole, thieno[3,4-b]thiophene, benzotriazole andr thiadiazole[3,4-c]pyridine, which are optionally substituted by L or R 1 or -Sp-R c ,
  • - L denotes F, Cl, CN, NO2, or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated.
  • Another embodiment of the invention relates to a polymer comprising one or more repeating units of formula I, 11 -17 or 11-1 to 15-13 and optionally one or more units Ar 6 , wherein at least one of the units of formula and the units Ar 6 is at least monosubstituted by -Sp-R c .
  • At least one group R 1 in the unit that is attached to an N atom denotes -Sp-R c ,
  • At least one unit Ar 6 is at least monosubstituted, preferably mono- or disubstituted, by -Sp-R c ,
  • Ar 6 are at least monosubstituted, preferably mono- or
  • the units Ar 6 are not substituted by -Sp-R c .
  • the polymer comprises one or more units Ar 6 , which preferably have electron donor properties, and are selected from the group consisting of the formulae D1 -D151 and their mirror images
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other have one of the meanings of R 1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of the substituents R 1 1 - 18 denotes Sp-R c .
  • Preferred units are selected from formulae D1 , D7, D10, D1 1 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D1 1 1 , D139, D140, D141 , D146 or D150 wherein preferably at least one of R 11 18 is different from H, and preferably at least one of R 1 1 - 18 denotes Sp-R c .
  • the polymer comprises one or more units Ar 6 , which preferably have electron acceptor properties, and are selected from the group consisting of the formulae A1 -A103 and their mirror images
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 independently of each other have one of the meanings of R 1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of the substituents R 1 1 - 18 denotes Sp-R c .
  • Preferred units are selected from formulae A1 , A6, A7, A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103 wherein preferably at least one of R 1 1 - 14 is different from H, and preferably at least one of R 1 1 - 18 denotes Sp-R c .
  • the polymer comprises one or more units Ar 6 which are selected from the group consisting of the formulae Sp1 -Sp18 and their mirror images
  • R 11 , R 12 , R 13 , R 14 independently of each other have one of the meanings of R 1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of R 1 1 - 14 denotes Sp-
  • R 11 and R 12 are H.
  • R 1 1 - 14 are H or F.
  • Very preferred are units selected from formulae Sp1 , Sp2, Sp6, Sp10,
  • polymers comprising, preferably consisting of, one or more, preferably two or more, units of formula I, 11 -17 or or 11 -1 to 15-13, and one or more units Ar 6 selected from the following groups
  • A2) the group consisting of the formulae D1 -D151 , very preferably from the formulae D1 , D7, D10, D11 , D19, D22, D29, D30, D35, D36,
  • the polymer comprises one or more of the units of formula I, 11-17 or or 11 -1 to 15-13 which are at least monosubstituted by - Sp-R c .
  • the polymer comprises one or more of the units Ar 6 which are at least monosubstituted by -Sp-R c .
  • the polymer comprises, very preferably consists of, one or more units selected from the following groups
  • Preferred polymers comprise one or more units of group 1 D and one or more units of group 2A. Further preferred polymers comprise one or more units of group 1 A and one or more units of group 2D. Further preferred polymers comprise one or more units of group 1 D and one or more units of group 2D, and optionally one or more units selected from group 3.
  • Further preferred polymers comprise one or more units of group 1A and one or more units of group 2A, and optionally one or more units selected from group 3.
  • the polymer comprises one or more units selected from groups 1 D and 2D, one or more units selected from groups 1 A and 2A, and one or more units selected from the group 3.
  • the polymer comprises, preferably consists of, one or more, preferably two or more, repeating units of formula 111 and/or M2, and optionally one or more repeating units of formula M3:
  • polymer contains at least one unit of formula 111 , M2 or M3 wherein at least one of U and C 1 4 is at least monosubstituted by -Sp-R c .
  • C 1 , C 2 , C 3 and C 4 are selected from groups 2A, 2D and 3 as defined above and below.
  • the polymer is selected of formula III: wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
  • B, C, D, E a unit of formula 111 , M2 or M3, x > 0 and ⁇ 1 , v, w, y, z > 0 and ⁇ 1 , v+w+x+y+z 1 , and n an integer >1 , preferably >5, and wherein at least one of A-E is at least monosubstituted by -Sp-R c .
  • the polymer comprises, very preferably consists of, one or more units selected from the group consisting of the following formulae and their mirror images
  • Preferred polymers are selected from formulae Pi-Px
  • the donor units D and 2D are selected from the group consisting of the formulae D1-D151 , very preferably of the formulae D1 , D7, D10, D11 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87,
  • the acceptor units A and 2A are selected from the group consisting of the formulae A1 -A103, very preferably of the formulae A1 , A6, A7,
  • the spacer units Sp are selected from the group consisting of the
  • Very preferred polymers are selected from the following subformulae
  • R c is preferably selected of formula M, very preferably of formula M1
  • Sp- R c is preferably selected of formula SM, very preferably of formula SM1.
  • polymer is selected of formula IV
  • R E1 -chain-R E2 IV wherein“chain” denotes a polymer chain selected from formulae III, Pi-Px, or P1 -P13, and R E1 and R E2 have independently of each other one of the meanings of L as defined above, or denote, independently of each other,
  • Preferred endcap groups R E1 and R E2 are H, C1-20 alkyl, or optionally substituted C6-12 aryl or C2-10 heteroaryl, very preferably H or phenyl.
  • indices v, w, x, y and z denote the mole fraction of the corresponding repeating units, such as units A-E in formula III, and n denotes the degree of polymerisation or total number of repeating units.
  • x, v, w, y and z are each preferably from 0.1 to 0.6, very preferably from 0.2 to 0.4.
  • the total number of repeating units n is preferably from 2 to 10,000, very preferably from 5 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
  • 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.
  • the invention further relates to monomers of formula V1 or V2
  • U, C 1 4 , a, b, c and d have the meanings of formula 111 , or one of the preferred meanings as described above and below
  • R R1 and R R2 are selected from Br, -B(OZ 2 )2 and Sn(Z 4 )3.
  • R R1 and R R2 have the meanings given above and below, and preferably denote Br, B(OZ 2 )2 or Sn(Z 4 )3, and U * is a unit selected from formulae P1 -P8 or PN1 -PN6 wherein n is 1 .
  • monomers and polymers of formulae I, 11 -17, 11 -1 to 15-13, 111 , M2, M3, III, Pi-Px, P1 -P13, IV, V1 -V3, V1 a-d and 11 -1 to 15-13 are selected from the following embodiments, including any combination thereof:
  • - n is from 5 to 1 ,000, most preferably from 10 to 2,000,
  • c and d are independently of each other 0, 1 or 2, preferably 0 or 1 , very preferably 0,
  • - a is 2, b is 1 or 2, c is 0 or 1 , preferably 0, and d is 0, 1 or 2, preferably 0 or 1 , very preferably 0,
  • R 1 1 - 18 is different from H and is selected from alkyl
  • alkoxy or thiaalkyl all of which are straight-chain or branched, have 1 to 25, preferably 1 to 18 C atoms, and are optionally fluorinated,
  • R 11 - 18 is different from H and is selected from the group consisting of aryl, heteroaryl, aryloxy, heteroaryloxy, arylalkyl and heteroarylalkyl, each of which has 4 to 20 ring atoms and optionally contains fused rings and is unsubstituted or substituted by one or more groups L as defined in formula I,
  • R E1 and R E2 are selected from H, C1 -20 alkyl, or optionally substituted Ce- 12 aryl or El-10 heteroaryl, very preferably H or phenyl,
  • R R1 and R R2 denote Br, B(OZ 2 )2 or Sn(Z 4 )3, wherein Z 2 and Z 4 are as defined in formula V1.
  • the polymers according to 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 of the present invention can be prepared from the
  • monomers which are preferably selected from formula V1 - V3 or V1 a-d, for example by copolymerising one or more monomers of formula V1 -V3 or V1 a-d with each other or with one or monomers of the following formulae in an aryl-aryl coupling reaction
  • the polymers can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, C-H activation coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling, Stille 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.
  • the polymers are prepared from monomers selected from
  • Another aspect of the invention is a process for preparing an polymer by coupling one or more identical or different monomers selected from
  • Preferred aryl-aryl coupling methods used in the synthesis methods as described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling,
  • 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 et al., Prog. Polym. Sci., 1993,
  • educts having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used.
  • Stille coupling educts having two reactive stannane groups or two reactive halide groups are preferably used.
  • Negishi coupling educts having two reactive organozinc groups or two reactive halide groups are preferably used.
  • 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(Ph3P)4.
  • Another preferred phosphine ligand is tris(o/f/?o-tolyl)phosphine, i.e. Pd(o-Tol3P)4.
  • 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(dibenzylideneacetone)dipalladium(0),
  • phosphine ligand for example triphenylphosphine, tris(o/f/?o- 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(0).
  • leaving groups of formula -O-SO2Z 0 can be used wherein Z° is an alkyl or aryl group, preferably C-MO alkyl or Ce-12 aryl. Particular examples of such leaving groups are tosylate, mesylate and triflate.
  • synthesis schemes shown hereinafter are illustrated in the synthesis schemes shown hereinafter.
  • T 11 and T 12 are terminal groups such as H, F, Cl, Br, I, B(OR) 2 , SnR 3 , ZnX, MgX, and Ar 3 5 , Sp and R c have the meanings as given above and below, Sp is for example (CH2) n with n being an integer from 1 to 20, and R c is for example 2,3-dimethyl-N- maleimide.
  • Novel methods of preparing repeating units of formula I and monomers and polymers comprising them as described above and below are another aspect of the invention.
  • the polymer according to the present invention can also be used in compositions, for example together with monomeric or polymeric compounds having charge-transport, semiconducting, electrically conducting, photoconducting and/or light emitting semiconducting properties, or for example with compounds having hole blocking or electron blocking properties for use as interlayers or charge blocking layers in PSCs or OLEDs.
  • compositions comprising one or more polymers according to the present invention and one or more small molecule compounds and/or polymers having one or more of a charge-transport, semiconducting, electrically conducting,
  • the invention further relates to a composition comprising one or more polymers according to the present invention, and further comprising one or more p-type organic semiconductors, preferably selected from conjugated polymers.
  • the invention further relates to a composition
  • a composition comprising a first n-type semiconductor which is a polymer according to the present invention, a second n-type semiconductor, which is preferably a fullerene or fullerene derivative, a non-fullerene acceptor small molecule, or an n-type
  • conjugated polymer and a p-type semiconductor, which is preferably a conjugated polymer.
  • the second n-type OSC compound is a non- fullerene acceptor (NFA) small molecule having an A-D-A structure as described above with an electron donating polycyclic core and two terminal electron withdrawing groups attached thereto.
  • NFA non- fullerene acceptor
  • Suitable and preferred NFA small molecules for use as second n-type OSC in this preferred embodiment are for example those disclosed in Y.
  • the second n-type OSC compound is a fullerene or substituted fullerene.
  • the fullerene is for example an indene-C 6 o-fullerene bisadduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C 6 o fullerene, also known as "PCBM-C60" or "C60PCBM", as disclosed for example in G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Science 1995, Vol. 270, p. 1789 ff and having the structure shown below, or structural analogous compounds with e.g. a C 61 fullerene group, a C 70 fullerene group, or a C 71 fullerene group, or an organic polymer (see for example Coakley, K. M. and McGehee
  • the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene of formula Full-I to form the active layer in an OPV or OPD device,
  • an n-type semiconductor such as a fullerene or substituted fullerene of formula Full-I
  • Cn denotes a fullerene composed of n carbon atoms
  • Adduct 1 is a primary adduct appended to the fullerene C n with any connectivity
  • Adduct 2 is a secondary adduct, or a combination of secondary adducts, appended to the fullerene C n with any connectivity, k is an integer > 1 , and
  • I is 0, an integer > 1 , or a non-integer > 0.
  • k preferably denotes 1 , 2, 3 or, 4, very preferably 1 or 2.
  • the fullerene C n in formula Full-I and its subformulae may be composed of any number n of carbon atoms
  • the number of carbon atoms n of which the fullerene C n is composed is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70.
  • the fullerene C n in formula Full-I and its subformulae is preferably selected from carbon based fullerenes, endohedral fullerenes, or mixtures thereof, very preferably from carbon based fullerenes.
  • Suitable and preferred carbon based fullerenes include, without limitation, (C 6 o-i h )[5,6]fullerene, (C 7 o- D5h )[5,6]fullerene, (C 76-D2* )[5,6]fullerene, (Cs4-
  • the endohedral fullerenes are preferably metallofullerenes.
  • Suitable and preferred metallofullerenes include, without limitation, l_a@C6o, l_a@C82, Y@Cs2, SC 3 N@C 8O , Y3N@C8O, SC3C2@C8O or a mixture of two or more of the aforementioned metallofullerenes.
  • the fullerene C n is substituted at a [6,6] and/or [5,6] bond, preferably substituted on at least one [6,6] bond.
  • Adductl Primary and secondary adducts, named "Adductl” and 'Adduct 2" in formula Full-I and its subformulae, are each preferably selected from the following formulae wherein
  • Ar s1 , Ar S2 denote, independently of each other, an aryl or heteroaryl group with 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic, and which is optionally substituted by one or more identical or different substituents having one of the meanings of L as defined above and below, Rs i R S2 R S3 R S4 anc
  • Preferred compounds of formula Full-I are selected from the following subformulae: Full-la
  • R S1 , R S2 , R S3 , R S4 R S5 and R S6 independently of each other denote H or have one of the meanings of R s as defined above and below.
  • the fullerene is PCBM-C60, PCBM-C70, bis-PCBM-C60, bis-PCBM-C70, ICMA-c60 (1 4'-dihydro-naphtho[2', 3': 1 ,2][5,6]fullerene- C60), ICBA, 0QDM-C6O (1 ',4'-dihydro-naphtho[2',3': 1 ,9][5,6]fullerene-C60- Ih), or bis-oQDM-C60.
  • the second n-type OSC compound is a small molecule which does not contain a fullerene moiety, and which is selected from naphthalene or perylene carboximide derivatives.
  • naphthalene or perylene carboximide derivatives for use as n-type OSC compounds are described for example in Adv. Sci. 2016, 3, 16001 17, Adv. Mater. 2016, 28, 8546-8551 , J. Am. Chem. Soc., 2016, 138, 7248- 7251 and J. Mater. Chem. A, 2016, 4, 17604.
  • Z 1 an electron withdrawing group, preferably having one of the preferred meanings as given above for formula T, very preferably CN, Y 1 , Y 2 H, F, Cl or CN,
  • G C, Si, Ge, C C or a four-valent aryl or heteroaryl group that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups R 1 or L,
  • the second n-type OSC compound is a conjugated OSC polymer.
  • Preferred n-type OSC polymers are described, for example, in Acc. Chem. Res., 2016, 49 (1 1 ), pp 2424-2434 and WO 2013/142841 A1 .
  • Preferred n-type conjugated OSC polymers for use as second n-type OSC compound in this preferred embodiment comprise one or more units derived from perylene or naphthalene are poly[[N,N'-bis(2- octyldodecyl)naphthalene-1 ,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'- bithiophene)], poly[[N,N'-bis(2-hexyldecyl)naphthalene-1 ,4,5,8- bis(dicarboximide)-2,6-diyl]-alt-5,5'-thiophene].
  • composition according to the present invention can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the compounds and/or 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 polymers according to the present invention or compositions 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. Further suitable and preferred solvents used include 1 ,2,4-trimethylbenzene,
  • solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1 -methylnaphthalene, 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, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1 ,5-dimethyltetraline,
  • propiophenone acetophenone, tetralin, 2-methylthiophene, 3- methylthiophene, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene, 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 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,
  • 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.
  • compositions 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, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.
  • 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, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.
  • the ratio 1 st polymer: 2 nd polymer is preferably from 5:1 to 1 :5 by weight, more preferably from 3:1 to 1 :3 by weight, most preferably 2:1 to 1 :2 by weight.
  • composition according to the present invention may also comprise a polymeric binder, preferably from 0.001 to 95% by weight.
  • binder include polystyrene (PS), polydimethylsilane (PDMS),
  • polypropylene PP
  • polymethylmethacrylate PMMA
  • a binder to be used in the formulation as described before which is preferably a polymer, may comprise either an insulating binder or a semiconducting binder, or mixtures thereof, may be referred to herein as the organic binder, the polymeric binder or simply the binder.
  • the polymeric binder comprises a weight average molecular weight in the range of 1 ,000 to 5,000,000 g/mol, especially 1 ,500 to 1 ,000,000 g/mol and more preferable 2,000 to 500,000 g/mol.
  • a weight average molecular weight in the range of 1 ,000 to 5,000,000 g/mol, especially 1 ,500 to 1 ,000,000 g/mol and more preferable 2,000 to 500,000 g/mol.
  • the polymer can have a polydispersity index M w /M n in the range of 1.0 to 10.0, more preferably in the range of 1.1 to 5.0 and most preferably in the range of 1.2 to 3.
  • the inert binder is a polymer having a glass transition temperature in the range of -70 to 160°C, preferably 0 to 150°C, more preferably 50 to 140°C and most preferably 70 to 130°C.
  • the glass transition temperature can be determined by measuring the DSC of the polymer (DIN EN ISO 11357, heating rate 10°C per minute).
  • the weight ratio of the polymeric binder to the OSC polymer according to the present invention is preferably in the range of 30:1 to 1 :30, particularly in the range of 5:1 to 1 :20 and more preferably in the range of 1 :2 to 1 : 10.
  • the binder preferably comprises repeating units derived from styrene monomers and/or olefin monomers.
  • Preferred polymeric binders can comprise at least 80 %, preferably 90 % and more preferably 99 % by weight of repeating units derived from styrene monomers and/or olefins.
  • Styrene monomers are well known in the art. These monomers include styrene, substituted styrenes with an alkyl substituent in the side chain, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • Olefin monomers consist of hydrogen and carbon atoms.
  • monomers include ethylene, propylene, butylenes, isoprene and 1 ,3- butadiene.
  • the polymeric binder is polystyrene having a weight average molecular weight in the range of 50,000 to 2,000,000 g/mol, preferably 100,000 to 750,000 g/mol, more preferably in the range of 150,000 to 600,000 g/mol and most preferably in the range of 200,000 to 500,000 g/mol.
  • Suitable binders are disclosed for example in US 2007/0102696 A1. Especially suitable and preferred binders are described in the following.
  • the binder should preferably be capable of forming a film, more preferably a flexible film.
  • Suitable polymers as binders include poly(1 ,3-butadiene), polyphenylene, polystyrene, poly(a-methylstyrene), poly(a-vinylnaphtalene),
  • polyisobutylene poly(vinyl cyclohexane), poly(vinylcinnamate), poly(4- vinylbiphenyl), 1 ,4-polyisoprene, polynorbornene, poly(styrene-block- butadiene); 31 % wt styrene, poly(styrene-block-butadiene-block-styrene); 30% wt styrene, poly(styrene-co-maleic anhydride) (and
  • ethylene/butylene 1 - 1.7% maleic anhydride
  • poly(styrene- block- ethylene/butylene-block-styrene) triblock polymer 13% styrene
  • poly(ethylene-co-octene) 1 :1 poly(ethylene-co-propylene-co-5-methylene-
  • 2-norbornene 50% ethylene, poly(ethylene-co-tetrafluoroethylene) 1 :1 , poly(isobutyl methacrylate), poly(isobutylene), poly(methyl methacrylate)- co-(fluorescein O-methacrylate) 80% methyl methacrylate, poly(methyl methacrylate-co-butyl methacrylate) 85% methyl methacrylate, poly(methyl methacrylate-co-ethyl acrylate) 5% ethyl acrylate, poly(propylene-co- butene) 12% 1 -butene, poly(styrene-co-allyl alcohol) 40% allyl alcohol, poly(styrene-co-maleic anhydride) 7% maleic anhydride, poly(styrene-co- maleic anhydride) cumene terminated (1.3:1 ), poly(styrene-co-methyl methacrylate) 40% styrene,
  • polystyrene-co-chloromethylstyrene 1 :1 polyvinylchloride, polyvinylcinnamate, polyvinylcyclohexane, polyvinylidenefluoride, polyvinylidenefluoride-co-hexafluoropropylene assume 1 :1 , poly(styrene- block-ethylene/propylene-block-styrene) 30% styrene, poly(styrene- block- ethylene/propylene-block-styrene) 18% styrene, poly(styrene- block- ethylene/propylene-block-styrene) 13% styrene, poly(styrene- block ethylene block-ethylene/propylene-block styrene) 32% styrene,
  • Preferred insulating binders to be used in the formulations as described before are polystryrene, poly(a-methylstyrene), polyvinylcinnamate, poly(4-vinylbiphenyl), poly(4-methylstyrene), and polymethyl methacrylate. Most preferred insulating binders are polystyrene and polymethyl methacrylate.
  • the binder can also be selected from crosslinkable binders, like e.g.
  • the binder can also be mesogenic or liquid crystalline.
  • the organic binder may itself be a semiconductor, in which case it will be referred to herein as a semiconducting binder.
  • the semiconducting binder is still preferably a binder of low permittivity as herein defined.
  • Semiconducting binders for use in the present invention preferably have a number average molecular weight (M n ) of at least 1500-2000, more preferably at least 3000, even more preferably at least 4000 and most preferably at least 5000.
  • the semiconducting binder preferably has a charge carrier mobility of at least 10 5 cm 2 V 1 s 1 , more preferably at least 10 4 cm 2 V 1 s 1 .
  • a preferred semiconducting binder comprises a homo-polymer or copolymer (including block-copolymer) containing arylamine (preferably triarylamine).
  • Another preferred embodiment of the invention relates to a polymer, or a composition comprising it, as described above and below, wherein the groups R c are crosslinked, preferably by photocrosslinking or thermal crosslinking.
  • Another preferred embodiment of the invention relates to a pattern or patterned film comprising a polymer, or a composition comprising it, as described above and below, wherein the groups R c are crosslinked.
  • the pattern or patterned a film is for example comprising, or consisting of, regions comprising the crosslinked polymer and regions without the polymer as described above and below.
  • Crosslinking of the groups R c can be achieved by conventional means and methods that are known to the skilled person and are described in the literature, for example by a photo- or thermal crosslinking reaction.
  • the composition comprising the polymer may further comprise an initiator, a catalyst or a sensitizer.
  • Patterns and patterned films can be made by means and methods that are known to the skilled person and are described in the literature, or in the examples below, for example by exposing the polymer through a photomask or shadow mask to light or other actinic radiation, e.g. UV light, causing a photocrosslinking reaction of the groups R c in the exposed regions, and subsequently rinsing the non-crosslinked polymer in the non- exposed regions.
  • actinic radiation e.g. UV light
  • polymers and compositions according to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electronic,
  • the polymers and compositions of the present invention are typically applied as thin layers or films.
  • the present invention also provides the use of the polymer or composition or layer in an electronic device.
  • the polymer or composition may be used as a high mobility semiconducting material in various devices and apparatus.
  • the polymer or composition 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 polymer or composition 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 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 compound according to the present invention can be carried out for example by photolithography, electron beam lithography or laser patterning.
  • 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.
  • Suitable solvents should be selected to ensure full dissolution of all components, like p-type and n-type OSCs, and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.
  • boundary conditions for example rheological properties
  • inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred.
  • spin coating alkylated benzenes like xylene and toluene are preferred.
  • the solvents should not have any detrimental effect on the chosen print head. Additionally, the solvents should preferably 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 derivatives, di-Ci-2-alkyl
  • a preferred solvent for depositing a polymer 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 inkjet fluid to be formed comprising the solvent with the 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, and 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 invention additionally provides an OE device comprising a polymer or composition or organic semiconducting layer according to the present invention.
  • Preferred OE devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, PSCs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarizing layers, antistatic films, conducting substrates and conducting patterns, .
  • Very preferred OE devices are OPV, PSC and OPD devices, OFETs, and OLEDs, in particular OPD, PSC and bulk heterojunction (BHJ) OPV devices.
  • the active semiconductor channel between the drain and source may comprise the polymer or composition of the invention.
  • the charge (hole or electron) injection or transport layer may comprise the polymer or composition of the invention.
  • An OPV or OPD device preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi-transparent substrate on one side of the photoactive layer, and a second metallic or semi-transparent electrode on the other side of the photoactive layer.
  • the OPV or OPD device comprises, between the photoactive 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 , NiO x , a conjugated polymer electrolyte, like for example PEDOTPSS, a conjugated polymer, like for example polytriarylamine (PTAA), an insulating polymer, like for example nafion, polyethyleneimine or polystyrenesulphonate, 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 ,1 '-biphenyl-4, 4'-diamine (TPD), or alternatively as hole
  • the OPV device can for example be of any type known from the literature (see e.g. Waldauf et ai, 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 polymer or polymer blend, for example of
  • PEDOTPSS poly(3,4-ethylenedioxythiophene): polystyrene- sulfonate
  • TBD N,N’-dyphenyl-N-N’-bis(3-methylphenyl)- 1 , 1’ biphenyl-4, 4’-diamine
  • NBD N,N’-dyphenyl-N-N’-bis(1 - napthylphenyl)-1 , 1’biphenyl-4, 4’-diamine
  • - a layer also referred to as "photoactive 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
  • photoactive layer comprising a p-type and an n-type organic semiconductor, which can exist for example as a p- type/n
  • a layer having electron transport properties for example comprising LiF or PFN,
  • 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
  • n-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):
  • a high work function metal or metal oxide electrode comprising for example ITO, serving as cathode
  • a layer having hole blocking properties preferably comprising an organic polymer, polymer blend, metal or metal oxide like TiO x , ZnO x , Ca, Mg, poly(ethyleneimine), poly(ethyleneimine) ethoxylated or poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9- dioctylfluorene)],
  • a photoactive 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 polymer or polymer blend, metal or metal oxide, for example PEDOTPSS, nafion, a substituted triaryl amine derivative like for example TBD or NBD, or WO x , MoO x , NiO x , Pd or Au,
  • 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
  • n-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/polymer/fullerene systems, as described above.
  • the photoactive layer When the photoactive 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. Pune. 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,
  • Another preferred embodiment of the present invention relates to the use of a polymer or composition according to the present invention as dye, hole transport layer, hole blocking layer, electron transport layer and/or electron blocking layer in a DSSC or a perovskite-based solar cell (PSC), and to a DSSC or PSC comprising a polymer or composition according to the present invention.
  • a polymer or composition according to the present invention as dye, hole transport layer, hole blocking layer, electron transport layer and/or electron blocking layer in a DSSC or a perovskite-based solar cell (PSC), and to a DSSC or PSC comprising a polymer or composition according to the present invention.
  • a preferred OE device according to the invention is a solar cell, preferably a PSC, comprising a light absorber which is at least in part inorganic as described below.
  • a solar cell comprising the light absorber according to the invention there are no restrictions per se with respect to the choice of the light absorber material which is at least in part inorganic.
  • the term“at least in part inorganic” means that the light absorber material may be selected from metalorganic complexes or materials which are substantially inorganic and possess preferably a crystalline structure where single positions in the crystalline structure may be allocated by organic ions.
  • the light absorber comprised in the solar cell according to the invention has an optical band-gap ⁇ 2.8 eV and > 0.8 eV.
  • the light absorber in the solar cell according to the invention has an optical band-gap ⁇ 2.2 eV and > 1.0 eV.
  • the light absorber used in the solar cell according to the invention does preferably not contain a fullerene.
  • the chemistry of fullerenes belongs to the field of organic chemistry. Therefore fullerenes do not fulfil the definition of being“at least in part inorganic” according to the invention.
  • the light absorber which is at least in part inorganic is a material having perovskite structure or a material having 2D crystalline perovskite structure.
  • perovskite as used above and below denotes generally a material having a perovskite crystalline structure or a 2D crystalline perovskite structure.
  • perovskite solar cell means a solar cell comprising a light absorber which is a material having perovskite structure or a material having 2D crystalline perovskite structure.
  • the light absorber which is at least in part inorganic is without limitation composed of a material having perovskite crystalline structure, a material having 2D crystalline perovskite structure (e.g. CrystEngComm, 2010,12, 2646-2662), Sb2S3 (stibnite), Sb 2 (S x Se( X -i))3 , PbS x Se( X -i), CdS x Se( X -i), ZnTe,
  • chalcopyrite e.g. Culn x Ga(i- X) (S y Se(i. y) )2
  • kesterite e.g. Cu2ZnSnS4, Cu2ZnSn(Se x S(i- X) )4, Cu2Zn(Sni- x Ge x )S4
  • metal oxide e.g. CuO, CU2O or a mixture thereof.
  • the light absorber which is at least in part inorganic is a perovskite.
  • x and y are each independently defined as follows: (0 ⁇ x ⁇ 1 ) and (0 ⁇ y ⁇ 1 ).
  • the light absorber is a special perovskite namely a metal halide perovskite as described in detail above and below.
  • the light absorber is an organic-inorganic hybrid metal halide perovskite contained in the perovskite solar cell (PSC).
  • the perovskite denotes a metal halide perovskite with the formula ABX3,
  • A is a monovalent organic cation, a metal cation or a mixture of two or more of these cations
  • B is a divalent cation
  • X is F, Cl, Br, I, BF 4 or a combination thereof.
  • the monovalent organic cation of the perovskite is selected from alkylammonium, wherein the alkyl group is straight chain or branched having 1 to 6 C atoms, formamidinium or guanidinium or wherein the metal cation is selected from K + , Cs + or Rb + .
  • Suitable and preferred divalent cations B are Ge 2+ , Sn 2+ or Pb 2+ .
  • Suitable and preferred perovskite materials are CsSnU, CFhNFhPb i- BF4)x)3,
  • x is each independently defined as follows: (0 ⁇ x ⁇ 1 ).
  • suitable and preferred perovskites may comprise two halides corresponding to formula Xa ( 3- X) Xb (X) , wherein Xa and Xb are each independently selected from Cl, Br, or I, and x is greater than 0 and less than 3.
  • Suitable and preferred perovskites are also disclosed in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
  • the materials are defined as mixed-anion perovskites comprising two or more different anions selected from halide anions and chalcogenide anions.
  • Preferred perovskites are disclosed on page 18, lines 5 to 17. As described, the perovskite is usually selected from
  • the invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as a layer between one electrode and the light absorber layer.
  • the invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is comprised in an electron-selective layer.
  • the electron selective layer is defined as a layer providing a high electron conductivity and a low hole conductivity favoring electron-charge transport.
  • the invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as electron transport material (ETM) or as hole blocking material as part of the electron selective layer.
  • ETM electron transport material
  • the polymer according to the present invention is employed as electron transport material (ETM).
  • ETM electron transport material
  • hole blocking material preferably, the polymer according to the present invention is employed as hole blocking material.
  • the device architecture of a PSC device according to the invention can be of any type known from the literature.
  • a first preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
  • a substrate which, in any combination, can be flexible or rigid and transparent, semi-transparent or non-transparent and electrically conductive or non-conductive;
  • a high work function electrode preferably comprising a doped metal oxide, for example fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide;
  • FTO fluorine-doped tin oxide
  • ITO tin-doped indium oxide
  • zinc oxide aluminum-doped zinc oxide
  • an electron-selective layer which comprises one or more electron transporting materials, at least one of which is a polymer according to the present invention, and which, in some cases, can also be a dense layer and/or be composed of nanoparticles, and which preferably comprises a metal oxide such as T1O2, Zn02, SnCte, Y2O5, Ga203, SrTiC , BaTiC or combinations thereof;
  • porous scaffold which can be conducting, semi-conducting or insulating, and which preferably comprises a metal oxide such as T1O2, Zn02, Sn02, Y2O5, Ga203, SrTi03, BaTiOs, AI2O3, Zr02, S1O2 or combinations thereof, and which is preferably composed of
  • a hole selective layer which comprises one or more hole transporting materials, and which, in some cases, can also comprise additives such as lithium salts, for example LiY, where Y is a
  • monovalent organic anion preferably bis(trifluoromethylsulfonyl)imide, tertiary amines such as 4-tert-butylpyridine, or any other covalent or ionic compounds, for example tris(2-(1 H-pyrazol-1 -yl)-4-tert- butylpyridine)-cobalt(lll) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
  • a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
  • a second preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
  • a substrate which, in any combination, can be flexible or rigid and transparent, semi-transparent or non-transparent and electrically conductive or non-conductive;
  • a high work function electrode preferably comprising a doped metal oxide, for example fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide;
  • FTO fluorine-doped tin oxide
  • ITO tin-doped indium oxide
  • zinc oxide aluminum-doped zinc oxide
  • a hole injection layer which, for example, changes the work function of the underlying electrode, and/or modifies the surface of the underlying layer and/or helps to planarize the rough surface of the underlying layer and which, in some cases, can also be a monolayer; optionally a hole selective layer, which comprises one or more hole transporting materials and which, in some cases, can also comprise additives such as lithium salts, for example LiY, where Y is a
  • monovalent organic anion preferably bis(trifluoromethylsulfonyl)imide, tertiary amines such as 4-tert-butylpyridine, or any other covalent or ionic compounds, for example tris(2-(1 H-pyrazol-1 -yl)-4-tert- butylpyridine)-cobalt(lll) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
  • a layer comprising a light absorber which is at least in part inorganic, particularly preferably a metal halide perovskite as described or preferably described above;
  • an electron-selective layer which comprises one or more electron transporting materials, at least one of which is a polymer according to the present invention and which, in some cases, can also be a dense layer and/or be composed of nanoparticles, and which, for example, can comprise a metal oxide such as T1O2, Zn02, SnCte, Y2O5, Ga203, SrTiC , BaTiC or combinations thereof, and/or which can comprise a substituted fullerene, for example [6,6]-phenyl C61 -butyric acid methyl ester, and/or which can comprise a molecular, oligomeric or polymeric electron-transport material, for example 2,9-Dimethyl-4,7-diphenyl-
  • a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
  • the polymers according to 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.
  • Formulations comprising the polymers according to 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 die coating or pad printing.
  • Formulations that can be used to produce electron selective layers in optoelectronic devices according to the invention, preferably in PSC devices comprise one or more polymers according to the present invention or preferred embodiments as described above in the form of blends or mixtures optionally together with one or more further electron transport materials and/or hole blocking materials and/or binders and/or other additives as described above and below, and one or more solvents.
  • the formulation may include or comprise, essentially consist of or consist of the said necessary or optional constituents as described above or below. All compounds or components which can be used in the
  • formulations are either known or commercially available, or can be synthesized by known processes.
  • the formulation as described before may be prepared by a process which comprises:
  • the solvent may be a single solvent for the polymer according to the present invention and the organic binder and/or further electron transport material may each be dissolved in a separate solvent followed by mixing the resultant solutions to mix the compounds.
  • the binder may be formed in situ by mixing or dissolving a polymer according to the present invention in a precursor of a binder, for example a liquid monomer, oligomer or crosslinkable polymer, optionally in the presence of a solvent, and depositing the mixture or solution, for example by dipping, spraying, painting or printing it, on a substrate to form a liquid layer and then curing the liquid monomer, oligomer or
  • crosslinkable polymer for example by exposure to radiation, heat or electron beams, to produce a solid layer.
  • a preformed binder it may be dissolved together with the polymer in a suitable solvent as described before, and the solution deposited for example by dipping, spraying, painting or printing it on a substrate to form a liquid layer and then removing the solvent to leave a solid layer.
  • solvents are chosen which are able to dissolve all ingredients of the formulation, and which upon evaporation from the solution blend give a coherent defect free layer.
  • the formulation as described before may comprise further additives and processing assistants.
  • additives and processing assistants include, inter alia, surface-active substances (surfactants), lubricants and greases, additives which modify the viscosity, additives which increase the conductivity, dispersants, hydrophobicizing agents, adhesion promoters, flow improvers, antifoams, deaerating agents, diluents, which may be reactive or unreactive, fillers, assistants, processing assistants, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.
  • Additives can be used to enhance the properties of the electron selective layer and/or the properties of any of the neighbouring layers and/or the performance of the optoelectronic device according to the invention.
  • Additives can also be used to facilitate the deposition, the processing or the formation of the electron selective layer and/or the deposition, the processing or the formation of any of the neighbouring layers.
  • one or more additives are used which enhance the electrical conductivity of the electron selective layer and/or passivate the surface of any of the neighbouring layers.
  • Suitable methods to incorporate one or more additives include, for example exposure to a vapor of the additive at atmospheric pressure or at reduced pressure, mixing a solution or solid containing one or more additives and a material or a formulation as described or preferably described before, bringing one or more additives into contact with a material or a formulation as described before, by thermal diffusion of one or more additives into a material or a formulation as described before, or by ion-implantation of one or more additives into a material or a
  • Additives used for this purpose can be organic, inorganic, metallic or hybrid materials.
  • Additives can be molecular compounds, for example organic molecules, salts, ionic liquids, coordination complexes or organometallic compounds, polymers or mixtures thereof.
  • Additives can also be particles, for example hybrid or inorganic particles, preferably nanoparticles, or carbon based materials such as fullerenes, carbon nanotubes or graphene flakes.
  • additives that can enhance the electrical conductivity are for example halogens (e.g. I2, CI2, Br2, ICI, ICI3, IBr and IF), Lewis acids (e.g. PF5, AsFs, SbFs, BF3, BCI3, SbCIs, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g. HF, HCI, HNO3, H2SO4, HCIO4, FSO3H and CISO3H), transition metal compounds (e.g.
  • halogens e.g. I2, CI2, Br2, ICI, ICI3, IBr and IF
  • Lewis acids e.g. PF5, AsFs, SbFs, BF3, BCI3, SbCIs, BBr3 and SO3
  • protonic acids e.g. HF, HCI, HNO3, H2SO4, HCIO4, FSO3H and CISO3H
  • transition metal compounds e.g.
  • FeC FeOCI, Fe(CI04)3, Fe(4- CHsCeFUSOsJs, TiCU, ZrCL, HfCU, NbF 5 , NbCIs, TaCIs, M0F5, M0CI5, WF 5 , WCI6, UFe and LnC (wherein Ln is a lanthanoid)), anions (e.g.
  • WO3, Re 2 07 and M0O3 metal- organic complexes of cobalt, iron, bismuth and molybdenum, (p- BrC6FU)3NSbCl6, bismuth(lll) tris(trifluoroacetate), FSO2OOSO2F, acetylcholine, R4N + , (R is an alkyl group), R4P + (R is a straight-chain or branched alkyl group 1 to 20), ReAs + (R is an alkyl group), RsS + (R is an alkyl group) and ionic liquids (e.g. 1-Ethyl-3-methylimidazolium
  • tris(bis(trifluoromethylsulfonyl)imide)) are cobalt complex salts as described in WO 2012/114315, WO 2012/114316, WO 2014/082706, WO 2014/082704, EP 2883881 or JP 2013-131477.
  • Suitable lithium salts are beside of lithium bis(trifluoromethylsulfonyl)imide, lithium tris(pentafluoroethyl)trifluorophosphate, lithium dicyanamide, lithium methylsulfate, lithium trifluormethanesulfonate, lithium tetracyanoborate, lithium dicyanamide, lithium tricyanomethide, lithium thiocyanate, lithium chloride, lithium bromide, lithium iodide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroantimonate, lithium hexafluoroarsenate or a combination of two or more.
  • a preferred lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
  • the formulation comprises from 0.1 mM to 50 mM, preferably from 5 to 20 mM of the lithium salt.
  • Suitable device structures for PSCs comprising a polymer according to the present invention and a mixed halide perovskite are described in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
  • Suitable device structures for PSCs comprising a polymer according to the present invention and a dielectric scaffold together with a perovskite are described in WO 2013/171518, claims 1 to 90 or WO 2013/171520, claims 1 to 94 which are entirely incorporated herein by reference.
  • Suitable device structures for PSCs comprising a polymer according to the present invention, a semiconductor and a perovskite are described in WO 2014/020499, claims 1 and 3 to 14, which is entirely incorporated herein by reference
  • the surface-increasing scaffold structure described therein comprises nanoparticles which are applied and/or fixed on a support layer, e.g. porous T1O2.
  • Suitable device structures for PSCs comprising a polymer according to the present invention and comprising a planar heterojunction are described in WO 2014/045021 , claims 1 to 39, which is entirely incorporated herein by reference.
  • Such a device is characterized in having a thin film of a light absorbing or light-emitting perovskite disposed between n-type (electron conducting) and p-type (hole-conducting) layers.
  • the thin film is a compact thin film.
  • the invention further relates to a method of preparing a PSC as described above or below, the method comprising the steps of:
  • the invention relates furthermore to a tandem device comprising at least one device according to the invention as described above and below.
  • the tandem device is a tandem solar cell.
  • the tandem device or tandem solar cell according to the invention may have two semi-cells wherein one of the semi cells comprises the compounds, oligomers or polymers in the active layer as described or preferably described above.
  • one of the semi cells comprises the compounds, oligomers or polymers in the active layer as described or preferably described above.
  • the other type of semi cell which may be any other type of device or solar cell known in the art.
  • tandem solar cells There are two different types of tandem solar cells known in the art.
  • the so called 2-terminal or monolithic tandem solar cells have only two connections.
  • the two subcells or synonymously semi cells
  • the current generated in both subcells is identical (current matching).
  • the gain in power conversion efficiency is due to an increase in voltage as the voltages of the two subcells add up.
  • tandem solar cells The other type of tandem solar cells is the so called 4-terminal or stacked tandem solar cell.
  • both subcells are operated independently. Therefore, both subcells can be operated at different voltages and can also generate different currents.
  • the power conversion efficiency of the tandem solar cell is the sum of the power conversion efficiencies of the two subcells.
  • the invention furthermore relates to a module comprising a device according to the invention as described before or preferably described before.
  • the polymers and compositions according to the present invention can also be used as dye or pigment in other applications, for example as an ink dye, laser dye, fluorescent marker, solvent dye, food dye, contrast dye or pigment in coloring paints, inks, plastics, fabrics, cosmetics, food and other materials.
  • the polymers and compositions of the present invention are also suitable for use in the semiconducting channel of an OFET. 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 polymer or a composition 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 polymer or a composition 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 polymers according to the invention and thus the processibility of large surfaces, preferred applications of these OFETs 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 polymer according to the present invention.
  • 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 monetary value, like stamps, tickets, shares, cheques etc.
  • the polymers and compositions hereinafter referred to as
  • materials 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.
  • 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
  • the materials according to the present invention 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 materials according to the present 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., MCiller et at,
  • the materials according to the present 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 al., Science, 1998, 279, 835-837.
  • a further aspect of the invention relates to both the oxidized and reduced form of the materials according to the present invention. Either loss or gain of electrons results in formation of a highly delocalized 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, 198, 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 delocalized ionic centers 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-implantation of the dopant into the semiconductor material.
  • suitable dopants are for example halogens (e.g., I2, CI2, Br2, ICI, ICI3, IBr and IF), Lewis acids (e.g., PF5, AsFs, SbFs, BF3, BCI3, SbCIs, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HNO3, H2SO4, HCIO4, FSO3H and CISO3H), transition metal compounds (e.g., FeC , FeOCI, Fe(CI04)3, Fe(4-CH 3 C 6 H4S03)3, TiCU, ZrCL, HfCU, NbF 5 , NbCIs, TaCIs, M0F5, M0CI5, WF5, WCI6, UFe and LnC (wherein Ln is a lanthanoid), anions (e.g., Cl , Br, I-, I3-, HSO4 ⁇ , SO4
  • Lewis acids e.
  • examples of dopants are cations (e.g., FT, 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), O2, XeOF4, (N02 + ) (SbFe ), (N02 + ) (SbCle ), (N0 2 + ) (BF4-), AgCI0 4 , H 2 lrCI 6 , La(N0 3 ) 3 6H2O, FSO2OOSO2F, Eu, acetylcholine, R4N + , (R is an alkyl group), R4P + (R is an alkyl group), R 6 AS + (R is an alkyl group), and RsS + (R is an alkyl group).
  • cations e.g., FT, Li + , Na + , K +
  • the conducting form of the materials according to the present invention can be used as an organic "metal” in applications including, but not limited to, charge injection layers and ITO planarizing layers in OLED
  • the materials 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.
  • OPEDs organic plasmon-emitting diodes
  • 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 polarization charge of the ferroelectric LCs.
  • this increased electrical conductivity can enhance the electroluminescence of the light emitting material.
  • the materials according to the present invention having mesogenic or liquid crystalline properties can form oriented anisotropic films as
  • the materials according to the present invention are suitable for use in liquid crystal (LC) windows, also known as smart windows.
  • LC liquid crystal
  • the materials according to the present invention may also be combined with photoisomerizable compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913 A1.
  • 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.
  • triphenylphosphine (670 mg, 2.55 mmol), 4,4,9,9-tetrakis(12- hydroxydodecyl)-4,9-dihydro-s-indaceno[1 , 2-6:5, 6-6']dithiophene (534 mg, 0.532 mmol) in anhydrous tetrahydrofuran (25 cm 3 ) was cooled to -78 °C. Diethyl azodicarboxylate (0.40 cm 3 , 2.5 mmol) was added dropwise and the mixture was stirred with cooling for 10 minutes.
  • 3,4-Dimethylmaleimide (320 mg, 2.55 mmol) was added in one portion and the flask was removed from the cooling bath and the gel was shaken manually at 20 °C until it was stirrable. The gel was gradually dissolved over ca 30 minutes to yield a solution. The solution was stirred at 20 °C for 18 hours. The volatiles were removed in vacuo and the crude chromatographed on silica (dichlorom ethane) to give the titled product (0.43 g, 57%) as a very thick yellow oil.
  • Top-gate thin-film organic field-effect transistors were fabricated on glass substrates with thermally evaporated Au source-drain electrodes at the thickness of 40 nm. A planarization layer was deposited prior to the electrodes evaporation. The electrodes were then treated with Merck Lisicon® M001 using a standard procedure. 7 mg/cm 3 solution of the organic semiconductor in dichlorobenzene was spin-coated on top (an optional annealing of the film was carried out at 100 °C, 150 °C or 200 °C for between 1 and 5 minutes followed by a spin-coated fluoropolymer dielectric material (Lisicon® D139 from Merck, Germany).
  • the field effect transistor device characteristics for a device using Polymer 4 as the active OSC material in top gate bottom contact configuration is shown in Fig. 1. Therein the mobility was calculated based on the first derivative of the linear regime and second derivative for the saturation regime. The dimensions of the device are 500 pm (W) and 20 pm (L).
  • a solution of Polymer 4 in chloroform containing 0.15% Omnipol TX was spin-coated on glass substrate to prepare a film.
  • the film was covered with a shadow mask and exposed to UV light of 254 nm at 1.536 J/cm 2 for 2 minutes.
  • Mesitylene was then puddled for 30 seconds and spun off.
  • the resulting film thickness left is 28.67 nm.
  • the smallest feature size is 10 pm (gap of transistor pattern).
  • Fig. 2 shows a microscopic image of the directly patterned film of Polymer 4 on bare glass.

Abstract

The invention relates to novel photo-crosslinkable organic semiconducting (OSC) polymers, to methods for their preparation and educts or intermediates used therein, to compositions and formulations containing them, to the use of the polymers and compositions as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photo-detectors (OPD), organic field effect transistors (OFET)and organic light emitting diodes (OLED), and to OE, OPV, PSC, OPD, OFET and OLED devices comprising these polymers or compositions.

Description

Organic Semiconducting Polymers
Technical Field The invention relates to novel photo-crosslinkable organic semiconducting (OSC) polymers, to methods for their preparation and educts or
intermediates used therein, to compositions and formulations containing them, to the use of the polymers and compositions as organic
semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photo-detectors (OPD), organic field effect transistors (OFET) and organic light emitting diodes (OLED), and to OE, OPV, PSC, OPD, OFET and OLED devices comprising these polymers or compositions.
Background
Carbon-based organic semiconducting materials (OSC) have attracted remarkable attention for more than two decades due to their commercial prospects for use in organic electronics. In contrast to traditional silicon based semiconductors, OSCs are solution processable. Consequently, organic electronic devices can be made flexible, unbreakable, stretchable, thin and light weight. They can also be manufactured in large area by cost effective roll-to-roll printing techniques at low temperature. It is particularly encouraging that some state-of-the-art application processes, such as electrophoretic display devices (EPD) driven by organic thin film transistor (OTFT) backplanes, and all organic liquid crystal display panels (OLCD), have been demonstrated and the transfer from laboratories to
manufacturing plants has been underway.
Organic electronic devices in which OSCs are used as actives materials are, in general, multi-layered sandwich structures. An OTFT device, e.g., is composed of minimum four layers, namely, the source and drain electrodes layer, the OSC active layer, the gate insulator/dielectric layer and the gate electrode. In practice, optimised devices have more layers such as surface modification and passivation layers. For bulk heterojunction OPV and OPD devices, although the donor and acceptor OSCs are mixed in the same layer, both electron and hole transporting layers are normally required in addition to the electrodes leading to multi layer stacks. A state-of-the-art flexible OLED device, however, consists of even more layer in the stack than the other devices mentioned above.
Multi-layered architectures of organic electronic devices are normally fabricated through a layer-by-layer deposition process. Metal electrodes are in most of the cases deposited by vapour evaporation under high vacuum although printed electrodes, subjected to further improvement, may also be possible. OSC layers, particularly polymeric, are mostly solution processed, which means that OSCs materials should be soluble in organic solvent to obtain uniformed solutions. The solvent should ideally be nontoxic to humans and animals, noncorrosive to the manufacturing tools and benign to the environment.
Furthermore, it is crucial that the solvents for different functional layers need to be“orthogonal”, which means the solvent of the layer being deposited should not dissolve or ingress into the previous layer directly underneath it. Otherwise, the previous layer will be removed, or the interface between these two layers will be damaged, or the morphology of the previous layer will be altered. In whichever case, the device
performances will be negatively impacted, even stop functioning.
However, finding orthogonal solvents is extremely challenging.
In this context, an alternative solution is to crosslink the OSC molecules in the films through chemical bonds after deposition, so that the material of the OSC layer is insolubilised to the solvent being used for the next layer of deposition. Hence, a photo-crosslinking process will enable fabrication of top-gate OTFTs with fewer restrictions on gate dielectric materials, reduce leakage, cross-talks and off-current. In OPV devices, a cross- linked active layer will minimise the migration of active molecules such as fullerenes, achieving additional thermal stability of morphology. As an immediate consequence of photo-crosslinking reactions, direct photo-patterning of photosensitive organic semiconducting polymers can be made possible. These polymers can be processed exactly like negative photoresists, which, as a result, give rise to single pixels or patterns of arbitrary size and shape. Although printing processes are the ultimate goal for mass production of organic electronic devices, many obstacles, such as registration accuracy, cross-talks with neighbouring pixels, device performances and so on, must be overcome prior to commercialisation. More than often, the devices still need to be printed into pre-patterned bank structures on the substrates. Although conventional photolithography technique could be used to pattern organic semiconductor films, the process of applying, developing and striping photoresists would usually cause re-dissolution, solvent infiltration as well as contamination.
Several different photoreaction functional groups have been investigated and disclosed for direct patterning of conjugated oligomers and polymers upon exposure to UV light, such as acrylates, methacrylates, cinnamates, oxetanes, azides and thiol-ene photo-clicking groups. However, most of these cross-linking technologies require additives like photoinitiators, photoacid generators (PAG) and/or crosslinkers. These additives can result in side reactions and side-products which remain in the materials matrix to become charge traps.
US6107452 discloses a class of photo-crosslinkable conjugated and non- conjugated polymers where the photo active vinyl groups are the end capping terminal groups. However, as there are only two crosslinkable groups per polymer chain, these concepts would be insufficient to render the semiconducting polymers insoluble to achieve micrometre sized patterns, particularly, when molecular weights are high.
W00210129A2 discloses photo-crosslinkable electroluminescent spirofluorene copolymers, using oxetane functional groups attached to the fluorene monomer units. However, this type of unsymmetrical substitution lead to disorder and eventually poor packing of the polymer molecules, which is particularly unfavourable to OTFT applications, where packing of the OSC molecules is of crucial to achieve high charge mobilities. This type of strategy was later proved to be harmful to OTFT performances by A. Charas, et al, ( Chem . Phys. Lett., 2008, 455, 189-191 ). W02006043087A1 discloses a class of photo-crosslinkable polymers, where the photoreacting groups, preferably styrene groups, are attached through a spacer moiety to a nitrogen atom forming triarylamine polymers. The general formula of the monomers is claimed as follows:
Figure imgf000005_0001
, in which X is the cross-linkable group.
C. B. Nielsen, et al, ( J . Am. Chem. Soc., 2008, 130 (30), pp 9734-9746) demonstrate using acrylate groups to pattern oligothiophene films. E. Scheler and P. Strohriegl (Chem. Mater., 2010, 22, 1410-1419) and F.-J. Kahle, et al, (J. Polym. Sci., Pt B, Polym. Phys., 2017, 55(1), 112-120) report using acrylate groups to pattern fluorene oligomers and polymers. T. Ube, et al, (J. Mater. Chem. C, 2017, 5, 1414— 1419) use cinnamate group to photo cross-link poly(3-alkylthiophene)s. However, these ester groups are thermal reactive as well, which is harmful to the stability and hence compromise the shelf life of OSC formulations. In addition, undesirable thermal cross-linking should be avoided during the
manufacturing process where thermal annealing is normally involved.
In addition to the above-mentioned photo-cross-linking methods, diene
(W02004093154A2), thiol-ene clicking ( Macromolecules , 2015, 48 (6), 1711-1722) and azide ( Nature Materials, 2010, 9, 152-158) have also been disclosed to photo-crosslink semiconducting polymers. However, these functional groups require either crosslinkers or photo initiators for curing. While the addition of such compounds may in some cases be tolerable by OLED, OPV, OPD and dielectrics applications, in case high mobility semiconducting materials for OTFTs, which are sensitive to defects, these reaction residues may induce additional trapping states for charge transport. Charge carriers travelling through the device will be captured easily resulting in reduced charge mobilities.
Therefore there is still a need for photo-crosslinkable semiconducting polymers which do not have the drawbacks as described above and show advantageous properties, especially one or more of a good processability from solution, a high solubility in organic solvents, especially in nontoxic, noncorrosive, environment-friendly and/or orthogonal solvents, a good structural organization, good film-forming properties, being applicable for example by printing methods, being processable like negative
photoresists, and enabling direct photo-patterning. In addition, they should be easy to synthesize, especially by methods suitable for mass
production.
It was an aim of the present invention to provide new photo-crosslinkable semiconducting polymers, which can overcome the drawbacks of the polymers known from prior art and provide one or more of the above- mentioned advantageous properties. Another aim of the invention was to extend the pool of photo-crosslinkable semiconducting polymers 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 surprisingly found that one or more of the above aims can be achieved by providing polymers as disclosed and claimed hereinafter. These polymers represent a novel class of photo-crosslinkable and photo-patternable semiconducting polymers comprising maleimide, for example 2,3-dimethylmaleimide (DMMI), as photoreactive groups, which can be directly crosslinked under UV radiation without the presence of photo-initiators or photo-crosslinkers. These polymers can be used as the active materials in organic electronic devices such as semiconducting layer in organic thin film transistors (OTFT), donor or acceptor component in organic photovoltaic cells (OPV) and organic photodetectors (OPD), and emissive or charge transporting layers in organic light emitting diodes (OLED). In another aspect, the present application also provides synthetic methods to incorporate pendent maleimide or DMMI groups to conjugated polymer main chains. Summary
The invention relates to a conjugated polymer comprising one or more repeating units of formula I
Figure imgf000007_0001
and/or one or more divalent repeating units Ar6, wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Ar1, Ar2 a group selected from the following formulae
Figure imgf000007_0002
U1, U2 CR1R2, SiR1R2, GeR1R2, C=CR1R2 or NR1,
Ar3, Ar4, Ar5 fused aryl or heteroaryl ring which has from 5 to 20 ring
atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Ar6 arylene or heteroarylene which has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L or R1,
R1, R2 H, F, Cl, CN, -Sp-Rc, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more Chh groups are each optionally replaced by -0-, -S-, -C(=0)-, -C(=S)-, -C(=0)-0-, -0-C(=0)-, -NR0-, -SiR°R00-, - CF2-, -CR°=CR00-, -CY1=CY2- or -CºC- in such a manner that 0 and/or S atoms are not linked directly to one another, and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN, and in which one or more CFI2 or CFI3 groups are each optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L, and the pair of R1 and R2, together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L, Sp a spacer group, a maleimide or maleimide containing group that is unsubstituted or substituted, preferably by C1-4 alkyl, very preferably by methyl,
L F, Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, R°, OR0,
SR°, -C(=0)X°, -C(=0)R°, -C(=0)-OR°, -O-C(=O)-R0, -NH2, - NHR°, -NR°R00, -C(=0)NHR°, -C(=0)NR°R°°, -SO3R0, - SO2R0, -OH, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30, preferably 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, preferably F, -CN, R°, -OR0, -SR°, - C(=0)-R°, -C(=0)-OR°, -0-C(=0)-R°, -O-C(=O)-OR0, -C(=0)- NHR°, or -C(=0)-NR°R00, RO ROO |_| or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12, C atoms that is optionally fluorinated,
X° halogen, preferably F or Cl, k 0 or an integer from 1 to 10, preferably 0, 1 , 2, 3, 4, 5, 6 or 7, very preferably 0, 1 , 2 or 3, most preferably 1 , wherein the conjugated polymer comprises a) at least one unit of formula I wherein at least two groups R1 and R2 that are attached to the same C, Si or Ge atom denote each -Sp-Rc, or wherein at least one group R1 that is attached to an N atom denotes -Sp- Rc, or b) at least one unit Ar6 which is substituted by at least one group R1 that denotes -Sp-Rc, or both a) and b).
The invention further relates to a polymer as described above and below wherein the groups Rc are crosslinked.
The invention further relates to a pattern or patterned film comprising a polymer as described above and below wherein the groups Rc are crosslinked.
The invention further relates to a monomer comprising a divalent unit of formula I or its subformulae which are at least monosubstituted by Rc, optionally further comprising one or more additional arylene or
heteroarylene units, and further comprising one or more reactive groups which can be reacted to form a polymer according to the present invention as described above and below. The invention further relates to novel synthesis methods for preparing repeating units of formula I that are at least monosubstituted by Rc and monomers and polymers comprising them, and novel intermediates used therein.
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 acceptor or n-type semiconductor. The invention further relates to the use of a polymer according to the present invention 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, and preferably further comprising one or more compounds having electron donor or electron acceptor properties.
The invention further relates to a composition, which may also be a polymer blend, comprising one or more polymers according to the present invention, and further comprising one or more additional compounds 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 composition comprising an n-type semiconductor which is a polymer according to the present invention, and further comprising one or more p-type organic semiconductors, preferably selected from conjugated polymers.
The invention further relates to a composition comprising a p-type semiconductor which is a polymer according to the present invention, and further comprising an n-type semiconductor, which is preferably a fullerene or fullerene derivative, a non-fullerene acceptor small molecule, or an n- type conjugated polymer. The invention further relates to a formulation comprising one or more polymers or a composition according to the present invention, and further comprising one or more solvents, preferably selected from organic solvents.
The invention further relates to an organic semiconducting formulation comprising one or more polymers according to the present invention, and further comprising one or more organic binders or precursors thereof, preferably having a permittivity e at 1 ,000 Hz and 20°C of 3.3 or less, and optionally one or more solvents preferably selected from organic solvents.
The invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which is prepared using a formulation according to the present invention.
The invention further relates to the use of a polymer or composition according to the present invention as semiconducting, charge transport, electrically conducting, photoconducting or light emitting material, or in an optical, electronic, optoelectronic, 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 semiconducting, charge transport, electrically conducting, photoconducting or light emitting material comprising a polymer or composition according to the present invention.
The invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a polymer, composition pattern or patterned film according to the present invention, or comprises a semiconducting, charge transport, electrically conducting, photoconducting or light emitting material according to the present invention. The optical, electronic, optoelectronic, electroluminescent and
photoluminescent deviced 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, dye-sensitized solar cells (DSSC), perovskite-based solar cells (PSC), laser diodes, Schottky diodes, photoconductors and
photodetectors.
Preferred devices are OFETs, OTFTs, OPVs, PSCs, OPDs and OLEDs, in particular OTFTs, PSCs, OPDs and bulk heterojunction (BH J) OPVs or inverted BH J OPVs.
Further preferred is the use of a polymer or composition according to the present invention as dye in a DSSC or a PSC. Further preferred is a DSSC or PSC comprising a polymer or composition according to the present invention.
The component of the above devices includes, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
The assembly comprising such a device or component includes, 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 polymers, compositions and formulations of the present invention can be used as electrode materials in batteries and in
components or devices for detecting and discriminating DNA sequences.
The invention further relates to a bulk heterojunction which comprises, or is being formed from, a composition comprising one or more polymers according to the present invention. The invention further relates to a bulk heterojunction (BHJ) OPV or OPD device or inverted BHJ OPV or OPD device, comprising such a bulk heterojunction. Brief Description of the Drawings
Fig. 1 shows the transistor characteristics for a top gate bottom contact field effect transistor according to Use Example 1 . Fig. 2 shows a microscopic image of a directly patterned polymer film according to Use Example 2.
Terms and Definitions
As used herein, the terms "indaceno-type group" and "indaceno group" mean a group comprising two cyclopentadiene rings, or heterocyclic or vinylidene derivatives thereof, that are fused to a central aromatic or heteroaromatic aromatic ring Ar, and which can have cis- or trans configuration, as exemplarily shown below
Figure imgf000013_0001
wherein U is e.g. C, Si or Ge and R is a carbyl or hydrocarbyl group.
In the units of formula I adjacent rings Ar1-5 are understood to be fused, i.e. having at least two atoms and one covalent bond in common. In the rings Ar1 and Ar2 of formula A1 and A2 the pi-electrons may also be delocalised into adjacent rings Ar3, Ar4 or Ar5, so that for example a ring
Figure imgf000014_0001
may also include for example its mesomer
As used herein, 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 International Union of Pure and Applied Chemistry, Compendium of
Chemical Technology, Gold Book, Version 2.3.2, 19. August 2012, pages 477 and 480.
As used herein, the term "donor unit" will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron donating or electron pushing property towards a neighboured conjugated unit. The term "acceptor unit" will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron accepting or electron withdrawing property towards a neighboured conjugated unit. The term "spacer unit" will be understood to mean a unit which can be conjugated or non-conjugated and is located between a donor and an acceptor unit, and is preferably selected such that it does not have electron accepting property towards a neighboured donor unit.
As used herein, the term "spacer unit" will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which is located between two donor units, or between two acceptor units, or between an acceptor unit and a donor unit, such that said donor and acceptor units are not connected directly with each other.
As used herein, the term "n-type" or "n-type semiconductor" 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 "conjugated" will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp2- hybridization (or optionally also sp-hybridization), 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, or with defects included by design, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
As used herein, the term "polymer" will be understood to mean a molecule of high relative molecular mass, the structure of which essentially comprises multiple repetitions 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, very preferably >10, 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”,“random polymer” 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 an asterisk (*) will be understood to mean a chemical linkage, usually a single bond, to an adjacent unit or to a terminal group in the polymer backbone.
In a ring, like for example a benzene or thiophene ring, an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring. As used herein, in a formula showing a ring, a polymer or a repeat unit a dashed line (— ) will be understood to mean a single bond.
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 polymerization reaction, like for example a group having the meaning of R31 or R32 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 polymerization reaction. Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerization reaction. In situ addition of an endcapper can also be used to terminate the polymerization 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 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 Appl. Chem., 1994, 66, 1134).
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, chlorobenzene 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 any monovalent or multivalent organic moiety which comprises at least one carbon atom either without any non-carbon atoms (like for
example -CºC-), or optionally combined with at least one non-carbon atom such as B, N, 0, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
As used herein, 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 B, 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 B, N, O, S, P, Si, Se, Sn, 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, and may include spiro-connected and/or fused rings.
Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has up to 40, preferably up to 25, very preferably up 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 1 to 40, preferably 6 to 40 C atoms, wherein each of these groups optionally contains one or more hetero atoms, preferably selected from B, N, 0, S, P, Si, Se, As, Te and Ge.
Further preferred carbyl and hydrocarbyl group include for example: a C-i- C40 alkyl group, a C1-C40 fluoroalkyl group, a C1-C40 alkoxy or oxaalkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C3-C40 allyl group, a C4-C40 alkyldienyl group, a C4-C40 polyenyl group, a C2-C40 ketone group, a C2-C40 ester group, a C6-C18 aryl group, a C6-C40 alkylaryl group, a C6-C40 arylalkyl group, a C4-C40 cycloalkyl group, a C4-C40 cycloalkenyl group, and the like. Preferred among the foregoing groups are a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C2-C20 alkenyl group, a C2 -C20 alkynyl group, a C3-C20 allyl group, a C4-C20 alkyldienyl group, a C2-C20 ketone group, a C2-C20 ester group, a C6-C12 aryl group, and a C4-C20 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 carbyl or hydrocarbyl group may be an acyclic group or a cyclic group. Where the carbyl or hydrocarbyl group is an acyclic group, it may be straight-chain or branched. Where the carbyl or hydrocarbyl group is a cyclic group, it may be a non-aromatic carbocyclic or heterocyclic group, or an aryl or heteroaryl group.
A non-aromatic carbocyclic group as referred to above and below is saturated or unsaturated and preferably has 4 to 30 ring C atoms. A non aromatic heterocyclic group as referred to above and below preferably has 4 to 30 ring C atoms, wherein one or more of the C ring atoms are each optionally replaced by a hetero atom, preferably selected from N, O, P, S, Si and Se, or by a -S(O)- or -S(0)2- group. The non-aromatic carbo- and heterocyclic groups are mono- or polycyclic, may also contain fused rings, preferably contain 1 , 2, 3 or 4 fused or unfused rings, and are optionally substituted with one or more groups L. L is selected from F, Cl, -CN, -NO2, -NC, -NCO, -NCS, -OCN, -SCN, -R°, - OR0, -SR°, -C(=0)X°, -C(=0)R°, -C(=0)-0R°, -0-C(=0)-R°, -NH2, -NHR°, - NR°R00, _C(=0)NHR°, -C(=0)NR°R00, -SO3R0, -SO2R0, -OH, -CFs, -SFs, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30, preferably 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, wherein X° is halogen, preferably F or Cl, and R°,
R00 each independently denote H or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12 C atoms that is optionally fluorinated. Preferably L is selected from F, -CN, R°, -OR0, -SR°, -C(=O)-R0, -C(=0)- OR°, -0-C(=0)-R°, -0-C(=0)-0R°, -C(=O)-NHR0 and -C(=0)-NR°R°°.
Further preferably L is selected from F or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl, fluoroalkoxy, alkylcarbonyl, alkoxycarbonyl, with 1 to 16 C atoms, or alkenyl or alkynyl with 2 to 16 C atoms.
Preferred non-aromatic carbocyclic or heterocyclic groups are
tetrahydrofuran, indane, pyran, pyrrolidine, piperidine, cyclopentane, cyclohexane, cycloheptane, cyclopentanone, cyclohexanone, dihydro- furan-2-one, tetrahydro-pyran-2-one and oxepan-2-one.
An aryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, is mono- or polycyclic and may also contain fused rings, preferably contains 1 , 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
A heteroaryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, wherein one or more of the ring C atoms are replaced by a hetero atom, preferably selected from N, O, S, Si and Se, is mono- or polycyclic and may also contain fused rings, preferably contains 1 , 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
An arylalkyl or heteroarylalkyl group as referred to above and below preferably denotes -(CH2)a-aryl or -(CH2)a-heteroaryl, wherein a is an integer from 1 to 6, preferably 1 , and "aryl" and "heteroaryl" have the meanings given above and below. A preferred arylalkyl group is benzyl which is optionally substituted by L.
As used herein, "arylene" will be understood to mean a divalent aryl group, and "heteroarylene" will be understood to mean a divalent heteroaryl group, including all preferred meanings of aryl and heteroaryl as given above and below.
Preferred aryl and heteroaryl groups are phenyl in which, in addition, one or more CH groups may each 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 aryl and heteroaryl groups are selected from phenyl, 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, 2,5-dithiophene-2',5'-diyl, 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-b]selenophene, 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, 4H-cyclopenta[2,1 -b;3,4-b']dithiophene,
7H-3,4-dithia-7-sila-cyclopenta[a]pentalene, 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 group or an alkoxy group, i.e., where the terminal CFh group is replaced by -0-, can be straight-chain or branched. Particularly preferred straight-chains have 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms and accordingly denote preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl or hexadecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, dodecoxy or hexadecoxy, furthermore methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, tridecoxy or tetradecoxy, for example.
An alkenyl group, i.e., wherein one or more Chh groups are each 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, Cs-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, 1 E-propenyl, 1 E-butenyl,
1 E-pentenyl, 1 E-hexenyl, 1 E-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-, can be straight-chain. Particularly preferred straight-chains are 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.
In an alkyl group wherein one CH2 group is replaced by -O- and one CH2 group is replaced by -C(O)-, these radicals are preferably neighboured. Accordingly, these radicals together form a carbonyloxy group -C(0)-0- 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, acetyloxym ethyl,
propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl,
2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl,
methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl,
3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)-butyl.
An alkyl group wherein two or more Chh groups are replaced by -0- and/or -C(0)0- 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 or 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), 1 -(thiopentyl), 1 -(thiohexyl),
1 -(thioheptyl), 1 -(thiooctyl), l -(thiononyl), 1 -(thiodecyl), l-(thioundecyl) or 1 -(thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is replaced.
A fluoroalkyl group can be perfluoroalkyl CjF2i+i , wherein i is an integer from 1 to 15, in particular CF3, C2F5, C3F7, C4F9, C5F11 , C6F13, C7F15 or C8F17, very preferably C6F13, or partially fluorinated alkyl, preferably with 1 to 15 C atoms, in particular 1 ,1-difluoroalkyl, all of the aforementioned being straight-chain or branched.
Preferably "fluoroalkyl" means a partially fluorinated (i.e. not
perfluorinated) alkyl group. Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, 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-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl, 3,7,11 -trimethyldodecyl, 2-propylpentyl, in particular 2-methylbutyl, 2- methylbutoxy, 2-methylpentoxy, 3-methyl-pentoxy, 2-ethyl-hexoxy, 2- butyloctoxyo, 2-hexyldecoxy, 2-octyldodecoxy, 3,7-dimethyloctoxy, 3,7,11 - trimethyldodecoxy, 1 -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-methoxy-octoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5- methylheptyloxy-carbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4- methylhexanoyloxy, 2-chloro-propionyloxy, 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 and 2- fluoromethyloctyloxy for example. Very preferred are 2-methylbutyl, 2- ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl,
3,7,11 -trimethyldodecyl, 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, the substituents on an aryl or heteroaryl ring are independently of each other selected from primary, secondary or tertiary alkyl, alkoxy, oxaalkyl, thioalkyl, alkylcarbonyl or alkoxycarbonyl with 1 to 30 C atoms, wherein one or more H atoms are each optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated, alkoxylated, alkylthiolated or esterified and has 4 to 30, preferably 5 to 20, ring atoms. Further preferred substituents are selected from the group consisting of the following formulae RSub1 RSub
Figure imgf000025_0003
SUB1 SUB2 SUB3
Figure imgf000025_0002
RSub RSub2
Figure imgf000025_0001
SUB4 SUB5 SUB6
Figure imgf000025_0004
SUB13 SUB14 SUB15
Figure imgf000026_0001
SUB16 SUB17 SUB18 wherein RSubi-3 each denote L as defined above and below and where at least, preferably all, of RSubi-3 is alkyl, alkoxy, oxaalkyl, thioalkyl, alkyl- carbonyl or alkoxycarbonyl with up to 24 C atoms, preferably up to 20 C atoms, that is optionally fluorinated, and wherein the dashed line denotes the link to the ring to which these groups are attached. Very preferred among these substituents are those wherein all RSubi-3 subgroups are identical.
As used herein, if an aryl(oxy) or heteroaryl(oxy) group is "alkylated or alkoxylated", this means that it is substituted with one or more alkyl or alkoxy groups having from 1 to 24 C-atoms and being straight-chain or branched and wherein one or more H atoms are each optionally
substituted by an F atom.
Above and below, Y1 and Y2 are independently of each other H, F, Cl or CN.
As used herein, -CO-, -C(=0)- and -C(O)- will be understood to mean a
Figure imgf000026_0002
carbonyl group, i.e. a group having the structure
As used herein, C=CR1 R2 will be understood to mean a group having the
Figure imgf000026_0003
structure
As used herein, "halogen" includes F, Cl, Br or I, preferably F, Cl or Br. A halogen atom that represents a substituent on a ring or chain is preferably F or Cl, very preferably F. A halogen atom that represents a reactive group in a monomer or an intermediate is preferably Br or I.
Above and below, the term "mirror image" means a moiety that can be obtained from another moiety by flipping it vertically or horizontally across an external symmetry plane or a symmetry plane extending through the moiety. For example the moiety
Figure imgf000027_0001
Detailed Description
The polymers according to the present invention are easy to synthesize and exhibit advantageous properties. They show good processibility for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods.
The polymers according to the present invention comprise maleimide groups as photo-active pendent group and can thus be advantageously used as photo-crosslinkable semiconducting polymers. They do not require additives like photo-initiators or photo-crosslinkers which can generally induce side-reactions and form side-products which, as a result, become additional trapping states and hence impact negatively on the charge mobilities.
Also, in contrast to photo-crosslinkable polyfluorenes as reported in prior art ( Chem . Phys. Lett., 2008, 455, 189-191 ; J. Polym. Sci., Pt B, Polym. Phys., 2017, 55(1), 112-120), where the photoactive groups are attached in one of the two solubilising chains, the maleimide groups in the polymers according to the present invention are introduced in a symmetrical pattern, which is of great benefit to the ordering of the polymer main chains and hence facilitates charge carrier mobilities in OTFT, OPV and OPD devices. In another aspect of this invention, the semiconducting polymers can be directly patterned like a conventional negative photoresist.
The synthesis of the repeating units of formula I and polymers comprising them can be achieved based on methods that are known to the skilled person and described in the literature, as will be further illustrated herein.
Preferably the conjugated polymer comprises at least one unit of formula I wherein at least two groups R1 and R2 that are attached to the same C, Si or Ge atom denote each -Sp-Rc, or wherein at least one group R1 that is attached to an N atom denotes -Sp-Rc, and optionally comprises at least one unit Ar6 which is substituted by at least one group R1 that denotes - Sp-Rc. Very preferably the conjugated polymer comprises at least one unit of formula I wherein U1 and U2 denote CR1R2 and at least two groups R1 and R2 that are attached to the same C atom denote each -Sp-Rc.
Preferred groups Ar1 and Ar2 in formula I are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000028_0001
A1 a A2a A1 b A2b
Especially preferred groups Ar1 and Ar2 are selected from formulae A1 a and A2a.
A first preferred embodiment of the present invention relates to units of formula I wherein k=0. Preferred units of formula I according to this first preferred embodiment are selected from the following subformula
Figure imgf000029_0001
wherein U1 Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula 11 are those wherein U1 denotes CR1R2. In the units of formula I where k>1 the groups Ar1 and Ar2 can be selected such that the resulting indaceno-type groups have trans- or cis- configuration.
A second preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1 , 2 or 3, and the indaceno-type groups have an all-trans-configuration, i.e. one of the two groups Ar1 and Ar2 that are fused to the same group Ar3 is of formula A1 and the other is of formula A2, as exemplarily illustrated below.
Figure imgf000029_0002
trans-configuration.
Preferred units of formula I according to this second preferred embodiment are selected from the following subformulae
Figure imgf000029_0003
Figure imgf000030_0002
wherein U1 , U2, Ar3, Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula I2-I4 are those wherein all of the groups U1 and U2 denote CR1 R2
A third preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1 , 2 or 3, and at least one, preferably all, indaceno-type groups have cis-configuration, i.e. the groups Ar1 and Ar2 that are fused to the same group Ar3 are both of formula A1 or both of formula A2, as exemplarily illustrated below.
Figure imgf000030_0001
r.is-r.nnfim iratinn
This third preferred embodiment includes units of formula I having an "all- cis" configuration as exemplarily shown in formula I5 and I6 below, and units of formula I including both trans-configuration and cis-configuration, as exemplarily shown in formula I7 below.
Preferred units of formula I according to this third preferred embodiment are selected from the following subformulae
Figure imgf000031_0002
wherein U1, U2, Ar3, Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula I5-I7 are those wherein all groups U1 and U2 denote CR1R2.
Especially preferred are units of formula 11 , I2, I3 and I4, very preferred those of formula 11 and I2.
Preferred groups Rc in formula I are selected from formula M
Figure imgf000031_0001
wherein Q1 and Q2 are each independently from one another H, or CnHhn+i wherein n is an integer from 1 to 16, more preferably Chh, C2H5, C3H7 or C4H9, very preferably H or CH3, most preferably CH3.
Preferred groups Rc in formula I are selected from formula M1
Figure imgf000032_0001
Preferred spacer groups Sp in formula I are selected from alkylene with 1 to 30, preferably 1 to 20, C atoms, wherein one or more, but not all, CFh groups are each optionally replaced by -0-, -S-, -C(=0)-, -C(=S)-, -C(=0)- 0-, -0-C(=0)-, -NR0-, -SiR°R00-, -CF2-, -CR°=CR00-, -CY1=CY2- or -CºC- 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 each optionally replaced by F, Cl, Br, I or CN.
Very preferred spacer groups Sp are selected from alkylene with 1 to 20, preferably 5 to 20, more preferably 5 to 16 C atoms.
Preferred groups -Sp-Rc in formula I are selected from formula SM
Figure imgf000032_0002
wherein n is an integer from 1 to 20, preferably 5 to 20, very preferably 8 to 16, and Q1 and Q2 are each independently from one another H, CFh, C2H5, C3FI7 or C4H9, very preferably FI or CFI3, most preferably CFI3.
Preferred groups -Sp-Rc in formula I are selected from formula SM1
Figure imgf000032_0003
wherein n is an integer from 1 to 20, preferably 5 to 20, very preferably 8 to 16. Preferred groups Ar3 in formula I, I2-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000033_0001
A3j A3k A31 A3v A3w A3x wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
W1 , W2, W3 S, O, Se or C=0, preferably S, W4 S, 0, Se, C=0 or NR5,
R5 8 one of the meanings given for R1 above and below.
Preferred groups Ar3 are selected from formulae A3b, A3d, A3f and A3t, very preferably from formulae A3b and A3d.
Further preferred groups Ar3 are selected from formula A3d wherein R5 and R6 denote F.
Further preferred groups Ar3 are selected from formulae A3e and A3f wherein R5 and R6 are different from FI. Preferred groups Ar4 in formula I, 11 -17 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000035_0001
Figure imgf000036_0001
A4v A4w A4x wherein W1, W2, W3 and R5-8 have the meanings given above, V1 denotes CR5 or N, and R9 has one of the meanings given for R5.
Preferred groups Ar4 are selected from formulae A4a, A4b, A4c, A4d, A4f, A4g, A4h, A4i, A4k, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v, very preferably from formula A4a, A4b, A4c, A4d, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v.
Further preferred groups Ar4 are selected from formulae A4r and A4s wherein R5 and R6 are different from H.
Preferred groups Ar5 in formula I, 11 -17 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000037_0001
Figure imgf000038_0001
A5v A5w A5x wherein W1, W2, W3, V1 and R5-9 have the meanings given above, Preferred groups Ar5 are selected from formulae A5a, A5b, A5c, A5d, A5f, A5g, A5h, A5i, A5k, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v, very preferably from formula A5a, A5b, A5c, A5d, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v. Further preferred groups Ar5 are selected from formulae A5r and A5s wherein R5 and R6 are different from H.
Very preferred groups Ar3 in formula I and I2-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000039_0001
A3g1 A3h1 A3h2 A3u1 wherein R5-8 have the meanings given above and below. Very preferred groups Ar3 are selected from formulae A3b1 , A3d1 , A3f1 and A3t1 , very preferably from formulae A3b1 and A3d1 .
Further preferred groups Ar3 are selected from formula A3d1 wherein R5 and R6 denote F.
Further preferred groups Ar3 are selected from formulae A3e1 and A3f1 wherein R5 and R6 are different from H.
Very preferred groups Ar4 in formula I and 11 -17 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000041_0001
Figure imgf000042_0001
A4v1 A4w1 A4x1 wherein R5-9 have the meanings given above and below. Very preferred groups Ar4 are selected from formulae A4a1 , A4b1 , A4c1 , A4d1 , A4f1 , A4g1 , A4h1 , A4i1 , A4k1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u and A4v1 , very preferably from formula A4a1 , A4b1 , A4c1 , A4d1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u1 and A4v1. Further preferred groups Ar4 are selected from formula A4r1 and A4s1 wherein R5 and R6 are different from H.
Very preferred groups Ar5 in formula I and 11-17 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000043_0001
A5g1 A5h1 A5i1
Figure imgf000044_0001
A5v1 A5w1 A5x1 wherein R5-9 have the meanings given above and below. Very preferred groups Ar5 are selected from formulae A5a1 , A5b1 , A5c1 , A5d1 , A5f1 , A5g1 , A5h1 , A5i1 , A5k1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u and A5v1 , very preferably from formula A5a1 , A5b1 , A5c1 , A5d1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u1 and A5v1. Further preferred groups Ar5 are selected from formula A5r1 and A5s1 wherein R5 and R6 are different from H.
Preferred units of formula I and 11-17 are selected from the the group consisting of the following subformulae
Figure imgf000045_0001
 -10-11-12-13 -14 -15 -16-17-18 -19-20 11-21
11-22
11-23
11-24
11-25
11-26
Figure imgf000049_0001
-27 -28-29-30 -31 -32 -SO-
Figure imgf000051_0001
 -3 -4-5 -6 -7 I2-8
12-9 2-10 2-112-12 -13-14-15 -16
Figure imgf000057_0001
-33-34-35-36-37-38 I2-39
Figure imgf000060_0001
I2-40
Figure imgf000060_0002
12-41
Figure imgf000060_0003
12 -42
Figure imgf000060_0004
I2-43
Figure imgf000060_0005
12 -44
Figure imgf000060_0006
35 -57-58-59-60-61
-64-65-66-67 I2-68
12-69
I2-70
12-71
I2-72
Figure imgf000065_0001
65
Figure imgf000066_0001
35
Figure imgf000067_0001


 -11
-12
I5-5
Figure imgf000071_0001
15-6
Figure imgf000071_0002
I5-7
15-8
I5-9
Figure imgf000071_0003
15-10
Figure imgf000071_0004
wherein R1 , R2, R5 and R6 have the meanings given above and below, R3 and R4 have one of the meanings given for R1 and R2 above and below, and the benzene and thiophene rings are optionally substituted in free positions by one or more groups R5, and wherein preferably in at least two groups R1 and R2 and/or at least two groups of R3 and R4, which are attached to the same C atom, denote each -Sp-Rc, and very preferably all groups R1 , R2, R3 and R4 denote -Sp-Rc.
In a preferred embodiment of the present invention, in the repeating units of formula I, 11 -17 and 11 -1 to 15-13 R1 and R2, when being different from - Sp-Rc, are selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1 -SUB6 above.
In another preferred embodiment of the present invention, in the repeating units of formula I, 11 -17 and 11 -1 to 15-13 R1 and R2, when being different from -Sp-Rc, are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4- position, 2,4-positions, 2,4,6-positions or 3,5-positions, or thiophene that is optionally substituted, preferably in 5-position, 4,5-positions or 3,5- positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, most preferably from formulae SUB7-SUB18 above. In a preferred embodiment of the present invention, in the repeating units of formula I, 11-17 and 11-1 to 15-13 at least one sustituent R5-9 denotes - Sp-Rc.
In another preferred embodiment of the present invention, in the repeating units of formula I, 11 -17 and 11 -1 to 15-13 R5-9 are H.
In another preferred embodiment of the present invention, in the repeating units of formula I, 11 -17 and 11 -1 to 15-13 at least one of R5-9 is different from H.
In a preferred embodiment of the present invention, in the repeating units of formula I, 11-17 and 11-1 to 15-13 R5-9, when being different from H, are each independently selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1 -SUB6 above.
In another preferred embodiment of the present invention, in the repeating units of formula I, 11 -17 and 11 -1 to 15-13 R5-9, when being different from FI, are each independently selected are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6-positions or 3,5- positions, or thiophene that is optionally substituted, preferably in 5- position, 4,5-positions or 3,5-positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, more preferably from formulae SUB7-SUB18 above, most preferably from formulae SUB14-SUB18 above.
Preferred aryl and heteroaryl groups R1-9, when being different from H, are each independently selected from the following formulae
Figure imgf000074_0001
Figure imgf000075_0001
35 wherein R21 27, independently of each other, and on each occurrence
identically or differently, denote H, F, Cl, CN, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more Chh groups are each optionally replaced by -0-, -S-, -C(=0)-, -C(=S)-, - C(=0)-0-, -0-C(=0)-, -NR0-, -SiR°R00-, -CF2-, -CR°=CR00-, -CY1=CY2- or - CºC- 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 each optionally replaced by F, Cl, Br, I or CN, and in which one or more CFh or CFh groups are each optionally replaced by a cationic or anionic group.
Very preferred aryl and heteroaryl groups R1-9, when being different from H, are each independently selected from formulae S1 , S4, S5, S7 and S10.
Most preferred aryl and heteroaryl groups R1-9 are each independently selected from formulae SUB7-SUB16 as defined above.
In another preferred embodiment one or more of R1-9 denote a straight- chain, branched or cyclic alkyl group with 1 to 50, preferably 2 to 50, very preferably 2 to 30, more preferably 2 to 24, most preferably 2 to 16 C atoms, in which one or more CFh or CFh groups are replaced by a cationic or anionic group.
The cationic group is preferably selected from the group consisting of phosphonium, sulfonium, ammonium, uronium, thiouronium, guanidinium or heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.
Preferred cationic groups are selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N- dialkylpyrrolidinium, 1 ,3-dialkylimidazolium, wherein "alkyl" preferably denotes a straight-chain or branched alkyl group with 1 to 12 C atoms and very preferably is selected from formulae SUB1 -6 .
Further preferred cationic groups are selected from the group consisting of the following formulae imidazolium 1H-pyrazohum 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium
Figure imgf000077_0001
Figure imgf000078_0001
wherein R1', R2', R3' and R4' denote, independently of each other, H, a straight-chain or branched alkyl group with 1 to 12 C atoms or non
aromatic carbo- or heterocyclic group or an aryl or heteroaryl group, each of the aforementioned groups having 3 to 20, preferably 5 to 15, ring atoms, being mono- or polycyclic, and optionally being substituted by one or more identical or different substituents L as defined above, or denote a link to the respective group R1 9
In the above cationic groups of the above-mentioned formulae any one of the groups R1', R2', R3' and R4' (if they replace a CFh group) can denote a link to the respective group R1 10, or two neighbored groups R1', R2', R3' or R4' (if they replace a CFh group) can denote a link to the respective group R1.
The anionic group is preferably selected from the group consisting of borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, very preferably from phosphate, sulfonate or carboxylate.
Further preferred repeating units of formula I, 11 -17 and 11 -1 to 15-13 are selected from the following preferred embodiments or any combination thereof:
- at least two groups R1 and R2 in the same unit that are attached to the same C, Si or Ge atom denote each -Sp-Rc,
- all groups R1 and R2 in the same unit that are attached to the same C,
Si or Ge atom denote each -Sp-Rc, at least one group R1 in the same unit that is attached to an N atom denotes -Sp-Rc,
all groups R1 in the same unit that are attached to an N atom denotes - Sp-Rc,
k is 0, 1 , 2 or 3, preferably 0, 1 or 2, very preferably 1 ,
U1 and U2 denote independently of each other CR1R2,
W1, W2 and W3 are S or Se, preferably S,
W4 is S or NR°, preferably S,
V1 is CR5,
V1 is N,
Ar1 and Ar2 are selected from formulae A1 a and A2a,
Ar3 is selected from formulae A3b, A3d, A3f and A3t, very preferably from formulae A3b and A3d,
Ar3 is selected from formulae A3b1 , A3d1 , A3f1 and A3t1 , very preferably from formulae A3b1 and A3d1 ,
in Ar3 all substituents R5-8 are H,
in Ar3 at least one, preferably one or two of R5-8 are different from H,
Ar3 is selected from formula A3d1 wherein R3 and R4 denote F,
Ar3 is selected from formulae A3e1 and A3f1 wherein R5 and R6 are different from H,
Ar4 is selected from formulae A4a, A4b, A4c, A4d, A4f, A4g, A4h, A4i, A4k, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v, very preferably from formula A4a, A4b, A4c, A4d, A4I, A4m, A4n, A4o, A4p, A4q, A4u and A4v,
Ar4 is selected from formulae A4a1 , A4b1 , A4c1 , A4d1 , A4f1 , A4g1 , A4h1 , A4i1 , A4k1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u and A4v1 , very preferably from formula A4a1 , A4b1 , A4c1 , A4d1 , A4I1 , A4m1 , A4n1 , A4o1 , A4p1 , A4q1 , A4u1 and A4v1 ,
Ar5 is selected from formulae A5a, A5b, A5c, A5d, A5f, A5g, A5h, A5i, A5k, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v, very preferably from formula A5a, A5b, A5c, A5d, A5I, A5m, A5n, A5o, A5p, A5q, A5u and A5v,
Ar5 is selected from formulae A5a1 , A5b1 , A5c1 , A5d1 , A5f1 , A5g1 , A5h1 , A5i1 , A5k1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u and A5v1 , very preferably from formula A5a1 , A5b1 , A5c1 , A5d1 , A5I1 , A5m1 , A5n1 , A5o1 , A5p1 , A5q1 , A5u1 and A5v1 ,
in one or both of Ar4 and Ar5 all substituents R5-9 are H,
in one or both of Ar4 and Ar5 at least one, preferably one or two of R5-9 are different from H,
R1 and R2 are different from H,
R1 and R2, when being different from H and -Sp-Rc, are each independently selected from F, Cl or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted by one or more F atoms, or alkyl or alkoxy having 1 to 12 C atoms that is optionally fluorinated, more preferably from formulae SUB1 -SUB6 above,
R1 and R2, when being different from FI and -Sp-Rc, are each independently selected from phenyl that is substituted, preferably in 4- position, or in 2,4-positions, or in 2,4,6-positions or in 3,5-positions, with alkyl or alkoxy having 1 to 20 C atoms, preferably 1 to 16 C atoms, very preferably 4-alkylphenyl wherein alkyl is C1 -16 alkyl, most preferably 4-methylphenyl, 4-hexylphenyl, 4-octylphenyl or 4- dodecylphenyl, or 4-alkoxyphenyl wherein alkoxy is C1 -16 alkoxy, most preferably 4-hexyloxyphenyl, 4-octyloxyphenyl or 4-dodecyloxyphenyl or 2,4-dialkylphenyl wherein alkyl is C1 -16 alkyl, most preferably 2,4- dihexylphenyl or 2,4-dioctylphenyl or 2,4-dialkoxyphenyl wherein alkoxy is C1 -16 alkoxy, most preferably 2,4-dihexyloxyphenyl or 2,4- dioctyloxyphenyl or 3,5-dialkylphenyl wherein alkyl is C1-16 alkyl, most preferably 3,5-dihexylphenyl or 3,5-dioctylphenyl or 3,5-dialkoxyphenyl wherein alkoxy is C1 -16 alkoxy, most preferably 3,5-dihexyloxyphenyl or 3,5-dioctyloxyphenyl, or 2,4,6-trialkylphenyl wherein alkyl is C1-16 alkyl, most preferably 2,4,6-trihexylphenyl or 2,4,6-trioctylphenyl or 2,4,6-trialkoxyphenyl wherein alkoxy is C1-16 alkoxy, most preferably 2,4,6-trihexyloxyphenyl or 2,4,6-trioctyloxyphenyl or 4-thioalkylphenyl wherein thioalkyl is C1 -16 thioalkyl, most preferably 4-thiohexylphenyl, 4-thiooctylphenyl or 4-thiododecylphenyl, or 2,4-dithioalkylphenyl wherein thioalkyl is C1 -16 thioalkyl, most preferably 2,4- dithiohexylphenyl or 2,4-dithiooctylphenyl, or 3,5-dithioalkylphenyl wherein thioalkyl is C1 -16 thioalkyl, most preferably 3,5- dithiohexylphenyl or 3,5-dithiooctylphenyl, or 2,4,6-trithioalkylphenyl wherein thioalkyl is C1 -16 thioalkyl, most preferably 2,4,6- trithiohexylphenyl or 2,4,6-trithiooctylphenyl, or from thiophene that is optionally substituted, preferably in 5-position, 4,5-positions or 3,5- positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, most preferably from formulae SUB7-SUB18 above,
R5 9 are H,
at least one of R5-9 denotes -Sp-Rc,
at least one of R5-9 is different from H,
R5-9, when being different from H and -Sp-Rc, are each independently selected from F, Cl, CN or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and
alkylcarbonyloxy, each having up to 20 C atoms and being
unsubstituted or substituted by one or more F atoms, preferably from F, or alkyl or alkoxy having up to 16 C atoms that is optionally fluorinated, more preferably from formulae SUB1 -SUB6 above,
R5-9, when being different from FI and -Sp-Rc, are each independently selected from aryl or heteroaryl, preferably phenyl or thiophene, each of which is optionally substituted with one or more groups L as defined in formula IA and has 4 to 30 ring atoms, preferably from phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6- positions or 3,5-positions, with alkyl or alkoxy having 1 to 20 C atoms, preferably 1 to 16 C atoms, more preferably from formulae SUB7- SUB18 above,
Ar6 is selected from thiophene, thiazole, thieno[3,2-b]thiophene, thiazolo[5,4-d]thiazole, benzene, 2,1 ,3-benzothiadiazole, 1 ,2,3- benzothiadiazole, thieno[3,4-b]thiophene, benzotriazole andr thiadiazole[3,4-c]pyridine, which are optionally substituted by L or R1 or -Sp-Rc,
- Ar6 is substituted by one or two groups -Sp-Rc,
- L denotes F, Cl, CN, NO2, or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated.
Another embodiment of the invention relates to a polymer comprising one or more repeating units of formula I, 11 -17 or 11-1 to 15-13 and optionally one or more units Ar6, wherein at least one of the units of formula and the units Ar6 is at least monosubstituted by -Sp-Rc.
Preferred polymers are selected from the following preferred embodiments or any combination thereof:
- in at least one unit of formula I, 11 -17 or 11 -1 to 15-13, preferably in all of these units, at least two groups R1 and R2 that are attached to the same C, Si or Ge atom denote each -Sp-Rc,
- in at least one unit of formula I, 11 -17 or 11 -1 to 15-13, preferably in all of these units, all groups R1 and R2 in the unit that are attached to the same C, Si or Ge atom denote each -Sp-Rc,
- in at least one unit of formula I, 11 -17 or 11 -1 to 15-13, preferably in all of these units, at least one group R1 in the unit that is attached to an N atom denotes -Sp-Rc,
- in at least one unit of formula I, 11 -17 or 11 -1 to 15-13, preferably in all of these units, all groups R1 in the unit that are attached to an N atom denotes -Sp-Rc,
- at least one unit Ar6 is at least monosubstituted, preferably mono- or disubstituted, by -Sp-Rc,
- all units Ar6 are at least monosubstituted, preferably mono- or
disubstituted, by -Sp-Rc,
- the units Ar6 are not substituted by -Sp-Rc. In a preferred embodiment the polymer comprises one or more units Ar6, which preferably have electron donor properties, and are selected from the group consisting of the formulae D1 -D151 and their mirror images
Figure imgf000083_0001

Figure imgf000085_0001
(D47) (D48)
Figure imgf000086_0001
(D57) (D58)

(D75) (76)
Figure imgf000089_0001
(D82)
Figure imgf000090_0001
Figure imgf000091_0001
 (D104) (D105) (D106)
Figure imgf000093_0001
(D119) (D120) (D121 ) (D122)
Figure imgf000094_0001
(D139) (D140)
(D147) (D148) wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of the substituents R1 1-18 denotes Sp-Rc. Preferred units are selected from formulae D1 , D7, D10, D1 1 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D1 1 1 , D139, D140, D141 , D146 or D150 wherein preferably at least one of R11 18 is different from H, and preferably at least one of R1 1-18 denotes Sp-Rc.
In another preferred embodiment the polymer comprises one or more units Ar6, which preferably have electron acceptor properties, and are selected from the group consisting of the formulae A1 -A103 and their mirror images
Figure imgf000098_0001
Figure imgf000099_0001

Figure imgf000101_0001
 02
Figure imgf000103_0001
Figure imgf000104_0001
 wherein R11, R12, R13, R14, R15 and R16 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of the substituents R1 1-18 denotes Sp-Rc.
Preferred units are selected from formulae A1 , A6, A7, A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103 wherein preferably at least one of R1 1-14 is different from H, and preferably at least one of R1 1-18 denotes Sp-Rc.
In a further preferred embodiment, the polymer comprises one or more units Ar6 which are selected from the group consisting of the formulae Sp1 -Sp18 and their mirror images
Sp1
Sp2
Sp3
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000107_0002
Figure imgf000107_0003
Figure imgf000107_0004
Figure imgf000107_0005
Figure imgf000107_0006
Figure imgf000107_0007
Figure imgf000108_0001
Figure imgf000108_0002
Figure imgf000108_0003
Figure imgf000108_0004
Figure imgf000108_0005
Figure imgf000108_0006
Sp17
Sp18
wherein R11, R12, R13, R14 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of R1 1-14 denotes Sp-
In the formulae Sp1 to Sp17 preferably R11 and R12 are H. In formula Sp18 preferably R1 1-14 are H or F. Very preferred are units selected from formulae Sp1 , Sp2, Sp6, Sp10,
Sp11 , Sp12, Sp13 and Sp14, wherein preferably one of R11 and R12 is FI or both R11 and R12 are FI.
Further preferred are polymers comprising, preferably consisting of, one or more, preferably two or more, units of formula I, 11 -17 or or 11 -1 to 15-13, and one or more units Ar6 selected from the following groups
A2) the group consisting of the formulae D1 -D151 , very preferably from the formulae D1 , D7, D10, D11 , D19, D22, D29, D30, D35, D36,
D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111 , D139, D140, D141 , D146 and D150,
and/or
B2) the group consisting of the formulae A1 -A103, very preferably from the formulae A1 , A6, A7, A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103,
and/or C2) the group consisting of the formulae Sp1 -Sp18, very preferably of the formulae Sp1 , Sp2, Sp6, Sp10, Sp11 , Sp12, Sp13 and Sp14.
In a preferred embodiment the polymer comprises one or more of the units of formula I, 11-17 or or 11 -1 to 15-13 which are at least monosubstituted by - Sp-Rc.
In another preferred embodiment the polymer comprises one or more of the units Ar6 which are at least monosubstituted by -Sp-Rc.
In another preferred embodiment, the polymer further comprises one or more units selected from -CY1=CY2- and -CºC-, wherein Y1 and Y2 are independently of each other H, F, Cl or CN. In another preferred embodiment, the polymer comprises, very preferably consists of, one or more units selected from the following groups
1A) the group consisting of units of formula I, 11 -17 and or 11 -1 to 15-13 which are selected from electron acceptor units,
1 D) the group consisting of formula I, 11 -17 and 11 -1 to 15-13 which are selected from electron donor units,
2A) the group consisting of units Ar6 which are selected from electron acceptor units, preferably selected from the group consisting of formulae A1 -A103,
2D) the group consisting of units Ar6 which are selected from electron donor units, preferably selected from the group consisting of formulae D1 -D151 ,
3) the group consisting of units Ar6 which are selected from spacer units, preferably selected from the group consisting of formulae Sp1 -Sp18. and wherein the polymer contains at least one unit selected from groups 1A and 1 D, and the polymer contains at least one unit of group 1 A, 1 D, 2A, 2D or 3 which is at least monosubstituted by -Sp-Rc.
Preferred polymers comprise one or more units of group 1 D and one or more units of group 2A. Further preferred polymers comprise one or more units of group 1 A and one or more units of group 2D. Further preferred polymers comprise one or more units of group 1 D and one or more units of group 2D, and optionally one or more units selected from group 3.
Further preferred polymers comprise one or more units of group 1A and one or more units of group 2A, and optionally one or more units selected from group 3.
Further preferably the polymer comprises one or more units selected from groups 1 D and 2D, one or more units selected from groups 1 A and 2A, and one or more units selected from the group 3.
Further preferably the polymer comprises, preferably consists of, one or more, preferably two or more, repeating units of formula 111 and/or M2, and optionally one or more repeating units of formula M3:
-(C1)a-U-(C2)b-(C3)c-(CV in
-(C1)a-(C2)b-U-(C3)c-(CV M2
-(C1)a-(C2)b-(C3)c-(CV M3 wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
U a unit selected from formula I, 11 -17 or 11 -1 to 15-13 as
defined above and below, preferably selected from groups 1A and 1 D,
C1-4 distinct units having one of the meanings of Ar6 as defined
above and below, preferably selected from groups 2A, 2D and 3 as defined above and below, a, b, c, d 0 or 1 , wherein in formula M3 a+b+c+d>1. and wherein the polymer contains at least one unit of formula 111 , M2 or M3 wherein at least one of U and C1 4 is at least monosubstituted by -Sp-Rc.
Preferably the polymer comprises one or more repeating units of formula 111 or M2 wherein a+b+c+d>1. Further preferably the polymer comprises one or more repeating units of formula 111 wherein b=1 and a=c=d=0 and one or more repeating units of formula M3 wherein a=b=0 and c=d=1.
Further preferably the polymer comprises two or more distinct repeating units of formula 111 wherein b=1 and a=c=d=0.
Further preferably C1, C2, C3 and C4 are selected from groups 2A, 2D and 3 as defined above and below. Further preferably the polymer is selected of formula III:
Figure imgf000112_0001
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
A a unit of formula 111 or M2,
B, C, D, E a unit of formula 111 , M2 or M3, x > 0 and < 1 , v, w, y, z > 0 and < 1 , v+w+x+y+z 1 , and n an integer >1 , preferably >5, and wherein at least one of A-E is at least monosubstituted by -Sp-Rc.
Further preferably the polymer comprises, very preferably consists of, one or more units selected from the group consisting of the following formulae and their mirror images
-(U)- U1
-(U-Sp)- U2
-(Sp-U-Sp)- U3
-(D-Sp)- U4
-(A-Sp)- U5
-(Sp-D-Sp)- U6
-(Sp-A-Sp)- U7
-(A-D)- U8
-(D)- U9
-(Sp-D-Sp-D)- U10
-(A)- U1 1
-(Sp-A-Sp-A)- U12 wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings U the meaning given in formula 111 ,
D a donor unit selected from groups 1 D and 2D as defined above,
A an acceptor unit selected from groups 1A and 2A as defined above,
Sp a spacer unit selected from the group 3 as defined above, and wherein the polymer contains at least one unit U, D, A or Sp which is at least monosubstituted by -Sp-Rc.
Preferred polymers are selected from formulae Pi-Px
-[(U-Sp]n- Pi
-[(U-Sp)x-(Ar6-Sp)y]n- Pii
-[(U-Sp)x-(A-Sp)y]n- Piii
-[(U-Sp)x-(D-Sp)y]n- Piv
-[(U-D)x-(U-Sp)y]n- Pv
-[(U-A)x-(U-Sp)y]n- Pvi
-[(D)x-(Sp-U-Sp)y]n- Pvii
-[(A)x-(Sp-U-Sp)y]n- Pviii
-[D-A]n- Pix
-[(D-Sp)x-(A-Sp)y]n- Pviii
-[A-D-A]n- Pix
-[Sp-U1-Sp-U2]n- Px wherein A, D and Sp are as defined in formulae U2-U12, A, D and Sp can each, in case of multiple occurrence, also have different meanings, U1 and U2 have one of the meanings given for U and are different from each other, x and y denote the molar fractions of the corresponding units, x and y are each, independently of one another, a non-integer >0 and <1 , with x+y=1 , and n is an integer >1 , and wherein the polymer contains at least one unit U, D, A or Sp which is at least monosubstituted by -Sp-Rc.
Further preferred are repeating units of formula U2-U12 and polymers of formulae Pi-Px wherein
a) the donor units D and 2D are selected from the group consisting of the formulae D1-D151 , very preferably of the formulae D1 , D7, D10, D11 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87,
D88, D89, D93, D94, D106, D111 , D139, D140, D141 , D146 and D150,
b) the acceptor units A and 2A are selected from the group consisting of the formulae A1 -A103, very preferably of the formulae A1 , A6, A7,
A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103,
and
c) the spacer units Sp are selected from the group consisting of the
formulae Sp1 -Sp18, very preferably of the formulae Sp1 , Sp2, Sp6, Sp10, Sp11 , Sp12, Sp13 and Sp14.
Very preferred polymers are selected from the following subformulae
Figure imgf000115_0001
wherein Rc, Sp, x, y and n have the meanings given above and below, Rc is preferably selected of formula M, very preferably of formula M1 , and Sp- Rc is preferably selected of formula SM, very preferably of formula SM1.
Further preferably the polymer is selected of formula IV
RE1-chain-RE2 IV wherein“chain” denotes a polymer chain selected from formulae III, Pi-Px, or P1 -P13, and RE1 and RE2 have independently of each other one of the meanings of L as defined above, or denote, independently of each other,
H, F, Br, Cl, I, -CH2CI, -CHO, -CR'=CR"2, -SiR'R"R"', -SiR'X'X", -SiR'R'X', - SnR'R"R"', -BR'R", -B(OR')(OR"), -B(OH)2, -0-S02-R', -CºCH, -CºC-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 preferably denote alkyl with 1 to 12 C atoms, and two of R', R" and R'" may also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group with 2 to 20 C atoms together with the respective hetero atom to which they are attached.
Preferred endcap groups RE1 and RE2 are H, C1-20 alkyl, or optionally substituted C6-12 aryl or C2-10 heteroaryl, very preferably H or phenyl.
In the polymers according to the present invention the indices v, w, x, y and z denote the mole fraction of the corresponding repeating units, such as units A-E in formula III, and n denotes the degree of polymerisation or total number of repeating units. These formulae include block copolymers, random or statistical copolymers and alternating copolymers, as well as homopolymers for the case when x>0 and v=w=y=z=0.
In the polymers according to the present invention wherein one of v, w, y and z is not 0 and the others of v, w, y and z are 0, x and the one of v, w, y and z which is not 0 are each preferably from 0.1 to 0.9, very preferably from 0.3 to 0.7.
In the polymers according to the present invention wherein two of v, w, y and z are not 0 and the others of v, w, y and z are 0, x and those of v, w, y and z which are not 0 are each preferably from 0.1 to 0.8, very preferably from 0.2 to 0.6.
In the polymers according to the present invention wherein three of v, w, y and z are not 0 and the others of v, w, y and z are 0, x and those of v, w, y and z which are not 0 are each preferably from 0.1 to 0.7, very preferably from 0.2 to 0.5.
In the polymers according to the present invention wherein all of v, w, y and z are not 0, x, v, w, y and z are each preferably from 0.1 to 0.6, very preferably from 0.2 to 0.4. In the polymers according to the present invention, the total number of repeating units n is preferably from 2 to 10,000, very preferably from 5 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. The invention further relates to monomers of formula V1 or V2
RR1-(C1)a-U-(C2)b-(C3)c-(C4)d-RR2 V1
RR1-(C1)a-(C2)b-U-(C3)c-(C4)d-RR2 V2 wherein U, C1 4, a, b, c and d have the meanings of formula 111 , or one of the preferred meanings as described above and below, and RR1 and RR2 are independently of each other selected from the group consisting of H, which is preferably an activated C-H bond, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, -SiMe2F, -SiMeF2, -O-SO2Z1, -B(OZ2)2, - CZ3=C(Z3)2, -CºCH, - CºCSi(Z1)3, -ZnX° and -Sn(Z4)3, wherein X° is halogen, Z1-4 are selected from the group consisting of alkyl and aryl, preferably C-M O alkyl and C6-i2 aryl, each being optionally substituted, and two groups Z2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, and wherein at least one of RR1 and RR2 is different from H, and preferably both of RR1 and RR2 are different from H.
Very preferred are monomers of formula V1 and V2 wherein a+b+c+d >1.
Further preferred are monomers of formula V1 wherein a+b+c+d=0.
Further preferred are monomers selected from the following subformulae
RR1 _U-RR2 Vi a RR1-C1-U-C2-RR2 V1 b
RR1-C1-U-RR2 V1 c
RR1-U-C2-RR2 V1 d wherein U, C1, C2, RR1 and RR2 are as defined in formula V1 .
Further preferred are monomers of formula V1 , V2 and V1 a-d wherein RR1 and RR2 are selected from Br, -B(OZ2)2 and Sn(Z4)3.
Further preferred are monomers of of formulae V1 , V2 and V1 a-V1 d wherein C1 and/or C2 are selected from groups A2, A3, A4, D2 and E2 as defined above.
Further preferred are monomers of formula V3 RRI_U*-Rr2 V3 wherein RR1 and RR2 have the meanings given above and below, and preferably denote Br, B(OZ2)2 or Sn(Z4)3, and U* is a unit selected from formulae P1 -P8 or PN1 -PN6 wherein n is 1 .
Further preferred units, monomers and polymers of formulae I, 11 -17, 11 -1 to 15-13, 111 , M2, M3, III, Pi-Px, P1 -P13, IV, V1 -V3, V1 a-d and 11 -1 to 15-13 are selected from the following embodiments, including any combination thereof:
n³5,
- n is from 5 to 1 ,000, most preferably from 10 to 2,000,
- a=b=1 and c and d are independently of each other 0, 1 or 2, preferably 0 or 1 , very preferably 0,
- a is 2, b is 1 or 2, c is 0 or 1 , preferably 0, and d is 0, 1 or 2, preferably 0 or 1 , very preferably 0,
- b=1 and a=c=d=0, - a=b=0 and c=d=1.
- one or more of R1 1-18 is different from H and is selected from alkyl,
alkoxy or thiaalkyl, all of which are straight-chain or branched, have 1 to 25, preferably 1 to 18 C atoms, and are optionally fluorinated,
- one or more of R1 1-18 is different from H and is selected from F, Cl, CN, - C(=0)-Rn, -C(=0)-0Rn, -C(=0)-NHRn and -C(=0)-NRnRm, wherein Rm and Rn are independently of each other straight-chain or branched alkyl with 1 to 25, preferably 1 to 18 C atoms that is optionally fluorinated,
- one or more of R11-18 is different from H and is selected from the group consisting of aryl, heteroaryl, aryloxy, heteroaryloxy, arylalkyl and heteroarylalkyl, each of which has 4 to 20 ring atoms and optionally contains fused rings and is unsubstituted or substituted by one or more groups L as defined in formula I,
- RE1 and RE2 are selected from H, C1 -20 alkyl, or optionally substituted Ce- 12 aryl or El-10 heteroaryl, very preferably H or phenyl,
- RR1 and RR2 denote Br, B(OZ2)2 or Sn(Z4)3, wherein Z2 and Z4 are as defined in formula V1.
The polymers according to 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 of the present invention can be prepared from the
corresponding monomers, which are preferably selected from formula V1 - V3 or V1 a-d, for example by copolymerising one or more monomers of formula V1 -V3 or V1 a-d with each other or with one or monomers of the following formulae in an aryl-aryl coupling reaction
RR1-C1_RR2 Ml
RR1 -C2_Rr2 M M
RR1-C3_RR2 RR1 _C4_RR2 M|V wherein C1 4, RR1 and RR2 have the meanings given in formula M2 and V1 or one of the preferred meanings given above and below.
For example, the polymers can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, C-H activation coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling, Stille 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 selected from
formulae V1 -V3, V1 a-d and MI-MIV as described above.
Another aspect of the invention is a process for preparing an polymer by coupling one or more identical or different monomers selected from
formulae V1 , V2, V3 and V1 a-d with each other and/or with one or more co-monomers, preferably selected from formulae MI-MIV, in a
polymerisation reaction, preferably in an aryl-aryl coupling reaction.
Preferred aryl-aryl coupling methods used in the synthesis methods as 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 et al., Prog. Polym. Sci., 1993,
17, 1153-1205, or WO 2004/022626 A1. Stille coupling is described for example in Z. Bao et al., J. Am. Chem. Soc., 1995, 117, 12426-12435 and C-H activation is described for example in M. Leclerc et al, Angew. Chem.
Int. Ed., 2012, 51 , 2068-2071.For example, when using Yamamoto coupling, educts having two reactive halide groups are preferably used.
When using Suzuki coupling, educts having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, educts having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, educts having two reactive organozinc groups or two reactive halide groups are preferably used.
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(Ph3P)4. Another preferred phosphine ligand is tris(o/f/?o-tolyl)phosphine, i.e. Pd(o-Tol3P)4. 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(dibenzylideneacetone)dipalladium(0),
bis(dibenzylideneacetone)palladium(0), or Pd(ll) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(o/f/?o- tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki coupling is performed in the presence of a base, for example sodium carbonate, potassium
carbonate, cesium 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(0). As alternatives to halogens as described above, leaving groups of formula -O-SO2Z0 can be used wherein Z° is an alkyl or aryl group, preferably C-MO alkyl or Ce-12 aryl. Particular examples of such leaving groups are tosylate, mesylate and triflate. Especially suitable and preferred synthesis methods of the repeating units of formula I and the conjugated polymers comprising them are illustrated in the synthesis schemes shown hereinafter.
Scheme 1
Figure imgf000125_0001
wherein Pg means a protecting group, T11 and T12 are terminal groups such as H, F, Cl, Br, I, B(OR)2, SnR3, ZnX, MgX, and Ar3 5, Sp and Rc have the meanings as given above and below, Sp is for example (CH2)n with n being an integer from 1 to 20, and Rc is for example 2,3-dimethyl-N- maleimide.
Novel methods of preparing repeating units of formula I and monomers and polymers comprising them as described above and below are another aspect of the invention.
The polymer according to the present invention can also be used in compositions, for example together with monomeric or polymeric compounds having charge-transport, semiconducting, electrically conducting, photoconducting and/or light emitting semiconducting properties, or for example with compounds having hole blocking or electron blocking properties for use as interlayers or charge blocking layers in PSCs or OLEDs.
Thus, another aspect of the invention relates to a composition comprising one or more polymers according to the present invention and one or more small molecule compounds and/or polymers having one or more of a charge-transport, semiconducting, electrically conducting,
photoconducting, hole blocking and electron blocking property.
The invention further relates to a composition comprising one or more polymers according to the present invention, and further comprising one or more p-type organic semiconductors, preferably selected from conjugated polymers.
The invention further relates to a composition comprising a first n-type semiconductor which is a polymer according to the present invention, a second n-type semiconductor, which is preferably a fullerene or fullerene derivative, a non-fullerene acceptor small molecule, or an n-type
conjugated polymer, and a p-type semiconductor, which is preferably a conjugated polymer.
In a preferred embodiment the second n-type OSC compound is a non- fullerene acceptor (NFA) small molecule having an A-D-A structure as described above with an electron donating polycyclic core and two terminal electron withdrawing groups attached thereto.
Suitable and preferred NFA small molecules for use as second n-type OSC in this preferred embodiment are for example those disclosed in Y.
Lin et al., Adv. Mater., 2015, 27, 1170; H. Lin et al., Adv. Mater., 2015, 27, 7299; N. Qiu et al., Adv. Mater., 2017, 29, 1604964; CN104557968 A and CN105315298 A, furthermore those disclosed in WO 2018/007479 A1.
In another preferred embodiment the second n-type OSC compound is a fullerene or substituted fullerene. The fullerene is for example an indene-C6o-fullerene bisadduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C6o fullerene, also known as "PCBM-C60" or "C60PCBM", as disclosed for example in G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Science 1995, Vol. 270, p. 1789 ff and having the structure shown below, or structural analogous compounds with e.g. a C61 fullerene group, a C70 fullerene group, or a C71 fullerene group, or an organic polymer (see for example Coakley, K. M. and McGehee
Figure imgf000127_0001
Preferably the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene of formula Full-I to form the active layer in an OPV or OPD device,
Figure imgf000127_0002
Cn denotes a fullerene composed of n carbon atoms,
optionally with one or more atoms trapped inside,
Adduct1 is a primary adduct appended to the fullerene Cn with any connectivity,
Adduct2 is a secondary adduct, or a combination of secondary adducts, appended to the fullerene Cn with any connectivity, k is an integer > 1 , and
I is 0, an integer > 1 , or a non-integer > 0.
In the formula Full-I and its subformulae, k preferably denotes 1 , 2, 3 or, 4, very preferably 1 or 2.
The fullerene Cn in formula Full-I and its subformulae may be composed of any number n of carbon atoms Preferably, in the compounds of formula XII and its subformulae the number of carbon atoms n of which the fullerene Cn is composed is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70. The fullerene Cn in formula Full-I and its subformulae is preferably selected from carbon based fullerenes, endohedral fullerenes, or mixtures thereof, very preferably from carbon based fullerenes.
Suitable and preferred carbon based fullerenes include, without limitation, (C6o-ih)[5,6]fullerene, (C7o-D5h)[5,6]fullerene, (C76-D2*)[5,6]fullerene, (Cs4-
D2*)[5,6]fullerene, (C84-D2d)[5,6]fullerene, or a mixture of two or more of the aforementioned carbon based fullerenes.
The endohedral fullerenes are preferably metallofullerenes. Suitable and preferred metallofullerenes include, without limitation, l_a@C6o, l_a@C82, Y@Cs2, SC3N@C8O, Y3N@C8O, SC3C2@C8O or a mixture of two or more of the aforementioned metallofullerenes.
Preferably the fullerene Cn is substituted at a [6,6] and/or [5,6] bond, preferably substituted on at least one [6,6] bond.
Primary and secondary adducts, named "Adductl" and 'Adduct 2" in formula Full-I and its subformulae, are each preferably selected from the following formulae
Figure imgf000129_0001
Figure imgf000130_0001
wherein
Ars1, ArS2 denote, independently of each other, an aryl or heteroaryl group with 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic, and which is optionally substituted by one or more identical or different substituents having one of the meanings of L as defined above and below, Rsi RS2 RS3 RS4 anc| RS5 independently of each other denote H, CN or have one of the meanings of L as defined above and below, and i is an integer from 1 to 20, preferably from 1 to 12. Preferred compounds of formula Full-I are selected from the following subformulae: Full-la
Full-lb
Figure imgf000131_0001
Full-lc
Figure imgf000131_0002
Full-Id
Figure imgf000132_0001
Full-le
Figure imgf000132_0002
Full-lf
RS1, RS2, RS3, RS4 RS5 and RS6 independently of each other denote H or have one of the meanings of Rs as defined above and below.
Most preferably the fullerene is PCBM-C60, PCBM-C70, bis-PCBM-C60, bis-PCBM-C70, ICMA-c60 (1 4'-dihydro-naphtho[2', 3': 1 ,2][5,6]fullerene- C60), ICBA, 0QDM-C6O (1 ',4'-dihydro-naphtho[2',3': 1 ,9][5,6]fullerene-C60- Ih), or bis-oQDM-C60.
In another preferred embodiment the second n-type OSC compound is a small molecule which does not contain a fullerene moiety, and which is selected from naphthalene or perylene carboximide derivatives.
Preferred naphthalene or perylene carboximide derivatives for use as n-type OSC compounds are described for example in Adv. Sci. 2016, 3, 16001 17, Adv. Mater. 2016, 28, 8546-8551 , J. Am. Chem. Soc., 2016, 138, 7248- 7251 and J. Mater. Chem. A, 2016, 4, 17604.
Preferred n-type OSC compounds of this preferred embodiment are selected from the following formulae
Figure imgf000134_0001
I5 I6
Figure imgf000138_0001
I7
Figure imgf000140_0001
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R1-10 Z1 , H, F, Cl, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CFh groups are optionally replaced by -0-, -S-, -C(=0)-, -C(=S)-, - C(=0)-0-, -0-C(=0)-, -NR0-, -SiR°R00-, -CF2-, -CR°=CR00-, - CY1=CY2- or -CºC- in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more FI atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CFh or CFh groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Z1 an electron withdrawing group, preferably having one of the preferred meanings as given above for formula T, very preferably CN, Y1, Y2 H, F, Cl or CN,
L F, Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, R°, OR0,
SR°, -C(=0)X°, -C(=0)R°, -C(=0)-0R°, -0-C(=0)-R°, -NH2, - NHR°, -NR°R00, -C(=0)NHR°, -C(=0)NR°R°°, -SO3R0, - SO2R0, -OH, -NO2, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30, preferably 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, preferably F, -CN, R°, -OR0, -SR°, -C(=0)-R°, -C(=0)-OR°, -0-C(=0)-R°, -O-C(=O)-OR0, - C(=0)-NHR°, or -C(=O)-NR0R00,
T1-4 -0-, -S-, -C(=0)-, -C(=S)-, -CR°R00-, -SiR°R00-, -NR0-, - CR°=CR00- or -CºC-,
G C, Si, Ge, C=C or a four-valent aryl or heteroaryl group that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups R1 or L,
^n1-n4 independently of each other, and on each occurrence
identically or differently arylene or heteroarylene that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups R1 or L, or CY1=CY2 or -CºC-, e, f, g, h 0 or an integer from 1 to 10. In another preferred embodiment the second n-type OSC compound is a conjugated OSC polymer. Preferred n-type OSC polymers are described, for example, in Acc. Chem. Res., 2016, 49 (1 1 ), pp 2424-2434 and WO 2013/142841 A1 . Preferred n-type conjugated OSC polymers for use as second n-type OSC compound in this preferred embodiment comprise one or more units derived from perylene or naphthalene are poly[[N,N'-bis(2- octyldodecyl)naphthalene-1 ,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'- bithiophene)], poly[[N,N'-bis(2-hexyldecyl)naphthalene-1 ,4,5,8- bis(dicarboximide)-2,6-diyl]-alt-5,5'-thiophene].
The composition according to the present invention can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the compounds and/or 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 polymers according to the present invention or compositions 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. Further suitable and preferred solvents used include 1 ,2,4-trimethylbenzene,
1 ,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, indane, 1 ,5- dimethyltetraline, decalin, 1-methylnaphthalene, 2,6-lutidine, 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, N,N-dimethylaniline, ethyl benzoate, 1 -fluoro-3,5-dimethoxy- benzene, 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- chlorofluoro-benzene, 1 -chloro-2,5-difluorobenzene, 4- chlorofluorobenzene, chloro-benzene, o-dichlorobenzene, 2- chlorofluorobenzene, p-xylene, m-xylene, o-xylene, a mixture of o-, m-, and p-xylene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, tetrahydrofuran, morpholine, 1 ,4-dioxane, 2-methylthiophene, 3-methylthiophene, chloroform, 1 ,2-dichloroethane, dichloromethane, carbon tetrachloride,
I ,2-dichloroethane, 1 ,1 ,1 -trichloroethane, 1 , 1 ,2,2-tetrachloroethane, acetone, methylethylketone, propiophenone, acetophenone,
cyclohexanone, ethyl acetate, n-butyl acetate, ethyl benzoate, ethyl benzoate, dimethylacetamide, dimethylsulfoxide, or mixtures of the aforementioned. Solvents with relatively low polarity are generally preferred. Examples of especially preferred solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1 -methylnaphthalene, 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, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1 ,5-dimethyltetraline,
propiophenone, acetophenone, tetralin, 2-methylthiophene, 3- methylthiophene, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene, 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 compositions 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, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.
In a composition according to the present invention comprising a first polymer, which is polymer according to the present invention, and a second conjugated polymer, the ratio 1st polymer: 2nd polymer is preferably from 5:1 to 1 :5 by weight, more preferably from 3:1 to 1 :3 by weight, most preferably 2:1 to 1 :2 by weight.
The composition according to the present invention may also comprise a polymeric binder, preferably from 0.001 to 95% by weight. Examples of binder include polystyrene (PS), polydimethylsilane (PDMS),
polypropylene (PP) and polymethylmethacrylate (PMMA).
A binder to be used in the formulation as described before, which is preferably a polymer, may comprise either an insulating binder or a semiconducting binder, or mixtures thereof, may be referred to herein as the organic binder, the polymeric binder or simply the binder.
Preferably, the polymeric binder comprises a weight average molecular weight in the range of 1 ,000 to 5,000,000 g/mol, especially 1 ,500 to 1 ,000,000 g/mol and more preferable 2,000 to 500,000 g/mol. Surprising effects can be achieved with polymers having a weight average molecular weight of at least 10,000 g/mol, more preferably at least 100,000 g/mol.
In particular, the polymer can have a polydispersity index Mw/Mn in the range of 1.0 to 10.0, more preferably in the range of 1.1 to 5.0 and most preferably in the range of 1.2 to 3. Preferably, the inert binder is a polymer having a glass transition temperature in the range of -70 to 160°C, preferably 0 to 150°C, more preferably 50 to 140°C and most preferably 70 to 130°C. The glass transition temperature can be determined by measuring the DSC of the polymer (DIN EN ISO 11357, heating rate 10°C per minute).
The weight ratio of the polymeric binder to the OSC polymer according to the present invention is preferably in the range of 30:1 to 1 :30, particularly in the range of 5:1 to 1 :20 and more preferably in the range of 1 :2 to 1 : 10.
According to a preferred embodiment the binder preferably comprises repeating units derived from styrene monomers and/or olefin monomers. Preferred polymeric binders can comprise at least 80 %, preferably 90 % and more preferably 99 % by weight of repeating units derived from styrene monomers and/or olefins.
Styrene monomers are well known in the art. These monomers include styrene, substituted styrenes with an alkyl substituent in the side chain, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
Olefin monomers consist of hydrogen and carbon atoms. These
monomers include ethylene, propylene, butylenes, isoprene and 1 ,3- butadiene.
According to a preferred embodiment of the present invention, the polymeric binder is polystyrene having a weight average molecular weight in the range of 50,000 to 2,000,000 g/mol, preferably 100,000 to 750,000 g/mol, more preferably in the range of 150,000 to 600,000 g/mol and most preferably in the range of 200,000 to 500,000 g/mol.
Further examples of suitable binders are disclosed for example in US 2007/0102696 A1. Especially suitable and preferred binders are described in the following. The binder should preferably be capable of forming a film, more preferably a flexible film. Suitable polymers as binders include poly(1 ,3-butadiene), polyphenylene, polystyrene, poly(a-methylstyrene), poly(a-vinylnaphtalene),
poly(vinyltoluene), polyethylene, cis-polybutadiene, polypropylene, polyisoprene, poly(4-methyl-1-pentene), poly (4-methylstyrene), poly(chorotrifluoroethylene), poly(2-methyl-1 ,3-butadiene), poly(p- xylylene), poly(a-a-a’-a’ tetrafluoro-p-xylylene), poly[1 ,1 -(2-methyl propane)bis(4-phenyl)carbonate], poly(cyclohexyl methacrylate), poly(chlorostyrene), poly(2,6-dimethyl-1 ,4-phenylene ether),
polyisobutylene, poly(vinyl cyclohexane), poly(vinylcinnamate), poly(4- vinylbiphenyl), 1 ,4-polyisoprene, polynorbornene, poly(styrene-block- butadiene); 31 % wt styrene, poly(styrene-block-butadiene-block-styrene); 30% wt styrene, poly(styrene-co-maleic anhydride) (and
ethylene/butylene) 1 - 1.7% maleic anhydride, poly(styrene- block- ethylene/butylene-block-styrene) triblock polymer 13% styrene,
poly(styrene- block-ethylene- propylene -block-styrene) triblock polymer 37% wt styrene, poly(styrene- block-ethylene/butylene-block-styrene) triblock polymer 29% wt styrene, poly(l-vinylnaphthalene), poly(1 - vinylpyrrolidone-co-styrene) 64% styrene, poly(1 -vinylpyrrolidone-co-vinyl acetate) 1.3:1 , poly(2-chlorostyrene), poly(2-vinylnaphthalene), poly(2- vinylpyridine-co-styrene) 1 :1 , poly(4,5-Difluoro-2,2-bis(CF3)-1 ,3-dioxole- co-tetrafluoroethylene) Teflon, poly(4-chlorostyrene), poly(4-methyl-1 - pentene), poly(4-methylstyrene), poly(4-vinylpyridine-co-styrene) 1 :1 , poly(alpha-methylstyrene), poly(butadiene-graft-poly(methyl acrylate-co- acrylonitrile)) 1 :1 :1 , poly(butyl methacrylate-co-isobutyl methacrylate) 1 :1 , poly(butyl methacrylate-co-methyl methacrylate) 1 :1 ,
poly(cyclohexylmethacrylate), poly(ethylene-co-1 -butene-co-1 -hexene)
1 :1 :1 , poly(ethylene-co-ethylacrylate-co-maleic anhydride); 2% anhydride, 32% ethyl acrylate, poly(ethylene-co-glycidyl methacrylate) 8% glycidyl methacrylate, poly(ethylene-co-methyl acrylate-co-glycidyl meth-acrylate) 8% glycidyl metha-crylate 25% methyl acrylate,
poly(ethylene-co-octene) 1 :1 , poly(ethylene-co-propylene-co-5-methylene-
2-norbornene) 50% ethylene, poly(ethylene-co-tetrafluoroethylene) 1 :1 , poly(isobutyl methacrylate), poly(isobutylene), poly(methyl methacrylate)- co-(fluorescein O-methacrylate) 80% methyl methacrylate, poly(methyl methacrylate-co-butyl methacrylate) 85% methyl methacrylate, poly(methyl methacrylate-co-ethyl acrylate) 5% ethyl acrylate, poly(propylene-co- butene) 12% 1 -butene, poly(styrene-co-allyl alcohol) 40% allyl alcohol, poly(styrene-co-maleic anhydride) 7% maleic anhydride, poly(styrene-co- maleic anhydride) cumene terminated (1.3:1 ), poly(styrene-co-methyl methacrylate) 40% styrene, poly(vinyltoluene-co-alpha-methylstyrene)
1 :1 , poly-2 -vinylpyridine, poly-4-vinylpyridine, poly-alpha-pinene, polymethylmethacrylate, polybenzylmethacrylate, polyethylmethacrylate, polyethylene, polyethylene terephthalate, polyethylene-co-ethylacrylate 18% ethyl acrylate, polyethylene-co-vinylacetate 12% vinyl acetate, polyethylene-graft-maleic anhydride 0.5% maleic anhydride,
polypropylene, polypropylene-graft-maleic anhydride 8-10% maleic anhydride, polystyrene poly(styrene-block- ethylene/butylene-block - styrene) graft maleic anhydride 2% maleic anhydride 1 :1 :1 others, poly(styrene-block-butadiene) branched 1 :1 , poly(styrene-block-butadiene- block-styrene), 30% styrene, poly(styrene-block-isoprene) 10% wt styrene, poly(styrene-block-isoprene-block-styrene) 17% wt styrene, poly(styrene- co-4-chloromethylstyrene-co-4-methoxymethylstyrene 2:1 :1 , polystyrene- co-acrylonitrile 25% acrylonitrile, polystyrene-co-alpha-methylstyrene 1 :1 , polystyrene-co-butadiene 4% butadiene, polystyrene-co-butadiene
45% styrene, polystyrene-co-chloromethylstyrene 1 :1 , polyvinylchloride, polyvinylcinnamate, polyvinylcyclohexane, polyvinylidenefluoride, polyvinylidenefluoride-co-hexafluoropropylene assume 1 :1 , poly(styrene- block-ethylene/propylene-block-styrene) 30% styrene, poly(styrene- block- ethylene/propylene-block-styrene) 18% styrene, poly(styrene- block- ethylene/propylene-block-styrene) 13% styrene, poly(styrene- block ethylene block-ethylene/propylene-block styrene) 32% styrene,
poly(styrene- block ethylene block-ethylene/propylene-block styrene) 30% styrene, poly(styrene- block-ethylene/butylene-block-styrene) 31 % styrene, poly(styrene- block-ethylene/butylene-block-styrene) 34% styrene, poly(styrene- block-ethylene/butylene-block-styrene) 30% styrene, poly(styrene- block-ethylene/butylene-block-styrene) 60%, styrene, branched or non-branched polystyrene-block- polybutadiene, polystyrene-block(polyethylene-ran-butylene)-block- polystyrene, polystyrene-block-polybutadiene-block-polystyrene, polystyrene-(ethylene-propylene)-diblock-copolymers (e.g. KRATON®- G1701 E, Shell), poly(propylene-co-ethylene) and poly(styrene-co- methylmethacrylate).
Preferred insulating binders to be used in the formulations as described before are polystryrene, poly(a-methylstyrene), polyvinylcinnamate, poly(4-vinylbiphenyl), poly(4-methylstyrene), and polymethyl methacrylate. Most preferred insulating binders are polystyrene and polymethyl methacrylate.
The binder can also be selected from crosslinkable binders, like e.g.
acrylates, epoxies, vinylethers, thiolenes etc. The binder can also be mesogenic or liquid crystalline.
The organic binder may itself be a semiconductor, in which case it will be referred to herein as a semiconducting binder. The semiconducting binder is still preferably a binder of low permittivity as herein defined.
Semiconducting binders for use in the present invention preferably have a number average molecular weight (Mn) of at least 1500-2000, more preferably at least 3000, even more preferably at least 4000 and most preferably at least 5000. The semiconducting binder preferably has a charge carrier mobility of at least 105cm2V 1s 1, more preferably at least 104cm2V 1s 1.
A preferred semiconducting binder comprises a homo-polymer or copolymer (including block-copolymer) containing arylamine (preferably triarylamine). Another preferred embodiment of the invention relates to a polymer, or a composition comprising it, as described above and below, wherein the groups Rc are crosslinked, preferably by photocrosslinking or thermal crosslinking. Another preferred embodiment of the invention relates to a pattern or patterned film comprising a polymer, or a composition comprising it, as described above and below, wherein the groups Rc are crosslinked. The pattern or patterned a film is for example comprising, or consisting of, regions comprising the crosslinked polymer and regions without the polymer as described above and below.
Crosslinking of the groups Rc can be achieved by conventional means and methods that are known to the skilled person and are described in the literature, for example by a photo- or thermal crosslinking reaction. In order to facilitate or enhance the crosslinking reaction, the composition comprising the polymer may further comprise an initiator, a catalyst or a sensitizer.
Patterns and patterned films can be made by means and methods that are known to the skilled person and are described in the literature, or in the examples below, for example by exposing the polymer through a photomask or shadow mask to light or other actinic radiation, e.g. UV light, causing a photocrosslinking reaction of the groups Rc in the exposed regions, and subsequently rinsing the non-crosslinked polymer in the non- exposed regions.
The polymers and compositions according to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electronic,
optoelectronic, electroluminescent or photoluminescent components or devices. In these devices, the polymers and compositions of the present invention are typically applied as thin layers or films.
Thus, the present invention also provides the use of the polymer or composition or layer in an electronic device. The polymer or composition may be used as a high mobility semiconducting material in various devices and apparatus. The polymer or composition 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 polymer or composition 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 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 compound 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 optoelectronic devices the
compounds, compositions 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.
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.
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.
Suitable solvents should be selected to ensure full dissolution of all components, like p-type and n-type OSCs, and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method. For inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred. For spin coating alkylated benzenes like xylene and toluene are preferred.
Apart from the requirements stated above the solvents should not have any detrimental effect on the chosen print head. Additionally, the solvents should preferably 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,/V-di-Ci-2-alkylanilines and other fluorinated or chlorinated aromatics.
A preferred solvent for depositing a polymer 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 inkjet fluid to be formed comprising the solvent with the 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, and 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 invention additionally provides an OE device comprising a polymer or composition or organic semiconducting layer according to the present invention.
Preferred OE devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, PSCs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarizing layers, antistatic films, conducting substrates and conducting patterns, . Very preferred OE devices are OPV, PSC and OPD devices, OFETs, and OLEDs, in particular OPD, PSC and bulk heterojunction (BHJ) OPV devices. In an OFET, for example, the active semiconductor channel between the drain and source may comprise the polymer or composition of the invention. As another example, in an OLED device, the charge (hole or electron) injection or transport layer may comprise the polymer or composition of the invention.
An OPV or OPD device according to the present invention preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi-transparent substrate on one side of the photoactive layer, and a second metallic or semi-transparent electrode on the other side of the photoactive layer.
Further preferably the OPV or OPD device comprises, between the photoactive 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, NiOx, a conjugated polymer electrolyte, like for example PEDOTPSS, a conjugated polymer, like for example polytriarylamine (PTAA), an insulating polymer, like for example nafion, polyethyleneimine or polystyrenesulphonate, 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 ,1 '-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]-b-poly[3-(6- trimethylammoniumhexyljthiophene], 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)-aluminum(lll) (Alq3), 4,7-diphenyl-1 ,10-phenanthroline.
The OPV device can for example be of any type known from the literature (see e.g. Waldauf et ai, 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 polymer or polymer blend, for example of
PEDOTPSS (poly(3,4-ethylenedioxythiophene): polystyrene- 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 "photoactive 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 or PFN,
- 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 n-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 an organic polymer, polymer blend, metal or metal oxide like TiOx, ZnOx, Ca, Mg, poly(ethyleneimine), poly(ethyleneimine) ethoxylated or poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9- dioctylfluorene)],
- a photoactive 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 polymer or polymer blend, metal or metal oxide, for example PEDOTPSS, nafion, a substituted triaryl amine derivative like for example TBD or NBD, or WOx, MoOx, NiOx, Pd or Au,
- 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 n-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/polymer/fullerene systems, as described above.
When the photoactive 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. Pune. 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, et al, Nat. Mater. , 2007, 6, 497 or Frechet et al. J.
Am. Chem. Soc., 2010, 132, 7595-7597.
Another preferred embodiment of the present invention relates to the use of a polymer or composition according to the present invention as dye, hole transport layer, hole blocking layer, electron transport layer and/or electron blocking layer in a DSSC or a perovskite-based solar cell (PSC), and to a DSSC or PSC comprising a polymer or composition according to the present invention.
DSSCs and PSCs can be manufactured as described in the literature, for example in Chem. Rev. 2010, 110, 6595-6663, Angew. Chem. Int. Ed. 2014, 53, 2-15 or in W02013171520A1 A preferred OE device according to the invention is a solar cell, preferably a PSC, comprising a light absorber which is at least in part inorganic as described below. In a solar cell comprising the light absorber according to the invention there are no restrictions per se with respect to the choice of the light absorber material which is at least in part inorganic.
The term“at least in part inorganic” means that the light absorber material may be selected from metalorganic complexes or materials which are substantially inorganic and possess preferably a crystalline structure where single positions in the crystalline structure may be allocated by organic ions. Preferably, the light absorber comprised in the solar cell according to the invention has an optical band-gap < 2.8 eV and > 0.8 eV.
Very preferably, the light absorber in the solar cell according to the invention has an optical band-gap < 2.2 eV and > 1.0 eV.
The light absorber used in the solar cell according to the invention does preferably not contain a fullerene. The chemistry of fullerenes belongs to the field of organic chemistry. Therefore fullerenes do not fulfil the definition of being“at least in part inorganic” according to the invention.
Preferably, the light absorber which is at least in part inorganic is a material having perovskite structure or a material having 2D crystalline perovskite structure. The term“perovskite” as used above and below denotes generally a material having a perovskite crystalline structure or a 2D crystalline perovskite structure.
The term perovskite solar cell (PSC) means a solar cell comprising a light absorber which is a material having perovskite structure or a material having 2D crystalline perovskite structure. The light absorber which is at least in part inorganic is without limitation composed of a material having perovskite crystalline structure, a material having 2D crystalline perovskite structure (e.g. CrystEngComm, 2010,12, 2646-2662), Sb2S3 (stibnite), Sb2(SxSe(X-i))3, PbSxSe(X-i), CdSxSe(X-i), ZnTe,
CdTe, ZnSxSe(x-i), InP, FeS, FeS2, Fe2S3, Fe2SiS4, Fe2GeS4, CU2S, CulnGa, Culn(SexS(i-X))2, Cu3SbxBi(X-i), (SySe(y-i))3, Cu2SnS3, SnSxSe(X-i), Ag2S, AgBiS2, BiSI, BiSel, Bi2(SxSe(X-i))3, BiS(i-X)Sexl, WSe2, AlSb, metal halides (e.g. Bib, Cs2Snl6), chalcopyrite (e.g. CulnxGa(i-X)(SySe(i.y))2), kesterite (e.g. Cu2ZnSnS4, Cu2ZnSn(SexS(i-X))4, Cu2Zn(Sni-xGex)S4) and metal oxide (e.g. CuO, CU2O) or a mixture thereof.
Preferably, the light absorber which is at least in part inorganic is a perovskite.
In the above definition for light absorber, x and y are each independently defined as follows: (0<x<1 ) and (0<y<1 ).
Very preferably, the light absorber is a special perovskite namely a metal halide perovskite as described in detail above and below. Most preferably, the light absorber is an organic-inorganic hybrid metal halide perovskite contained in the perovskite solar cell (PSC).
In one particularly preferred embodiment of the invention, the perovskite denotes a metal halide perovskite with the formula ABX3,
where
A is a monovalent organic cation, a metal cation or a mixture of two or more of these cations
B is a divalent cation and
X is F, Cl, Br, I, BF4 or a combination thereof.
Preferably, the monovalent organic cation of the perovskite is selected from alkylammonium, wherein the alkyl group is straight chain or branched having 1 to 6 C atoms, formamidinium or guanidinium or wherein the metal cation is selected from K+, Cs+ or Rb+. Suitable and preferred divalent cations B are Ge2+, Sn2+ or Pb2+.
Suitable and preferred perovskite materials are CsSnU, CFhNFhPb i- BF4)x)3,
Figure imgf000158_0001
wherein x is each independently defined as follows: (0<x<1 ).
Further suitable and preferred perovskites may comprise two halides corresponding to formula Xa(3-X)Xb(X), wherein Xa and Xb are each independently selected from Cl, Br, or I, and x is greater than 0 and less than 3.
Suitable and preferred perovskites are also disclosed in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference. The materials are defined as mixed-anion perovskites comprising two or more different anions selected from halide anions and chalcogenide anions. Preferred perovskites are disclosed on page 18, lines 5 to 17. As described, the perovskite is usually selected from
CH3NH3PbBrl2, CFhNFhPbBrCh, CH3NH3PblBr2, CH3NH3PblCI2,
CH3NH3SnF2Br, CH3NH3SnF2l and (H2N=CH-NH2)Pbl3zBr3(i-z), wherein z is greater than 0 and less than 1.
The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as a layer between one electrode and the light absorber layer.
The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is comprised in an electron-selective layer.
The electron selective layer is defined as a layer providing a high electron conductivity and a low hole conductivity favoring electron-charge transport. The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as electron transport material (ETM) or as hole blocking material as part of the electron selective layer.
Preferably, the polymer according to the present invention is employed as electron transport material (ETM). In an alternative preferred embodiment, the polymer according to the present invention is employed as hole blocking material.
The device architecture of a PSC device according to the invention can be of any type known from the literature.
A first preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
optionally a substrate which, in any combination, can be flexible or rigid and transparent, semi-transparent or non-transparent and electrically conductive or non-conductive;
a high work function electrode, preferably comprising a doped metal oxide, for example fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide;
- an electron-selective layer which comprises one or more electron transporting materials, at least one of which is a polymer according to the present invention, and which, in some cases, can also be a dense layer and/or be composed of nanoparticles, and which preferably comprises a metal oxide such as T1O2, Zn02, SnCte, Y2O5, Ga203, SrTiC , BaTiC or combinations thereof;
optionally a porous scaffold which can be conducting, semi-conducting or insulating, and which preferably comprises a metal oxide such as T1O2, Zn02, Sn02, Y2O5, Ga203, SrTi03, BaTiOs, AI2O3, Zr02, S1O2 or combinations thereof, and which is preferably composed of
nanoparticles, nanorods, nanoflakes, nanotubes or nanocolumns; a layer comprising a light absorber which is at least in part inorganic, particularly preferably a metal halide perovskite as described above which, in some cases, can also be a dense or porous layer and which optionally partly or fully infiltrates into the underlying layer;
- optionally a hole selective layer, which comprises one or more hole transporting materials, and which, in some cases, can also comprise additives such as lithium salts, for example LiY, where Y is a
monovalent organic anion, preferably bis(trifluoromethylsulfonyl)imide, tertiary amines such as 4-tert-butylpyridine, or any other covalent or ionic compounds, for example tris(2-(1 H-pyrazol-1 -yl)-4-tert- butylpyridine)-cobalt(lll) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
and a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
A second preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
optionally a substrate which, in any combination, can be flexible or rigid and transparent, semi-transparent or non-transparent and electrically conductive or non-conductive;
a high work function electrode, preferably comprising a doped metal oxide, for example fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide;
optionally a hole injection layer which, for example, changes the work function of the underlying electrode, and/or modifies the surface of the underlying layer and/or helps to planarize the rough surface of the underlying layer and which, in some cases, can also be a monolayer; optionally a hole selective layer, which comprises one or more hole transporting materials and which, in some cases, can also comprise additives such as lithium salts, for example LiY, where Y is a
monovalent organic anion, preferably bis(trifluoromethylsulfonyl)imide, tertiary amines such as 4-tert-butylpyridine, or any other covalent or ionic compounds, for example tris(2-(1 H-pyrazol-1 -yl)-4-tert- butylpyridine)-cobalt(lll) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
a layer comprising a light absorber which is at least in part inorganic, particularly preferably a metal halide perovskite as described or preferably described above;
an electron-selective layer, which comprises one or more electron transporting materials, at least one of which is a polymer according to the present invention and which, in some cases, can also be a dense layer and/or be composed of nanoparticles, and which, for example, can comprise a metal oxide such as T1O2, Zn02, SnCte, Y2O5, Ga203, SrTiC , BaTiC or combinations thereof, and/or which can comprise a substituted fullerene, for example [6,6]-phenyl C61 -butyric acid methyl ester, and/or which can comprise a molecular, oligomeric or polymeric electron-transport material, for example 2,9-Dimethyl-4,7-diphenyl-
1 ,10-phenanthroline, or a mixture thereof;
and a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
To produce electron selective layers in PSC devices according to the invention, the polymers according to the present invention, optionally together with other compounds or additives in the form of blends or mixtures, may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. Formulations comprising the polymers according to 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 die coating or pad printing. For the fabrication of PSC devices and modules, deposition techniques for large area coating are preferred, for example slot die coating or spray coating. Formulations that can be used to produce electron selective layers in optoelectronic devices according to the invention, preferably in PSC devices comprise one or more polymers according to the present invention or preferred embodiments as described above in the form of blends or mixtures optionally together with one or more further electron transport materials and/or hole blocking materials and/or binders and/or other additives as described above and below, and one or more solvents.
The formulation may include or comprise, essentially consist of or consist of the said necessary or optional constituents as described above or below. All compounds or components which can be used in the
formulations are either known or commercially available, or can be synthesized by known processes. The formulation as described before may be prepared by a process which comprises:
(i) first mixing a polymer according to the present invention, optionally a binder or a precursor of a binder as described before, optionally a further electron transport material, optionally one or more further additives as described above and below and a solvent or solvent mixture as described above and below and
(ii) applying such mixture to a substrate; and optionally evaporating the solvent(s) to form an electron selective layer according to the present invention.
In step (i) the solvent may be a single solvent for the polymer according to the present invention and the organic binder and/or further electron transport material may each be dissolved in a separate solvent followed by mixing the resultant solutions to mix the compounds.
Alternatively, the binder may be formed in situ by mixing or dissolving a polymer according to the present invention in a precursor of a binder, for example a liquid monomer, oligomer or crosslinkable polymer, optionally in the presence of a solvent, and depositing the mixture or solution, for example by dipping, spraying, painting or printing it, on a substrate to form a liquid layer and then curing the liquid monomer, oligomer or
crosslinkable polymer, for example by exposure to radiation, heat or electron beams, to produce a solid layer. If a preformed binder is used it may be dissolved together with the polymer in a suitable solvent as described before, and the solution deposited for example by dipping, spraying, painting or printing it on a substrate to form a liquid layer and then removing the solvent to leave a solid layer. It will be appreciated that solvents are chosen which are able to dissolve all ingredients of the formulation, and which upon evaporation from the solution blend give a coherent defect free layer.
Besides the said components, the formulation as described before may comprise further additives and processing assistants. These include, inter alia, surface-active substances (surfactants), lubricants and greases, additives which modify the viscosity, additives which increase the conductivity, dispersants, hydrophobicizing agents, adhesion promoters, flow improvers, antifoams, deaerating agents, diluents, which may be reactive or unreactive, fillers, assistants, processing assistants, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.
Additives can be used to enhance the properties of the electron selective layer and/or the properties of any of the neighbouring layers and/or the performance of the optoelectronic device according to the invention.
Additives can also be used to facilitate the deposition, the processing or the formation of the electron selective layer and/or the deposition, the processing or the formation of any of the neighbouring layers. Preferably, one or more additives are used which enhance the electrical conductivity of the electron selective layer and/or passivate the surface of any of the neighbouring layers.
Suitable methods to incorporate one or more additives include, for example exposure to a vapor of the additive at atmospheric pressure or at reduced pressure, mixing a solution or solid containing one or more additives and a material or a formulation as described or preferably described before, bringing one or more additives into contact with a material or a formulation as described before, by thermal diffusion of one or more additives into a material or a formulation as described before, or by ion-implantation of one or more additives into a material or a
formulation as described before. Additives used for this purpose can be organic, inorganic, metallic or hybrid materials. Additives can be molecular compounds, for example organic molecules, salts, ionic liquids, coordination complexes or organometallic compounds, polymers or mixtures thereof. Additives can also be particles, for example hybrid or inorganic particles, preferably nanoparticles, or carbon based materials such as fullerenes, carbon nanotubes or graphene flakes.
Examples for additives that can enhance the electrical conductivity are for example halogens (e.g. I2, CI2, Br2, ICI, ICI3, IBr and IF), Lewis acids (e.g. PF5, AsFs, SbFs, BF3, BCI3, SbCIs, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g. HF, HCI, HNO3, H2SO4, HCIO4, FSO3H and CISO3H), transition metal compounds (e.g. FeC , FeOCI, Fe(CI04)3, Fe(4- CHsCeFUSOsJs, TiCU, ZrCL, HfCU, NbF5, NbCIs, TaCIs, M0F5, M0CI5, WF5, WCI6, UFe and LnC (wherein Ln is a lanthanoid)), anions (e.g. Cl , Br, h, I3-, HSO4·, S04 2 , NO3·, CIO4-, BF4-, PFe , AsFe , SbF6 , FeC , Fe(CN)6 3 , and anions of various sulfonic acids, such as aryl-SC ), cations (e.g. H+, Li+, Na+, K+, Rb+, Cs+, Co3+ and Fe3+), O2, redox active salts (e.g. XeOF4, (N02 +) (SbFe ), (N02 +) (SbCle ), (N02 +) (BF4 ), NOBF4, NOPFe, AgCI04, H2lrCl6 and La(N03)3 6H2O), strongly electron-accepting organic molecules (e.g. 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4- TCNQ)), transition metal oxides (e.g. WO3, Re207 and M0O3), metal- organic complexes of cobalt, iron, bismuth and molybdenum, (p- BrC6FU)3NSbCl6, bismuth(lll) tris(trifluoroacetate), FSO2OOSO2F, acetylcholine, R4N+, (R is an alkyl group), R4P+ (R is a straight-chain or branched alkyl group 1 to 20), ReAs+ (R is an alkyl group), RsS+ (R is an alkyl group) and ionic liquids (e.g. 1-Ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide). Suitable cobalt complexes beside of tris(2-(1 H-pyrazol-1 -yl)-4-tert-butylpyridine)-cobalt(l 11)
tris(bis(trifluoromethylsulfonyl)imide)) are cobalt complex salts as described in WO 2012/114315, WO 2012/114316, WO 2014/082706, WO 2014/082704, EP 2883881 or JP 2013-131477. Suitable lithium salts are beside of lithium bis(trifluoromethylsulfonyl)imide, lithium tris(pentafluoroethyl)trifluorophosphate, lithium dicyanamide, lithium methylsulfate, lithium trifluormethanesulfonate, lithium tetracyanoborate, lithium dicyanamide, lithium tricyanomethide, lithium thiocyanate, lithium chloride, lithium bromide, lithium iodide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroantimonate, lithium hexafluoroarsenate or a combination of two or more. A preferred lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
Preferably, the formulation comprises from 0.1 mM to 50 mM, preferably from 5 to 20 mM of the lithium salt.
Suitable device structures for PSCs comprising a polymer according to the present invention and a mixed halide perovskite are described in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
Suitable device structures for PSCs comprising a polymer according to the present invention and a dielectric scaffold together with a perovskite are described in WO 2013/171518, claims 1 to 90 or WO 2013/171520, claims 1 to 94 which are entirely incorporated herein by reference.
Suitable device structures for PSCs comprising a polymer according to the present invention, a semiconductor and a perovskite are described in WO 2014/020499, claims 1 and 3 to 14, which is entirely incorporated herein by reference The surface-increasing scaffold structure described therein comprises nanoparticles which are applied and/or fixed on a support layer, e.g. porous T1O2.
Suitable device structures for PSCs comprising a polymer according to the present invention and comprising a planar heterojunction are described in WO 2014/045021 , claims 1 to 39, which is entirely incorporated herein by reference. Such a device is characterized in having a thin film of a light absorbing or light-emitting perovskite disposed between n-type (electron conducting) and p-type (hole-conducting) layers. Preferably, the thin film is a compact thin film.
The invention further relates to a method of preparing a PSC as described above or below, the method comprising the steps of:
- providing a first and a second electrode;
- providing an electron selective layer comprising a polymer according to the present invention. The invention relates furthermore to a tandem device comprising at least one device according to the invention as described above and below. Preferably, the tandem device is a tandem solar cell.
The tandem device or tandem solar cell according to the invention may have two semi-cells wherein one of the semi cells comprises the compounds, oligomers or polymers in the active layer as described or preferably described above. There exists no restriction for the choice of the other type of semi cell which may be any other type of device or solar cell known in the art.
There are two different types of tandem solar cells known in the art. The so called 2-terminal or monolithic tandem solar cells have only two connections. The two subcells (or synonymously semi cells) are connected in series. Therefore, the current generated in both subcells is identical (current matching). The gain in power conversion efficiency is due to an increase in voltage as the voltages of the two subcells add up.
The other type of tandem solar cells is the so called 4-terminal or stacked tandem solar cell. In this case, both subcells are operated independently. Therefore, both subcells can be operated at different voltages and can also generate different currents. The power conversion efficiency of the tandem solar cell is the sum of the power conversion efficiencies of the two subcells.
The invention furthermore relates to a module comprising a device according to the invention as described before or preferably described before. The polymers and compositions according to the present invention can also be used as dye or pigment in other applications, for example as an ink dye, laser dye, fluorescent marker, solvent dye, food dye, contrast dye or pigment in coloring paints, inks, plastics, fabrics, cosmetics, food and other materials.
The polymers and compositions of the present invention are also suitable for use in the semiconducting channel of an OFET. 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 polymer or a composition 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 polymers according to the invention and thus the processibility of large surfaces, preferred applications of these OFETs 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 polymer according to the present invention.
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 constant) 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 monetary value, like stamps, tickets, shares, cheques etc. Alternatively, the polymers and compositions (hereinafter referred to as
"materials") according to the present 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 materials according to the present invention 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 materials according to the present 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., MCiller et at,
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 the present 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 al., Science, 1998, 279, 835-837.
A further aspect of the invention relates to both the oxidized and reduced form of the materials according to the present invention. Either loss or gain of electrons results in formation of a highly delocalized 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, 198, 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 delocalized ionic centers 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-implantation of the dopant into the semiconductor material.
When electrons are used as carriers, suitable dopants are for example halogens (e.g., I2, CI2, Br2, ICI, ICI3, IBr and IF), Lewis acids (e.g., PF5, AsFs, SbFs, BF3, BCI3, SbCIs, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HNO3, H2SO4, HCIO4, FSO3H and CISO3H), transition metal compounds (e.g., FeC , FeOCI, Fe(CI04)3, Fe(4-CH3C6H4S03)3, TiCU, ZrCL, HfCU, NbF5, NbCIs, TaCIs, M0F5, M0CI5, WF5, WCI6, UFe and LnC (wherein Ln is a lanthanoid), anions (e.g., Cl , Br, I-, I3-, HSO4·, SO42-, NO3·, CIO4·, BF4-, PFe , AsFe , SbF6 , FeCU , Fe(CN)63 , and anions of various sulfonic acids, such as aryl-SC ). When holes are used as carriers, examples of dopants are cations (e.g., FT, 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), O2, XeOF4, (N02+) (SbFe ), (N02+) (SbCle ), (N02 +) (BF4-), AgCI04, H2lrCI6, La(N03)3 6H2O, FSO2OOSO2F, Eu, acetylcholine, R4N+, (R is an alkyl group), R4P+ (R is an alkyl group), R6AS+ (R is an alkyl group), and RsS+ (R is an alkyl group).
The conducting form of the materials according to the present invention can be used as an organic "metal" in applications including, but not limited to, charge injection layers and ITO planarizing 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 materials 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 polarization 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 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.
According to another use, the materials according to the present invention are suitable for use in liquid crystal (LC) windows, also known as smart windows.
The materials according to the present invention may also be combined with photoisomerizable 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 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.
Monomer Examples
Monomer 1
( 1 1 -BromoundecyloxyHe/f-butyldimethylsilane To a solution of fe/f-butyldimethylsilyl chloride (16.58 g, 1 10.0 mmol) and 1 H-imidazole (14.98 g, 220.0 mmol) in anhydrous dichloromethane (200 cm3) was added a solution of 1 1 -bromoundecan-1 -ol (25.12 g, 100.0 mmol) in dichloromethane (50 cm3) under stirring within 20 minutes. The mixture was stirred at 23 °C for 1 hour and then the volatiles removed in vacuo. Petroleum ether (40-60 °C, 200 cm3) was added to the residue, the suspension filtered through Celite and the volatiles removed in vacuo. The crude was then passed through a silica plug (petroleum ether 40-60 °C) to give the titled compound (34.02 g, 93%) as a colourless liquid. El (m/z): 363. 1H NMR (400 MHz, CDCIs) 3.59 (t, J = 6.6 Hz, 2H), 3.40 (t, J = 6.9 Hz, 2H), 1.90 - 1 .79 (m, 2H), 1 .50 (m, 2H), 1 .45 - 1 .37 (m, 2H), 1 .28 (m, 12H), 0.89 (s, 9H), 0.04 (s, 6H).
4,4,9,9-Tetrakisd 1 -fe/f-butyldimethylsiloxyundecyl)-4,9-dihvdro-s- indacenoM , 2-6:5, 6-6'1dithiophene
Figure imgf000173_0001
A mixture of 4,9-dihydro-s-indaceno[1 , 2-6:5, 6-£>']dithiophene (2.000 g, 7.508 mmol), anhydrous A/,/V-dimethylformamide (60 cm3), (1 1 - bromoundecyloxy)-fe/f-butyldimethylsilane (13.72 g, 37.54 mmol) and sodium iodide (100 mg, 0.667 mmol) was degassed by bubbling nitrogen for 30 minutes, followed by the addition of sodium hydride (1.50 g, 37.5 mmol, 60% dispersion in mineral oil). The mixture was stirred at 20 °C for 0.5 hours and at 100 °C for 16 hours. The mixture was cooled to 20 °C then the volatiles removed in vacuo. Petroleum ether (40-60 °C, 100 cm3) was added and the mixture filtered through Celite. The volatiles removed in vacuo and the residue purified by chromatography on silica (30% dichloromethane in petroleum ether 40-60 °C) to give the titled compound (5.21 g, 49%) as a thick yellow oil. 1H NMR (400 MHz, CDCIs) 7.27 (s,
1 H), 7.25 (d, J = 4.8 Hz, 1 H), 6.96 (d, J = 4.8 Hz, 1 H), 3.58 (dt, J = 9.6, 6.7 Hz, 4H), 1.97 (ddd, J = 13.1 , 11.0, 5.4 Hz, 2H), 1.83 (ddd, J = 13.2, 10.9, 5.5 Hz, 2H), 1.54 - 1.43 (m, 4H), 1.35 - 1.04 (m, 28H), 0.89 (s, 18H), 0.79 (m, 4H), 0.04 (s, 12H).
4,4,9,9-Tetrakisd 1-hvdroxyundecyl)-4,9-dihvdro-s-indaceno[1 ,2-b:5,6- b'ldithiophene
Figure imgf000174_0001
4,4,9,9-Tetrakis(11-fe/f-butyldimethylsiloxyundecyl)-4,9-dihydro-s- indaceno[1 ,2-b:5,6-b']dithiophene (5.20 g, 3.70 mmol) was dissolved in tetrahydrofuran (50 cm3) followed by the addition of tetrabutylammonium fluoride (19 cm3, 19 mmol, 1.0 M in tetrahydrofuran). The solution was stirred at 20 °C for 2 hours. The volatiles were removed in vacuo, diethyl ether (50 cm3) added and the solution washed with water (3 x 50 cm3).
The ether phase was dried over anhydrous magnesium sulfate, filtered and the volatiles removed in vacuo. The residue was purified by chromatography on silica (30-40% acetone in dichloromethane) to give the titled compound (2.96 g, 84%) as a thick yellow oil. 1H NMR (400 MHz, CDCI3) 7.26 (s, 1 H), 7.25 (d, J = 4.8 Hz, 1 H), 6.95 (d, J = 4.8 Hz, 1 H), 3.60 (t, J = 6.7 Hz, 4H), 1 .96 (ddd, J = 13.1 , 1 1 .1 , 5.3 Hz, 2H), 1 .84 (ddd, J = 13.3, 1 1 .0, 5.3 Hz, 2H), 1 .51 (dt, J = 8.1 , 6.6 Hz, 4H), 1 .34 - 1 .00 (m,
28H), 0.89 - 0.72 (m, 4H).
4,4,9,9-TetrakisM 1 -(2,3-dimethyl-N-maleimido)undecyl1-4,9-dihydro-s- indacenoM , 2-6:5, 6-6'1dithiophene
Figure imgf000175_0001
To a mixture of triphenylphosphine (4.097 g, 15.619 mmol), 4, 4,9,9- tetrakis(1 1 -hydroxyundecyl)-4,9-dihydro-s-indaceno[1 ,2-6:5, 6- 6']dithiophene (2.960 g, 3.124 mmol), anhydrous tetrahydrofuran (100 cm3) and 3,4-dimethylmaleimide (1.954 g, 15.619 mmol) at -78 °C was added diethyl azodicarboxylate (2.46 cm3, 15.6 mmol) dropwise. The cooling bath was removed and the reaction mixture stirred for 30 minutes. The solution re-cooled to -78 °C and stirred for 10 minutes before removing the cooling and stirring the reaction mixture at 23 °C for 18 hours. The volatiles were removed in vacuo. The residue was purified by chromatography on silica (dichloromethane) to give the titled compound (2.64 g, 61 %) as a thick yellow oil which solidified upon standing. 1H NMR (400 MHz, CDCI3) 7.20 (s, 1 H), 7.18 (d, J = 4.9 Hz, 1 H), 6.89 (d, J = 4.8 Hz, 1 H), 3.41 - 3.32 (m, 4H), 1.87 (m+s, 14H), 1 .76 (ddd, J = 13.3, 1 1 .0, 5.5 Hz, 2H), 1 .44 (t, J = 7.2 Hz, 4H), 1 .22 - 0.92 (m, 28H), 0.84 - 0.69 (m, 4H). 13C NMR (101 MHz, CDCI3) 172.29, 172.26, 155.02, 153.19, 141 .55, 136.90, 135.46, 126.08, 121 .70, 1 13.08, 53.57, 53.40, 39.01 , 37.91 ,
29.96, 29.50, 29.45, 29.42, 29.39, 29.27, 29.13, 28.66, 26.73, 24.13, 8.63. 2,7-Dibromo-4,4,9,9-tetrakis[1 1 -(2,3-dimethyl-N-maleimido)undecyl1-4,9- dihydro-s-indacenoM ,2-b:5,6-b'1dithiophene (Monomer 1 )
Figure imgf000176_0001
To a solution of 4,4,9,9-tetrakis[1 1 -(2,3-dimethyl-N-maleimido)undecyl]- 4,9-dihydro-s-indaceno[1 ,2-b:5,6-b']dithiophene (2.500 g, 1 .817 mmol) in dichloromethane (40 cm3) was added acetic acid (10 cm3). The solution was cooled to 0 °C followed by the addition of /V-bromosuccinimide (698 mg, 3.882 mmol). The mixture was stirred at 20 °C for 1 hour and the volatiles removed in vacuo. The residue was purified by chromatography on silica (dichloromethane) to give Monomer 1 (2.54 g, 91 %) as a thick yellow oil which solidified into a yellow solid after vacuum drying and standing. 1H NMR (400 MHz, dichloromethane-d2) 7.16 (d, J = 1 .7 Hz, 1 H), 6.93 (d, J = 1.7 Hz, 1 H), 3.32 (t, J = 7.2 Hz, 4H), 1 .86 (m, 2H), 1 .83 (s, 12H), 1 .76 (dt, J = 13.1 , 6.7 Hz, 2H), 1 .41 (t, J = 7.1 Hz, 4H), 1 .22 - 0.93 (m, 28H), 0.83 - 0.56 (m, 4H). 13C NMR (101 MHz, CD2CI2) 172.19,
154.23, 152.18, 141 .85, 136.86, 135.49, 124.99, 1 13.10, 1 12.21 , 54.78, 38.87, 37.79, 29.88, 29.51 , 29.50, 29.48, 29.45, 29.27, 29.18, 28.66,
26.76, 24.09, 8.33.
Monomer 2
( 12-Bromododecyloxy)-fe/f-butyldimethylsilane To a solution of fe/f-butyldimethylsilyl chloride (3.125 g, 20.74 mmol) and 1 H-imidazole (2.823 g, 41 .47 mmol) in anhydrous dichloromethane (50 cm3) was added a solution of 12-bromododecan-1 -ol (5.000 g, 18.85 mmol) in anhydrous dichloromethane (10 cm3) over 5 minutes. The mixture was stirred at 20 °C for 2 hours and then the volatiles removed in vacuo. Petroleum ether (40-60 °C, 50 cm3) was added, the suspension filtered through Celite and the volatiles removed in vacuo. The crude was passed through a silica plugg (n-pentane) to give the titled compound (6.79 g, 95%) as a colourless liquid. El (m/z): 379. 1H NMR (400 MHz, CDCIs) 3.59 (t, J = 6.6 Hz, 2H), 3.40 (t, J = 6.9 Hz, 2H), 1 .85 (p, J = 7.0 Hz, 2H), 1 .50 (t, J = 6.6 Hz, 2H), 1 .45 - 1 .37 (m, 2H), 1.34 - 1 .22 (m, 14H), 0.89 (s, 9H), 0.04 (s, 6H). 13C NMR (101 MHz, CDCIs) -5.25, 18.37, 25.80, 25.99, 28.18, 28.77, 29.43, 29.51 , 29.54, 29.60, 32.85, 32.89, 33.98, 63.31 .
4,4,9,9-Tetrakis(12-fe/f-butyldimethylsiloxydodecyl)-4,9-dihydro-s- indacenoM ,2-b:5,6-b'1dithiophene
Figure imgf000177_0001
A mixture of 4,9-dihydro-s-indaceno[1 ,2-b:5,6-b']dithiophene (800 mg, 3.00 mmol), anhydrous A/,/V-dimethylformamide (30 cm3), (12- bromododecyloxy)-fe/f-butyldimethylsilane (5.698 g, 15.02 mmol) and sodium iodide (100 mg, 0.667 mmol) was degassed by bubbling nitrogen for 30 minutes, followed by the addition of sodium hydride (601 mg, 15.0 mmol, 60% dispersion in mineral oil). The mixture was stirred at 50 °C for 1 hour and at 100 °C for 16 hours. The mixture was cooled to 23 °C then the volatiles removed in vacuo . Petroleum ether (80-100 °C, 50 cm3) was added and the mixture was filtered through Celite. The filtrate was purified by chromatography on silica (20% dichloromethane in petroleum ether 40- 60 °C) to give the titled product (2.62 g, 60%) as a yellow oil. 1H NMR (400 MHz, CDCIs) 7.30 (s, 1 H), 7.26 (d, J = 4.8 Hz, 1 H), 6.96 (d, J = 4.8 Hz,
1 H), 3.55 (t, J = 6.6 Hz, 4H), 1 .97 (ddd, J = 13.1 , 10.9, 5.6 Hz, 2H), 1 .85 (ddd, J = 13.2, 10.7, 5.6 Hz, 2H), 1 .48 - 1 .39 (m, 4H), 1.33 - 1 .01 (m,
32H), 0.86 (s, 18H), 0.83 - 0.73 (m, 4H), 0.01 (s, 12H). 13C NMR (101 MHz, CD2CI2) 155.81 , 153.85, 142.15, 136.22, 126.80, 122.32, 1 13.72, 63.78, 39.71 , 33.51 , 30.58, 30.25, 30.19, 30.16, 30.04, 29.96, 26.46,
26.42, 26.33, 24.79, 18.80, -4.99.
4,4,9,9-Tetrakis(12-hvdroxydodecyl)-4,9-dihydro-s-indaceno[1 ,2-b:5,6- b'ldithiophene
Figure imgf000178_0001
To a solution of 4,4,9,9-tetrakis(12-fe/f-butyldimethylsiloxydodecyl)-4,9- dihydro-s-indaceno[1 ,2-b:5,6-b']dithiophene (2.810 g, 1 .924 mmol) in anhydrous tetrahydrofuran (40 cm3) was added tetrabutylammonium fluoride (10 cm3, 10 mmol, 1 .0 M in tetrahydrofuran). The solution was stirred at 20 °C for 2 hours. The volatiles were removed in vacuo, ditheyl ether (50 cm3) added and the solution washed with water (3 x 50 cm3).
The ether phase was dried over anhydrous magnesium sulfate, filtered and the volatiles removed in vacuo . The residue was purified by chromatography on silica (30-40% acetone in dichloromethane) to give the titled compound (1 .87 g, 97%) as a thick yellow oil. 1H NMR (400 MHz,
CDCIs) 7.27 (s, 1 H), 7.25 (d, J = 4.8 Hz, 1 H), 6.95 (d, J = 4.8 Hz, 1 H), 3.61 (t, J = 6.6 Hz, 4H), 2.17 (s, 2H), 1.97 (ddd, J = 13.2, 1 1 .1 , 5.4 Hz, 2H),
1 .84 (ddd, J = 13.2, 10.9, 5.4 Hz, 2H), 1 .36 - 1 .01 (m, 32H), 0.81 (dq, J = 10.4, 5.0 Hz, 4H). 13C NMR (101 MHz, CDCIs) 155.05, 153.19, 141 .60, 135.53, 126.08, 121 .69, 1 13.09, 63.04, 53.63, 39.1 1 , 32.78, 30.92, 29.99,
29.58, 29.56, 29.54, 29.52, 29.39, 29.33, 25.72, 24.14.
4,4,9,9-Tetrakis[12-(2,3-dimethyl-N-maleimido)dodecyl1-4,9-dihydro-s- indacenoM , 2-6:5, 6-6'1dithiophene
Figure imgf000179_0001
A solution of triphenylphosphine (670 mg, 2.55 mmol), 4,4,9,9-tetrakis(12- hydroxydodecyl)-4,9-dihydro-s-indaceno[1 , 2-6:5, 6-6']dithiophene (534 mg, 0.532 mmol) in anhydrous tetrahydrofuran (25 cm3) was cooled to -78 °C. Diethyl azodicarboxylate (0.40 cm3, 2.5 mmol) was added dropwise and the mixture was stirred with cooling for 10 minutes. 3,4-Dimethylmaleimide (320 mg, 2.55 mmol) was added in one portion and the flask was removed from the cooling bath and the gel was shaken manually at 20 °C until it was stirrable. The gel was gradually dissolved over ca 30 minutes to yield a solution. The solution was stirred at 20 °C for 18 hours. The volatiles were removed in vacuo and the crude chromatographed on silica (dichlorom ethane) to give the titled product (0.43 g, 57%) as a very thick yellow oil. 1H NMR (400 MHz, DCM -d2) 7.29 (s, 1 H), 7.25 (d, J = 4.7, 1 H), 6.95 (d, J = 4.9, 1 H), 3.38 (t, J = 7.2 Hz, 4H), 2.02 - 1 .91 (m, 2H), 1 .88 (s, 12H), 1 .82 (m, 2H), 1 .47 (p, J = 7.3 Hz, 4H), 1 .30 - 0.94 (m, 32H), 0.77 (dp, J = 13.8, 7.3 Hz, 4H). 13C NMR (101 MHz, CD2CI2) 172.75, 155.78, 153.82, 142.09, 137.43, 136.16, 126.79, 122.31 , 1 13.70, 39.64, 38.37, 30.53, 30.1 1 , 30.07, 29.90, 29.74, 29.23, 27.35, 24.75, 8.90, 8.87.
2,7-Dibromo-4,4,9,9-tetrakis[12-(2,3-dimethyl-N-maleimido)dodecyl1-4,9- dihvdro-s-indaceno[1 ,2-b:5,6-b'1dithiophene (Monomer 2)
Figure imgf000180_0001
Monomer 2
To a solution of 4,4,9, 9-tetrakis[12-(2,3-dimethyl-N-maleimido)dodecyl]- 4,9-dihydro-s-indaceno[1 ,2-b:5,6-b']dithiophene (750 mg, 0.524 mmol) in anhydrous dichloromethane (20 cm3) was added acetic acid (5 cm3). The solution was cooled to 0 °C followed by the addition of N- bromosuccinimide (193 mg, 1 .08 mmol) in one portion. The mixture was stirred at 20 °C for 1 hour before the volatiles were removed in vacuo .
The residue was purified by chromatography on silica (dichloromethane) to give Monomer 2 (737 mg, 89%) as a thick yellow oil which solidified upon standing. 1H NMR (400 MHz, CD2CI2) 7.23 (s, 1 H), 7.00 (s, 1 H), 3.40 (t, J = 7.2 Hz, 4H), 2.01 - 1 .92 (m, 2H), 1 .90 (s, 12H), 1 .87 - 1 .76 (m, 2H), 1 .49 (t, J = 7.1 Hz, 4H), 1 .29 - 0.99 (m, 32H), 0.89 - 0.64 (m, 4H). 13C NMR (101 MHz, CD2CI2) 172.76, 154.79, 152.74, 142.42, 137.42, 136.06, 125.54, 1 13.66, 1 12.79, 55.35, 39.45, 38.36, 30.43, 30.12, 30.10, 30.08, 29.85, 29.75, 29.24, 27.35, 24.64, 8.90.
Polymer Examples
Polymer 1
Figure imgf000181_0001
Polymer 1
To a degassed mixture of Monomer 1 (443.3 mg, 0.289 mmol), 4,7- bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-2, 1 ,3-benzothiadiazole (1 12.2 mg, 0.289 mmol), anhydrous tetrahydrofuran (4.0 cm3), aqueous sodium carbonate solution (0.58 cm3, 1 .2 mmol, 2.0 M) and Aliquat 336 (10 mg) was added tris(dibenzylideneacetone) dipalladium(O) (5.3 mg, 0.006 mmol) and tri(o-tolyl)phospine (7.0 mg, 0.023 mmol) the mixture further degassed over 5 minutes. The mixture was heated at reflux for 15 minutes. Anhydrous toluene (4.0 cm3) was added and the mixture was stirred at reflux for 4 hours. Toluene (5 cm3) was added and the solution cooled briefly then precipitated into methanol (150 cm3). The solid was collected by filtration, washed with water and acetone. The solid was subjected to Soxhlet extraction (acetone, petroleum ether (80-100 °C) and chloroform). The chloroform fraction was concentrated in vacuo and then precipitated into methanol. The solid was collected by filtration to give Polymer 1 (380 mg, 87%) as a brown/blue solid. GPC (chlorobenzene,
50 °C) Mn = 65,000 g/mol, Mw = 185,000 g/mol. Polymer 2
Figure imgf000182_0001
To a degassed mixture of Monomer 1 (461.9 mg, 0.301 mmol), 4,7- bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-2, 1 ,3-benzothiadiazole (155.8 mg, 0.402 mmol), anhydrous tetrahydrofuran (5.0 cm3), aqueous sodium carbonate solution (0.80 cm3, 1.6 mmol, 2.0 M) and Aliquat 336 (10 mg) was added tris(dibenzylideneacetone)di-palladium(0) (7.4 mg,
0.008 mmol) and tri(o-tolyl)phospine (9.8 mg, 0.032 mmol) and the mixture degassed for an additional 10 minutes. The mixture was heated at reflux for 15 minutes. Anhydrous toluene (5.0 cm3) was added and the mixture heated at reflux for 1.5 hours. Toluene (5 cm3) was added, the solution cooled briefly then precipitated into methanol (150 cm3). The solid was collected by suction filtration, washed with water and acetone. The solid subjected to Soxhlet extraction (acetone, petroleum ether (80-100 °C) and chloroform). The chloroform solution was concentrated in vacuo before precipitation in methanol. The solid collected by filtration to give Polymer 2 (520 mg, 92%) as a brown/blue solid. GPC (chlorobenzene, 50 °C) Mn =
120,000 g/mol, Mw = 470,000 g/mol.
Polymer 3 To a degassed mixture of 2,7-dibromo-4,4,9,9-tetrahexadecyl-4,9-dihydro- s-indaceno[1 ,2-b:5,6-b']dithiophene (288.8 mg, 0.218 mmol), Monomer 1 (335.1 mg; 0.218 mmol), 4,7-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)-2, 1 ,3-benzothiadiazole (169.6 mg, 0.437 mmol), anhydrous
teatrahydrofuran (5.0 cm3), aqueous sodium carbonate solution (0.87 cm3, 1 .8 mmol, 2.0 M) and Aliquat 336 (10 mg) was added
tris(dibenzylideneacetone)di-palladium(0) (8.0 mg, 0.009 mmol) and tri(o- tolyl)phospine (10.6 mg, 0.035 mmol) and the mixture degassed for an additional 10 minutes. The mixture was heated at reflux for 15 minutes. Anhydrous toluene (5.0 cm3) was added and the mixture heated at reflux for 2 hours. Toluene (5 cm3) was added, the solution cooled briefly then precipitated into methanol (150 cm3). The solid was collected by suction filtration, washed with water and acetone. The solid was subjected to
Soxhlet extraction (acetone, petroleum ether (80-100 °C) and chloroform). The chloroform solution was concentrated in vacuo before precipitation in methanol. The solid was collected by filtration to give Polymer 3 (570 mg, 93%) as a brown/blue solid. GPC (chlorobenzene, 50 °C) Mn = 148,000 g/mol, Mw = 447,000 g/mol. PDI = 3.02
Polymer 4
Figure imgf000184_0001
To a degassed mixture of 2,7-dibromo-4,4,9,9-tetrahexadecyl-4,9-dihydro- s-indaceno[1 ,2-b:5,6-b']dithiophene (446.5 mg, 0.338 mmol), Monomer 1 (172.7 mg, 0.1 13 mmol), 4,7-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)-2, 1 ,3-benzothiadiazole (174.8 mg, 0.450 mmol), anhydrous
tetrahydrofuran (5.0 cm3), aqueous sodium carbonate solution (0.90 cm3,
1 .8 mmol, 2.0 M) and Aliquat 336 (10 mg) was added
tris(dibenzylideneacetone)di-palladium(0) (8.2 mg, 0.009 mmol) and tri(o- tolyl)phospine (10.9 mg, 0.036 mmol) and the mixture degassed for an additional 10 minutes. The mixture was heated at reflux for 15 minutes. Anhydrous toluene (5.0 cm3) was added and the mixture was heated at reflux for 2 hours. Toluene (5 cm3) was added, the solution cooled briefly then precipitated into methanol (150 cm3). The solid was collected by suction filtration, washed with water and acetone. The solid was subjected to Soxhlet extraction (acetone, petroleum ether (80-100 °C) and
chloroform). The chloroform solution was concentrated in vacu0 before precipitation in methanol. The solid was collected by filtration to give Polymer 4 (530 mg, 85%) as a brown/blue solid. GPC (chlorobenzene,
50 °C) Mn = 120,000 g/mol, Mw = 243,000 g/mol.
Use Example 1
Field-effect transistor fabrication and measurements Top-gate thin-film organic field-effect transistors (OFETs) were fabricated on glass substrates with thermally evaporated Au source-drain electrodes at the thickness of 40 nm. A planarization layer was deposited prior to the electrodes evaporation. The electrodes were then treated with Merck Lisicon® M001 using a standard procedure. 7 mg/cm3 solution of the organic semiconductor in dichlorobenzene was spin-coated on top (an optional annealing of the film was carried out at 100 °C, 150 °C or 200 °C for between 1 and 5 minutes followed by a spin-coated fluoropolymer dielectric material (Lisicon® D139 from Merck, Germany). Finally, a thermally evaporated Ag 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 (psat) was calculated for the compound. Field-effect mobility was calculated in the saturation regime (Vd > (Vg-Vo)) using equation (1 ):
Figure imgf000185_0001
where W was the channel width, L the channel length, C, the capacitance of insulating layer, Vg the gate voltage, Vo the turn-on voltage, and psat was the charge carrier mobility in the saturation regime. Turn-on voltage (Vo) was determined as the onset of source-drain current. The field effect transistor device characteristics for a device using Polymer 4 as the active OSC material in top gate bottom contact configuration is shown in Fig. 1. Therein the mobility was calculated based on the first derivative of the linear regime and second derivative for the saturation regime. The dimensions of the device are 500 pm (W) and 20 pm (L).
Use Example 2
Demonstration of photopatterning of the polymers
A solution of Polymer 4 in chloroform containing 0.15% Omnipol TX was spin-coated on glass substrate to prepare a film. The film was covered with a shadow mask and exposed to UV light of 254 nm at 1.536 J/cm2 for 2 minutes. Mesitylene was then puddled for 30 seconds and spun off. The resulting film thickness left is 28.67 nm. The smallest feature size is 10 pm (gap of transistor pattern).
Fig. 2 shows a microscopic image of the directly patterned film of Polymer 4 on bare glass.

Claims

Claims
1 . A conjugated polymer comprising one or more repeating units of formula I
Figure imgf000187_0001
and/or one or more divalent repeating units Ar6, wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Ar1, Ar2 a group selected from the following formulae
Figure imgf000187_0002
U1, U2 CR1R2, SiR1R2, GeR1R2, C=CR1 R2 or NR1,
Ar3, Ar4, Ar5 fused aryl or heteroaryl ring which has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Ar6 arylene or heteroarylene which has from 5 to 20 ring
atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L or R1,
R1, R2 H, F, Cl, CN, -Sp-Rc, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH2 groups are each optionally replaced by - 0-, -S-, -C(=0)-, -C(=S)-, -C(=0)-0- -0-C(=0)-, -NR0-, - SiR°R00-, -CF2-, -CR°=CR00-, -CY1=CY2- or -CºC- 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 each optionally replaced by F, Cl, Br, I or CN, and in which one or more CH2 or Chh groups are each optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L, and the pair of R1 and R2, together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Sp a spacer group,
Rc a maleimide or maleimide containing group that is
unsubstituted or substituted, preferably by C1-4 alkyl, very preferably by methyl,
L F, Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, R°,
OR0, SR°, -C(=0)X°, -C(=0)R°, -C(=0)-OR°, -O-C(=O)-R0, -NH2, -NHR°, -NR°R00, -C(=0)NHR°, -C(=0)NR°R00, - SO3R0, -SO2R0, -OH, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30, preferably 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, preferably F, -CN, R°, -OR0, -SR°, -C(=0)-R°, -C(=0)-OR°, -O-C(=O)-R0, -O- C(=0)-OR°, -C(=0)-NHR°, or -C(=O)-NR0R00, RO ROO |_| or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12, C atoms that is optionally fluorinated,
X° halogen, preferably F or Cl, k 0 or an integer from 1 to 10, preferably 0, 1 , 2, 3, 4, 5, 6 or
7, very preferably 0, 1 , 2 or 3, most preferably 1 , wherein the conjugated polymer comprises a) at least one unit of formula I wherein at least two groups R1 and R2 that are attached to the same C, Si or Ge atom denote each -Sp-Rc, or wherein at least one group R1 that is attached to an N atom denotes -Sp-Rc, or b) at least one unit Ar6 which is substituted by at least one group R1 that denotes -Sp-Rc, or both a) and b).
2. The conjugated polymer according to claim 1 , characterized in that the repeating units of formula I are selected from the following subformulae
Figure imgf000189_0001
wherein U1 , U2, Ar3, Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in claim 1
3. The conjugated polymer according to claim 1 or 2, characterized in that the groups Ar1 and Ar2 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000190_0001
A1 a A2a A1 b A2b wherein R1 and R2 have the meanings given in claim 1 . 4. The conjugated polymer according to one or more of claims 1 to 3, characterized in that the groups Ar3 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000191_0001
A3j A3k A31
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings W1, W2, W3 S, 0, Se or C=0, preferably S,
W4 S, 0, Se, C=0 or NR5, R5 8 one of the meanings given for R1 in claim 1.
5. The conjugated polymer according to one or more of claims 1 to 4, characterized in that the groups Ar4 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000193_0001
A4v A4w A4x wherein W1, W2, W3 and R5-8 have the meanings given in caim 4, V1 denotes CR5 or N, and R9 has one of the meanings given for R5.
6. The conjugated polymer according to one or more of claims 1 to 5, characterized in that the groups Ar5 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000195_0001
A5m A5n A5o 7. The conjugated polymer according to one or more of claims 1 to 6, characterized in that the groups Ar3 are on each occurrence identically or differently selected from the following formulae and their mirror images
/S
Figure imgf000196_0001
A3a1
Figure imgf000196_0002
A3o1 A3p1 A3q1
Figure imgf000198_0001
wherein R5-8 have the meanings given in claim 4. 8. The conjugated polymer according to one or more of claims 1 to 7, characterized in that the groups Ar4 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000198_0002
Figure imgf000199_0001
A4s1 A4t1 A4u1
Figure imgf000200_0001
A4v1 A4w1 A4x1 wherein R5-9 have the meanings given in claim 4 and 5.
9. The conjugated polymer according to one or more of claims 1 to 8, characterized in that the groups Ar5 are on each occurrence identically or differently selected from the following formulae and their mirror images
Figure imgf000200_0002
Figure imgf000201_0001
A5v1 A5w1 A5x1 wherein R5-9 have the meanings given in claim 4 and 5. 10. The conjugated polymer according to one or more of claims 1 to 9, characterized in that the units of formula I are selected from the following subformulae
Figure imgf000202_0001

Figure imgf000204_0001
-18 -19 -20-21-22-23
Figure imgf000206_0001
-30-31-32-33-34 -35 -36 -37-38-39-40-41 12-1
12-2
I2-3
12-4
I2-5 12-6
Figure imgf000210_0001
12-7
I2-8
Figure imgf000210_0002
12-9
Figure imgf000210_0003
12-12
12-13
Figure imgf000211_0001
12-14
12-15
Figure imgf000213_0001
I2-20
12-21
Figure imgf000213_0002
I2-22
Figure imgf000213_0003
I2-23
Figure imgf000213_0004
I2-24
Figure imgf000213_0005
-25 -26-27 -28 -29 I2-30
12-31
Figure imgf000215_0001
I2-32
I2-33
Figure imgf000215_0002
I2-34
Figure imgf000215_0003
Figure imgf000215_0004
I2-35 12 -42
Figure imgf000217_0001
12-43
Figure imgf000217_0002
I2-44
Figure imgf000217_0003
12-45
Figure imgf000217_0004
12 -46
Figure imgf000217_0005
12-47
Figure imgf000218_0001
10
15
Figure imgf000218_0002
20
Figure imgf000218_0003
Figure imgf000218_0004
Figure imgf000218_0005
35 I2-54
Figure imgf000219_0001
I2-55
Figure imgf000219_0002
Figure imgf000219_0003
I2-56
Figure imgf000219_0004
I2-57
Figure imgf000219_0005
I2-58
Figure imgf000219_0006
I2-59
Figure imgf000220_0001
-66-67-68-69-70
Figure imgf000222_0001
13-1
13-2
I3-3
13-4
I3-5
Figure imgf000223_0001

-9 14-10
Figure imgf000226_0001
Figure imgf000226_0002
Figure imgf000226_0003
-2
-3 -4-5 -6-7-8-9 wherein R1 , R2, R5 and R6 have the meanings given in claim 1 and 4, R3 and R4 have one of the meanings given for R1 and R2, and the benzene and thiophene rings are optionally substituted in free positions by one or more groups R5. 1 . The conjugated polymer according to one or more of claims 1 to 10, characterized in that Rc is selected from formula M
Figure imgf000228_0001
wherein Q1 and Q2 are each independently from one another H, Chh, C2H5, C3H7 or C4H9, very preferably H or CH3, most preferably CH3. 12. The conjugated polymer according to one or more of claims 1 to 11 , characterized in that Sp is selected from alkylene with 1 to 30, preferably 1 to 20, C atoms, wherein one or more, but not all, CH2 groups are each optionally replaced by -0-, -S-, -C(=0)-, -C(=S)-, - C(=0)-0-, -0-C(=0)-, -NR0-, -SiR°R00-, -CF2-, -CR°=CR00-, - CY1=CY2- or -CºC- 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 each optionally replaced by F, Cl, Br, I or CN.
13. The conjugated polymer according to one or more of claims 1 to 12, characterized in that it comprises one or more units Ar6, which preferably have electron donor properties, and are selected from the group consisting of the formulae D1 -D151 and their mirror images
Figure imgf000229_0001
Figure imgf000230_0001
Figure imgf000231_0001

Figure imgf000232_0001
(D63) (D64)
35
35

Figure imgf000239_0001
(D110) (D111) (D112)
(D125) (D126)
Figure imgf000241_0001
(D143) (D144)
Figure imgf000243_0001
(D151 ) wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently of each other have one of the meanings of R1 as given in claim 1 , and preferably at least one of the substituents R11-18 denotes Sp-Rc.
14. The conjugated polymer according to one or more of claims 1 to 13, characterized in that it comprises one or more units Ar6, which preferably have electron acceptor properties, and are selected from the group consisting of the formulae A1 -A103 and their mirror images
Figure imgf000244_0001
(A5) (A6) (A7) (A8)
Figure imgf000245_0001
Figure imgf000247_0001

Figure imgf000248_0001

Figure imgf000249_0001


Figure imgf000251_0001
(A96) (A97) (A98)
Figure imgf000252_0001
wherein R11, R12, R13, R14, R15 and R16 independently of each other have one of the meanings of R1 as given in claim 1 , and preferably at least one of the substituents R11-16 denotes Sp-Rc.
15. The conjugated polymer according to one or more of claims 1 to 14, characterized in that it comprises one or more units Ar6, which are selected from the group consisting of the formulae Sp1 -Sp18 and their mirror images Sp1
Sp2
Sp3
Sp4
Sp5
Sp6
Sp7 Sp14
Sp15
Sp16
Sp17
Sp18
wherein R11, R12, R13, R14 independently of each other have one of the meanings of R1 as given in claim 1 , and preferably at least one of R11 14 denotes Sp-Rc.
16. The conjugated polymer according to one or more of claims 1 to 15, characterized in that it comprises, preferably consists of, one or more, preferably two or more, units of formula I, 11 -17 or 11 -1 to 15-13, and one or more units Ar6 selected from the following groups
A2) the group consisting of the formulae D1 -D151 , very preferably from the formulae D1 , D7, D10, D1 1 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D1 1 1 , D139, D140, D141 , D146 and D150,
and/or
B2) the group consisting of the formulae A1 -A103, very preferably from the formulae A1 , A6, A7, A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103,
and/or
C2) the group consisting of the formulae Sp1 -Sp18, very preferably of the formulae Sp1 , Sp2, Sp6, Sp10, Sp1 1 , Sp12, Sp13 and Sp14.
17. The conjugated polymer according to one or more of claims 1 to 16, characterized in that it comprises one or more units selected from - CY1=CY2- and -CºC-, wherein Y1 and Y2 are independently of each other H, F, Cl or CN.
18. The conjugated polymer according to one or more of claims 1 to 17, characterized in that it comprises one or more units, preferably consists of, one or more units selected from the following groups
1A) the group consisting of units of formula I, 11 -17 and 11 -1 to 15-13 which are selected from electron acceptor units,
1 D) the group consisting of formula I, 11 -17 and 11 -1 to 15-13 which are selected from electron donor units,
2A) the group consisting of units Ar6 which are selected from electron acceptor units, preferably selected from the group consisting of formulae A1 -A103,
2D) the group consisting of units Ar6 which are selected from electron donor units, preferably selected from the group consisting of formulae D1 -D151 ,
3) the group consisting of units Ar6 which are selected from spacer units, preferably selected from the group consisting of formulae Sp1 -Sp18,
and wherein the polymer contains at least one unit selected from groups 1 A and 1 D, and the polymer contains at least one unit of group 1 A, 1 D, 2A, 2D or 3 which is at least monosubstituted by -Sp-Rc.
19. The conjugated polymer according to one or more of claims 1 to 18, characterized in that it comprises, preferably consists of, one or more, preferably two or more, repeating units of formula 111 and/or M2, and optionally one or more repeating units of formula M3:
-(C1)a-U-(C2)b-(C3)c-(CV 111
-(C1)a-(C2)b-U-(C3)c-(CV M2
-(C1)a-(C2)b-(C3)c-(CV M3 wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
U a unit selected from formula I, 11 -17 or 11 -1 to 15-13 as defined in any of claims 1 to 10, preferably selected from groups 1A and 1 D,
C1 4 distinct units having one of the meanings of Ar6 as defined in any if claims 13 to 16, preferably selected from groups 2A, 2D and 3, a, b, c, d 0 or 1 , wherein in formula M3 a+b+c+d>1 , and wherein the polymer contains at least one unit of formula 111 , M2 or M3 wherein at least one of U and C1 4 is at least monosubstituted by -Sp-Rc.
20. The conjugated polymer according to one or more of claims 1 to 19, characterized in that it selected of formula III:
Figure imgf000258_0001
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following
meanings
A a unit of formula 111 or M2,
B, C, D, E a unit of formula 111 , M2 or M3, x > 0 and < 1 , v, w, y, z > 0 and < 1 , v+w+x+y+z 1 , and n an integer >1 , preferably >5, and wherein at least one of A-E is at least monosubstituted by -Sp-Rc.
21. The conjugated polymer according to one or more of claims 1 to 20, characterized in that it comprises, very preferably consists of, one or more units selected from the group consisting of the following formulae and their mirror images
-(U)- U1 -(U-SP)- U2
-(Sp-U-Sp)- U3
-(D-Sp)- U4
-(A-Sp)- U5 -(Sp-D-Sp)- U6
-(Sp-A-Sp)- U7
-(A-D)- U8
-(D)- U9 -(Sp-D-Sp-D)- U10
-(A)- U11
-(Sp-A-Sp-A)- U12 wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following
meanings u the meaning given in claim 19,
D a donor unit selected from groups 1 D and 2D as defined in claim 18, A an acceptor unit selected from groups 1 A and 2A as defined in claim 18,
Sp a spacer unit selected from the group 3 as defined in claim 18, and wherein the polymer contains at least one unit U, D, A or Sp which is at least monosubstituted by -Sp-Rc.
22. The conjugated polymer according to one or more of claims 1 to 21 , characterized in that it is selected from formulae Pi-Px
-[(U-Sp]n- Pi -[(U-Sp)x-(Ar6-Sp)y]n- Pii
-[(U-Sp)x-(A-Sp)y]n- Piii
-[(U-Sp)x-(D-Sp)y]n- Piv
-[(U-D)x-(U-Sp)y]n- Pv _[(U-A)x-(U-Sp)y]n- Pvi
-[(D)x-(Sp-U-Sp)y]n- Pvii
-[(A)x-(Sp-U-Sp)y]n- Pviii
-[D-A]n- Pix
-[(D-Sp)x-(A-Sp)y]n- Pviii -[A-D-A]n- Pix
-[Sp-U1-Sp-U2]n- Px wherein A, D and Sp are as defined in formulae U2-U12, A, D and Sp can each, in case of multiple occurrence, also have different meanings, U1 and U2 have one of the meanings given for U and are different from each other, x and y denote the molar fractions of the corresponding units, x and y are each, independently of one another, a non-integer >0 and <1 , with x+y=1 , and n is an integer >1 , and wherein the polymer contains at least one unit U, D, A or Sp which is at least monosubstituted by -Sp-Rc.
23. The conjugated polymer according to one or more of claims 1 to 22, characterized in that it in the formulae U2-U12 and Pi-Px a) the donor units D and 2D are selected from the group consisting of the formulae D1 -D151 , very preferably of the formulae D1 , D7, D10, D1 1 , D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D1 1 1 , D139, D140, D141 , D146 and D150,
b) the acceptor units A and 2A are selected from the group
consisting of the formulae A1 -A103, very preferably of the formulae A1 , A6, A7, A15, A16, A20, A36, A49, A74, A78, A84, A88, A92, A94, A98, A102 and A103,
and
c) the spacer units Sp are selected from the group consisting of the formulae Sp1 -Sp18, very preferably of the formulae Sp1 , Sp2, Sp6, Sp10, Sp1 1 , Sp12, Sp13 and Sp14.
24. The conjugated polymer according to one or more of claims 1 to 23, it is selected from the following subformulae
Figure imgf000261_0001
wherein Rc has the meanings given in claim 1 or 11 , Sp has the meanings given in claim 1 or 12, Ar6 has the meanings given in claim 1 , 13, 14 or 15, x, y and n have the meanings given in claim 20.
25. The conjugated polymer according to one or more of claims 1 to 24, wherein the groups Rc are crosslinked.
26. A composition comprising one or more polymers according to one or more of claims 1 to 25, and further comprising one or more compounds having one or more of a semiconducting, hole or electron transporting, hole or electron blocking, electrically conducting, photoconducting, photoactive or light emitting property, and/or a binder.
27. Use of a polymer according to one or more of claims 1 to 25, or of a composition according to claim 25, in an electronic or optoelectronic device, or in a component of such a device or in an assembly comprising such a device.
28. A formulation comprising one or more polymers according to one or more of claims 1 to 24 or a composition according to claim 26, and further comprising one or more solvents selected from organic solvents.
29. A pattern or patterned film comprising a polymer according to one or more of claims 1 to 25 or a composition according to claim 26 wherein the groups Rc are crosslinked.
30. An electronic or optoelectronic device, or a component thereof, or an assembly comprising it, which comprises a polymer, composition or patterned film according to one or more of claims 1 to 26.
31. The electronic or optoelectronic device according to claim 30, which is selected from organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic light emitting electro-chemical cells (OLEC), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye-sensitized solar cells (DSSC), perovskite-based solar cells (PSC), organic photoelectrochemical cells (OPEC), laser diodes, Schottky diodes, photoconductors,
photodetectors, thermoelectric devices and LC windows.
32. The component according to claim 30, which is selected from charge injection layers, charge transport layers, interlayers, planarizing layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
33. The assembly according to claim 30, which is selected from
integrated circuits (IC), radio frequency identification (RFID) tags, security markings, security devices, flat panel displays, backlights of flat panel displays, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips. 34. A monomer of formula V1 or V2
RR1-(C1)a-U-(C2)b-(C3)c-(C4)d-RR2 V1
RR1-(C1)a-(C2)b-U-(C3)c-(C4)d-RR2 V2 wherein U, C1 4, a, b, c and d have the meanings of claim 19, and RR1 and RR2 are independently of each other selected from the group consisting of H, an activated C-H bond, Cl, Br, I, O-tosylate, 0- triflate, O-mesylate, O-nonaflate, -SiMe2F, -SiMeF2, -O-SO2Z1, - B(0Z2)2, -CZ3=C(Z3)2, -CºCH, - CºCSi(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 cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, and wherein at least one of RR1 and RR2 is different from H.
35. The monomer of claim 34, which is selected from the following
subformulae
RRI_U-RR2 Vi a
RR1-C1-U-C2-RR2 V1 b
RR1-C1-U-RR2 V1 C RR1-U-C2-RR2 V1 d
wherein U, C1, C2, RR1 and RR2 are as defined in claim 34.
36. A process of preparing a polymer according to any of claims 1 to 24, by copolymerising one or more monomers of formula V1 , V2 or V1 a- d as defined in claim 34 and 35 with each other or with one or monomers of the following formulae in an aryl-aryl coupling reaction
Figure imgf000266_0001
wherein C1 4, RR1 and RR2 have the meanings given in claim 34.
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