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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
  • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
  • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
  • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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  • 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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  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
  • H10K85/211—Fullerenes, e.g. C60
  • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
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  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/50—Photovoltaic [PV] devices
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  • Y02E10/00—Energy generation through renewable energy sources
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• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to novel fullerene derivatives, to methods for their preparation and educts or intermediates used therein, to mixtures and formulations containing them, to the use of the fullerene derivatives, mixtures and formulations as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising, or being prepared from, these fullerene derivatives, mixtures or formulations.
• OE organic electronic
• OPD organic photovoltaic
• OPD organic photodetectors
• organic semiconducting (OSC) materials in order to produce more versatile, lower cost electronic devices.
• OFETs organic field effect transistors
• OLEDs organic light emitting diodes
• OPDs organic photodetectors
• OCV organic photovoltaic cells
• sensors memory elements and logic circuits to name just a few.
• the organic semiconducting materials are typically present in the electronic device in the form of a thin layer, for example of between 50 and 300 nm thickness.
• the photosensitive layer in an OPV or OPD device is typically composed of at least two materials, a p-type semiconductor such as a polymer, an oligomer or a define molecular unit and a n-type semiconductor such as a fullerene derivative, graphene, a metal oxide, or quantum dots.
• a p-type semiconductor such as a polymer, an oligomer or a define molecular unit
• a n-type semiconductor such as a fullerene derivative, graphene, a metal oxide, or quantum dots.
• Figure 1 shows some known fullerene derivatives, including Fullerene 1 and the respective multiple adducts both described in WO2008/018931 and WO2010/087655, Fullerene 2 and the respective multiple adducts both described in US 8,217,260, Fullerene 3 described in JP 2012-094829, Fullerene 4 described in WO 2009/008323 and JP 2011-98906 and Fullerene 5 and the respective multiple adducts both described in JP 2011-181719.
• the physical properties of these fullerene derivatives such as solubility, light stability, thermal stability are limiting their use in commercial applications.
• fullerene derivatives which are easy to synthesize, especially by methods suitable for mass production, show good structural organization and film-forming properties, exhibit good electronic properties, especially a high charge carrier mobility, a good processability, especially a high solubility in organic solvents, and high light and thermal stability. It was an aim of the present invention to provide fullerene derivatives that provide one or more of the above-mentioned advantageous properties.
• Another aim of the invention was to extend the pool of n-type OSC materials available to the expert.
• Other aims of the present invention are immediately evident to the expert from the following detailed description.
• cyclohexadiene fullerenes as disclosed and claimed hereinafter. Surprisingly it was found that these cyclohexadiene fullerenes demonstrate one or more of the improved properties as described above, especially for use in OPV/OPD applications, compared to the fullerenes disclosed in prior art.
• KR 1128833 B1 describes an organic/inorganic hybrid solar cell containing a fullerene derivative and a dye in an inorganic semiconductor, where the fullerene derivative, including one monosubstituted cyclohexadiene fullerene example, contains at least one of carboxylic acid group, anhydride group, phosphoric acid group, siloxane group, and sulfonic acid group.
• the fullerene derivative including one monosubstituted cyclohexadiene fullerene example, contains at least one of carboxylic acid group, anhydride group, phosphoric acid group, siloxane group, and sulfonic acid group.
• such groups have the drawback that they can act as charge traps in an OPV device configuration and liberate acidic protons (H + ) that are detrimental for the performance and lifetime of the OPV device.
• the invention relates to compounds of formula I, including isomers thereof,
• C n denotes a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside,
• Adduct is a secondary adduct, or a combination of secondary adducts, appended to the fullerene C n with any connectivity, m is 0, an integer > 1 , or a non-integer > 0, o is an integer > 1 ,
• R 1 , R 2 , R 3 , R 4 independently of each other denote H, halogen, CN, R 5 or R 6 ,
• R 5 denotes a saturated or unsaturated, non-aromatic carbo- or heterocyclic group, or an aryl, heteroaryl, aryloxy or
• heteroaryloxy group wherein each of the aforementioned groups has 3 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is optionally substituted by one or more halogen atoms or CN groups, or by one or more identical or different groups R 6 ,
• Y 1 and Y 2 denote independently of each other H, F, CI or CN,
• R° and R' oo denote independently of each other H or an optionally
• the invention further relates to the use of compounds of formula I as electron acceptor or n-type semiconductor.
• the invention further relates to the use of compounds of formula I as electron acceptor or n-type component in a semiconducting material, organic electronic device or component of an organic electronic device.
• the invention further relates to a mixture comprising two or more fullerene derivatives, one or more of which are a compound of formula I.
• the invention further relates to a mixture comprising one or more compounds of formula I, preferably as electron acceptor or n-type component, and further comprising one or more semiconducting compounds, which preferably have electron donor or p-type properties.
• the invention further relates to a mixture comprising one or more compounds of formula I and one or more p-type organic semiconductor compounds, preferably selected from conjugated organic polymers.
• the invention further relates to a mixture comprising one or more compounds of formula I and one or more compounds which are selected from compounds having one or more of a semiconducting, charge transport, hole transport, electron transport, hole blocking, electron blocking, electrically conducting, photoconducting and light emitting property.
• the invention further relates to the use of a compound of formula I or a mixture comprising it as semiconducting, charge transport, electrically conducting, photoconducting, thermoelectric or light emitting material, or in an optical, electrooptical, electronic, electroluminescent, photoluminescent or thermoelectric 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, thermoelectric or light emitting material, which comprises a compound of formula I or a mixture comprising it as described above and below.
• the invention further relates to a formulation comprising one or more compounds of formula I, or a mixture or material comprising it as described above and below, and further comprising one or more solvents, preferably selected from organic solvents.
• the invention further relates to an optical, electrooptical, electronic,
• electroluminescent, photoluminescent or thermoelectric device or a
• the invention further relates to an optical, electrooptical, electronic,
• electroluminescent, photoluminescent or thermoelectric device or a
• the optical, electrooptical, electronic, electroluminescent, photoluminescent and thermoelectric devices include, without limitation, organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, photoconductors, photodetectors and thermoelectric devices.
• OFET organic field effect transistors
• OFT organic thin film transistors
• OLED organic light emitting diodes
• OLET organic light emitting transistors
• OLET organic light emitting transistors
• OLED organic light emitting transistors
• OLET organic photovoltaic devices
• OPD organic photodetectors
• organic solar cells laser diodes, Schottky diodes, photoconductors, photodetectors and thermoelectric devices.
• the components of the above devices include, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
• charge injection layers charge transport layers
• interlayers interlayers
• planarising layers antistatic films
• PEM polymer electrolyte membranes
• conducting substrates conducting patterns.
• the assemblies comprising such devices or components include, without limitation, integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containing 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
• the compounds, mixtures or materials 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 mixture comprising one or more compounds of formula I and one or more p-type organic semiconductor compounds that are selected from conjugated organic polymers.
• the invention further relates to a bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device, comprising such a bulk heterojunction .
• BHJ bulk heterojunction
• fullerene will be understood to mean a compound composed of an even number of carbon atoms, which form a cage-like fused- ring having a surface which comprises six-membered rings and five- membered rings, usually with twelve five-membered rings and the rest six- membered rings, optionally with one or more atoms trapped inside.
• the surface of the fullerene may also contain hetero atoms like B or N.
• endohedral fullerene will be understood to mean a fullerene with one or more atoms trapped inside.
• metalofullerene will be understood to mean an endohedral fullerene wherein the atoms trapped inside are selected from metal atoms.
• carbon based fullerene will be understood to mean a fullerene without any atoms trapped inside, and wherein the surface is comprised only of carbon atoms.
• polymer will be understood to mean a molecule of relatively high molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from
• oligomer will be understood to mean a molecule of intermediate molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass (Pure Appl. Chem., 1996, 68, 2291 ).
• a polymer will be understood to mean a compound having > 1 , i.e. at least 2 repeat units, preferably > 5 repeat units, and an oligomer will be understood to mean a compound with > 1 and ⁇ 10, preferably ⁇ 5, repeat units.
• polymer will be understood to mean a molecule that encompasses a backbone (also referred to as “main chain”) of one or more distinct types of repeat units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms "oligomer”,
• copolymer "homopolymer” and the like.
• polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto.
• residues and other elements while normally removed during post polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media.
• an asterisk ( * ) will be understood to mean a chemical linkage to an adjacent unit or to a terminal group in the polymer backbone.
• an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring.
• the terms “repeat unit”, “repeating unit” and “monomeric unit” are used interchangeably and will be understood to mean the constitutional repeating unit (CRU), which is the smallest constitutional unit the repetition of which constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain (Pure Appl. Chem., 1996, 68, 2291 ).
• the term “unit” will be understood to mean a structural unit which can be a repeating unit on its own, or can together with other units form a constitutional repeating unit.
• terminal group will be understood to mean a group that terminates a polymer backbone.
• the expression "in terminal position in the backbone” will be understood to mean a divalent unit or repeat unit that is linked at one side to such a terminal group and at the other side to another repeat unit.
• Such terminal groups include endcap groups, or reactive groups that are attached to a monomer forming the polymer backbone which did not participate in the polymerisation reaction, like for example a group having the meaning of R 5 or R 6 as defined below.
• endcap group will be understood to mean a group that is attached to, or replacing, a terminal group of the polymer backbone.
• the endcap group can be introduced into the polymer by an endcapping process. Endcapping can be carried out for example by reacting the terminal groups of the polymer backbone with a monofunctional compound
• endcapper like for example an alkyi- or arylhaiide, an alkyi- or arylstannane or an alkyi- or arylboronate.
• the endcapper can be added for example after the polymerisation reaction. Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerisation reaction. In situ addition of an endcapper can also be used to terminate the polymerisation reaction and thus control the molecular weight of the forming polymer.
• Typical endcap groups are for example H, phenyl and lower alkyl.
• small molecule will be understood to mean a monomeric compound which typically does not contain a reactive group by which it can be reacted to form a polymer, and which is designated to be used in monomeric form.
• monomer unless stated otherwise will be understood to mean a monomeric compound that carries one or more reactive functional groups by which it can be reacted to form a polymer.
• Electrode 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.
• 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
• 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.
• conjugated will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp 2 -hybridisation (or optionally also sp-hybridisation), and wherein these C atoms may also be replaced by hetero atoms. In the simplest case this is for example a compound with alternating C-C single and double (or triple) bonds, but is also inclusive of compounds with aromatic units like for example 1 ,4-phenylene.
• the term "mainly” in this connection will be understood to mean that a compound with naturally (spontaneously) occurring defects, or with defects included by design, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
• the molecular weight is given as the number average molecular weight M n or weight average molecular weight M w , which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran,
• 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 -C ⁇ C-), or optionally combined with at least one non-carbon atom such as N, O, S, P, B, Si, Se, As, Te or Ge (for example carbonyl etc.).
• the term "hydrocarbyl group” will be understood to mean a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example N, O, S, P, B, Si, Se, As, Te or Ge.
• hetero atom will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean N, O, S, P, B, Si, Se, As, Te or Ge.
• a carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, and may include spiro-connected and/or fused rings.
• Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore alkylaryloxy, arylcarbonyl,
• aryloxycarbonyl arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, wherein all these groups do optionally contain one or more hetero atoms, preferably selected from B, N, O, S, P, Si, Se, As, Te and Ge.
• carbyl and hydrocarbyl groups include for example: a C1-C40 alkyl group, a Ci-C 40 fluoroalkyl group, a C1-C40 alkoxy or oxaalkyl group, a C2- C40 alkenyl group, a C 2 -C 4 o 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 C 6 -C 8 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.
• Ci-C 2 o alkyl group a C1-C20 fluoroalkyl group, a C 2 -C 2 o alkenyl group, a C 2 -C 2 o alkynyl group, a C3-C 20 allyl group, a C4-C20 alkyldienyl group, a C 2 -C 2 o ketone group, a C2-C20 ester group, a C6-C12 aryl group, and a C4-C20 polyenyl group, respectively.
• groups having carbon atoms and groups having hetero atoms like e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.
• the carbyl or hydrocarbyl group may be an acyclic group or a cyclic group.
• carbyl or hydrocarbyl group is an acyclic group, it may be straight- chain or branched.
• 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 optionally replaced by a hetero atom, preferably selected from N, O, 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, wherein
• Preferred substituents L are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyi, thioalkyi, fluoroalkyi and fluoroalkoxy with 1 to 12 C atoms or alkenyl or alkynyl with 2 to 12 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 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 ring C atoms, wherein one or more of the C ring 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
• 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 be replaced by N, naphthalene, thiophene,
• Very preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3-b]furan, se
• aryl and heteroaryl groups are those selected from the groups shown hereinafter.
• An alkyl or alkoxy group i.e., where the terminal CH 2 group is replaced by -0-, can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7, 8 or 12 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or dodecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy or dodecoxy furthermore methyl, nonyl, decyl, undecyl, , tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, , tridecoxy or tetradecoxy, for example.
• alkenyl groups are C2-C 7 -1 E-alkenyl, C 4 -C -3E-alkenyl, C 5 -C7-4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C2-C 7 -1 E- alkenyl, C 4 -C 7 -3E-alkenyl and C5-C 7 -4-alkenyl.
• 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.
• radicals together form a carbonyloxy group -C(O)-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, acetyloxy methyl, propionyloxymethyl,
• butyryloxymethyl pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,
• An alkyl group wherein two or more CH 2 groups are replaced by -O- 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,
• a fluoroalkyl group is preferably perfluoroalkyl CiF 2i+ i, wherein i is an integer from 1 to 15, in particular CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F , C 6 F 13 , C 7 Fi 5 or C 8 Fi 7 , very preferably CeFi 3 , or partially fluorinated alkyl, in particular 1 ,1 - difluoroalkyl, all of which are straight-chain or branched.
• the alkyl groups are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.
• Very preferred groups of this type are selected from the group consisting of the following formulae
• ALK denotes optionally fluorinated and straight-chain or branched, preferably straight-chain, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C- atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached. Especially preferred among these groups are those wherein all ALK
• halogen includes F, CI, Br or I, preferably F, CI or Br.
• the compounds of formula I are easy to synthesize, especially by methods suitable for mass production, and exhibit advantageous properties. For example, they show good structural organization and film-forming properties, exhibit good electronic properties, especially high charge carrier mobility, a good processability, especially a high solubility in organic solvents, and high light and thermal stability
• the compounds of formula I are especially suitable as electron acceptor or n- type semiconductor, especially in semiconducting materials containing both donor and acceptor components, and for the preparation of a mixture of p-type and n-type semiconductors which are suitable for use in BHJ OPV devices.
• the monosubstituted or polysubstituted cyclohexadiene fullerenes of formula I, or a mixture comprising two or more fullerene derivatives, one or more of which are selected from formula I is blended with a further p-type semiconductor such as a polymer, an oligomer or a defined molecular unit to form the active layer in the OPV/OPD device (also referred to as "photoactive layer").
• a further p-type semiconductor such as a polymer, an oligomer or a defined molecular unit to form the active layer in the OPV/OPD device (also referred to as "photoactive layer").
• the OPV/OPD device is usually further composed of a first, transparent or semi-transparent electrode, typically provided on a transparent or semi- transparent substrate, on one side of the active layer and a second metallic or semi-transparent electrode on the other side of the active layer.
• Additional interfacial layer(s) acting as hole blocking layer, hole transporting layer, electron blocking layer and/or electron transporting layer typically comprising a metal oxide (for example, ZnO x , TiO x , ZTO, MoO x , NiO x ), a salt (for example: LiF, NaF), a conjugated polymer electrolyte (for example: PEDOT:PSS or PFN), a conjugated polymer (for example: PTAA) or an organic compound (for example: NPB, Alq 3 , TPD), can be inserted between the active layer and an electrode.
• a metal oxide for example, ZnO x , TiO x , ZTO, MoO x , NiO x
• a salt for example: LiF, NaF
• a conjugated polymer electrolyte for example: PEDOT:PSS or PFN
• a conjugated polymer for example: PTAA
• organic compound for example: NPB, Alq 3 , TPD
• Electron accepting and/or donating unit(s) in position R 1 to R 4 reduce the fullerene band-gap and therefore the potential for improved light absorption.
• ii) Additional fine-tuning of the electronic energies (HOMO/LUMO levels) by careful selection of electron accepting and/or donating unit(s) in position R 1 to R 4 increases the open circuit potential (V oc ).
• o preferably denotes 1 , 2, 3 or, 4, very preferably 1 or 2.
• the number of carbon atoms n of which the fullerene C n is composed is preferably 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70.
• the fullerene C n in formula 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- ih)[5,6]fullerene, (C 70- D5h)[5,6]fullerene, (C 76- D2*)[5,6]fullerene, (C 84-
• the endohedral fullerenes are preferably metallofullerenes.
• Suitable and preferred metallofullerenes include, without limitation, La@C6o, La@C 8 2,
• the fullerene C n is substituted at a [6,6] and/or [5,6] bond, preferably substituted on at least one [6,6] bond.
• the fullerene C n may have any number (m) of secondary adducts appended, named "Adduct" in formula I.
• the secondary adduct may be any possible adduct or combination of adducts with any connectivity to the fullerene.
• all adducts may be connected to one another in any combination in the finished product or during synthesis, to facilitate preferred properties in the finished product.
• the number m of secondary adducts appended to the fullerene C n is 0, an integer ⁇ 1 , or a non- integer > 0 like 0.5 or 1.5, and is preferably 0, 1 or 2.
• the number m of the secondary adducts appended to the fullerene C n is 0.
• the number m of the secondary adducts appended to the fullerene C n is >0, preferably 1 or 2.
• R S1 , R S2 , R S3 , R S4 and R S5 independently of each other denote H, halogen or CN, or have one of the meanings of R 5 or R 6 as given in formula I, and
• Ar s1 and Ar S2 are 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 substituted by one or more identical or different substituents R s , wherein R s denotes halogen, preferably F, or a straight-chain, branched or cyclic alkyl moiety with 1 to 30, preferably 4 to 20, very preferably 5 to 15, C atoms, in which one or more CH 2 groups are optionally replaced by -0-, -S-, -C(O)-, - C(S)-, -C(O)-O-, -O-C(O)-, -S(0) 2 -, -NR 0 -, -SiR°R 00 -, -CF 2 -, wherein R° and R oc have one of the meanings given above and below.
• R 1 , R 2 , R 3 and R 4 are independently of each other selected from H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 4 to 20 C atoms, in which one or more CH 2 groups are optionally replaced by - 0-, -S-, -C(O)-, -C(S)-, -C(0)-O-, -O-C(O)-, -NR 0 -, -SiR°R 00 -, -CF 2 -, or a carbocyclic or heterocyclic group selected from the following formulae
• R 000 has one of the meanings of R 00 different from H
• in formula C-1 at least one of R 1 , R 2 , R 3 , R 4 and R 15 is different from H and in formula C- 4 at least one of R 11 , R 12 and R 3 is different from H.
• each of the aforementioned formulae at least one substituent R 11 , R 2 , R 13 , R 14 , R 15 , R 6 , R 17 or R 8 is different from H.
• the linkage to the cyclohexadiene fullerene is preferably located in 2-position (relative to the hetero atom), and the substituent R 13 in 5-position is preferably different from H.
• the linkage to the cyclohexadiene fullerene is preferably located in 2-position (relative to the hetero atom), and the
• substituent R 13 in 5-position is preferably different from H.
• the linkage to the cyclohexadiene fullerene is preferably located in 2-position (relative to the hetero atom).
• R 1 , R 2 , R 3 and R 4 are independently of each other selected selected from H, straight-chain branched or cyclic alkyl with 1 to 30, preferably 4 to 20, C atoms, -0-, -COOR 000 , -COR 000 , CONR°R 000 , -F, -CI, -NR°R 000 , or a carbocyclic or heterocyclic group selected from the following formulae
• R 000 has one of the meanings of R 00 different from H
• R 11 is different from H.
• R 6 is straight-chain, branched or cyclic alkyl with 1 to 30, preferably 4 to 30, very preferably 4 to 20 C atoms, in which one or more CH 2 groups are optionally replaced by -0-, -S-, -C(O)-, -C(S)-, -C(O)-0-, -O-C(O)-, -NR 0 -, - SiR°R 00 -, -CF 2 -, and wherein one or more H atoms are replaced by fluorine atoms, wherein R° and R 00 have one of the meanings given above and below.
• R 6 are selected from alkyl, fluoroalkyl, alkoxy and thioalkyl having 1 to 30, preferably 4 to 30, very preferably 4 to 20, most preferably 5 to 15 C atoms.
• R° and R 00 preferably denote, independently of each other, H or alkyl with 1 to 12 C-atoms.
• R 000 preferably denotes alkyl with 1 to 12 C atoms.
• cyclohexadiene fullerenes of formula I and its subformulae can be prepared by Danishefsky's diene cycloaddition, see for example J. Org. Chem. 1996, 60, 6353-6361 , J. Am. Chem. Soc. 2000, 122, 8333-8334, ene-diyne cycloaddition, see for example, J. Am. Chem. Soc. 1998, 120, 12232-12236,
• the compounds of formula I or its subformulae can also be used in mixtures, for example together with other monomeric compounds, or polymers, having one or more of a semiconducting, charge transport, hole transport, electron transport, hole blocking, electron blocking, electrically conducting,
• fullerene mixture comprising one or more fullerene derivatives of formula I or its subformulae or of a preferred embodiment as described above and below (hereinafter simply referred to as “fullerene derivative of this invention”), and one or more additional compounds, preferably having one or more of a semiconducting, charge transport, hole transport, electron transport, hole blocking, electron blocking, electrically conducting, photoconducting and light emitting property.
• additional compounds in the fullerene mixture can be selected for example from fullerene derivatives other than those of this invention, or from conjugated organic polymers.
• the fullerene mixture can be prepared by conventional methods that are described in prior art and known to the skilled person.
• a preferred embodiment of the present invention relates to a fullerene mixture, comprising one or more fullerene derivatives, at least one of which is a fullerene derivative of this invention, and further comprising one or more conjugated organic polymers, which are preferably selected from electron donor, or p-type, semiconducting polymers.
• a fullerene mixture is especially suitable for use in the photoactive layer of an OPV or OPD device.
• the fullerene(s) and polymer(s) are selected such that the fullerene mixture forms a bulk heterojunction (BHJ).
• a suitable conjugated organic polymer for use in a fullerene mixture according to the present invention can be selected from polymers as described in prior art, for example in
• a preferred polymer is selected from the group consisting of poly(3-substituted thiophene) and poly(3-substituted selenophene), for example poly(3-alkyl thiophene) or poly(3-alkyl selenophene), preferably poly(3-hexyl thiophene) or poly(3-hexyl selenophene).
• a further preferred polymer comprises one or more repeating units selected from formulae lla and lib:
• A is arylene or heteroarylene with 5 to 30 ring atoms that is
• D is arylene or heteroarylene with 5 to 30 ring atoms that is
• A is optionally substituted by one or more groups R s , and preferably has electron donor property
• Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and
• arylene or heteroarylene that is different from A and D preferably has 5 to 30 ring atoms, and is optionally substituted, preferably by one or more groups R s , is on each occurrence identically or differently F, Br, CI, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(0)NR°R°°, -C(O)X 0 , -C(O)R 0 , - C(O)OR°, -NH 2 , -NR°R 00 , -SH, -SR°, -S0 3 H, -SO 2 R°, -OH, -NO 2 , CF 3 , -SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, are independently of each other H or optionally substituted Ci-4o carbyl or
• the polymer comprises at least one repeating unit of formula Ma wherein b is at least 1. Further preferably the polymer comprises at least one repeating unit of formula lla wherein b is at least 1 , and at least one repeating unit of formula lib wherein b is at least 1.
• a further preferred polymer comprises, in addition to the units of formula lla and/or lib, one or more repeating units selected from monocyclic or polycyclic arylene or heteroarylene groups that are optionally substituted.
• Additional repeating units are preferably selected of formula III -[(Ar 1 )a-(Ar 2 )c-(Ar 3 ) d ]- III wherein Ar 1 , Ar 2 , Ar 3 , a, c and d are as defined in formula lla.
• polymer is selected of formula IV:
• A, B, C independently of each other denote a distinct unit of formula lla, Mb or III, x is > 0 and ⁇ 1 , y is > 0 and ⁇ 1 , z is > 0 and ⁇ 1, x+y+z is 1 , and n is an integer >1.
• B or C denotes a unit of formula lla.
• B and C denotes a unit of formula lla and one of B and C denotes a unit of formula Mb.
• a preferred polymer of formula IV is selected from the following formulae
• the total number of repeating units n is preferably from 2 to 10,000.
• the total number of repeating units n is preferably > 5, very preferably > 10, most preferably ⁇ 50, and preferably ⁇ 500, very preferably ⁇ 1 ,000, most preferably ⁇ 2,000, including any combination of the aforementioned lower and upper limits of n.
• the polymer can be a homopolymer or copolymer, like a statistical or random copolymer, alternating copolymer or block copolymer, or a combination of the aforementioned.
• a polymer selected from the following groups: - Group A consisting of homopolymers of the unit D or (Ar 1 -D) or (Ar'-D-Ar 2 ) or (Ar 1 -D-Ar 3 ) or (D-Ai ⁇ -Ar 3 ) or (Ar'-D-Ar ⁇ -Ar 3 ) or (D-Ar 1 -D), i.e. where all repeating units are identical,
• Group B consisting of random or alternating copolymers formed by
• a preferred polymer of formula IV and IVa to IVk is selected of formula V
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 1 1 0 8 independently of each other denote H or have one of the meanings of R s as defined above and below.
• Ar 1 , Ar 2 and Ar 3 are selected from the group consisting of the following formulae
• the polymer can be prepared for example from monomers selected from the following formulae
• R 23 -(Ar 1 )a-A-(Ar 2 ) c -R 24 Vic VId wherein A, D, Ar , Ar 2 , a and b have the meanings of formula lla and lib, or one of the preferred meanings as described above and below, and R 23 and R 24 are, preferably independently of each other, selected from the group
• X° is halogen, preferably CI, Br or I, Z 1"4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z 2 may also together form a cyclic group.
• Suitable monomers are for example selected from the following subformulae
• the polymer can be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature. Other methods of preparation can be taken from the examples.
• the polymers can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, C-H activation coupling, Heck coupling or Buchwald coupling. Suzuki coupling, Stille coupling and Yamamoto coupling are especially preferred.
• the monomers which are Yamamoto coupling, Suzuki coupling, Stille coupling and Yamamoto coupling are especially preferred.
• 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 polymer can be prepared by coupling one or more monomers selected from formulae Vla-Vld and their subformulae in an aryl-aryl coupling reaction, wherein R 23 and R 24 are selected from CI, Br, I, -B(OZ 2 ) 2 and -Sn(Z ) 3 .
• Preferred aryl-aryl coupling and polymerisation methods used in the processes described above and below are Yamamoto coupling, Kumada coupling,
• Negishi coupling Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C-H activation coupling, Ullmann coupling or Buchwald coupling.
• Suzuki coupling is described for example in WO
• Yamamoto coupling is described in for example in T. Yamamoto et a/., Prog. Polym. Sci., 1993, 17, 1153-1205, or WO 2004/022626 A1 , and Stille coupling is described for example in Z. Bao et al., J. Am. Chem. Soc, 1995, 117, 12426-12435.
• monomers having two reactive halide groups are
• 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(Ph 3 P) 4 .
• Another preferred phosphine ligand is tris(orf/70-tolyl)phosphine, i.e. Pd(o-Tol 3 P) 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(dibenzyl-ideneacetone)dipalladium(0), bis(dibenzylideneacetone)- palladium(O), or Pd(ll) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(orf/7o-tolyl)phosphine or tri(tert-butyl)phosphine.
• Suzuki polymerisation is performed in the presence of a base, for example sodium carbonate, potassium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or
• Yamamoto polymerisation employs a Ni(0) complex, for example bis(1 ,5-cyclooctadienyl) nickel(O).
• Suzuki and Stille polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers.
• Statistical or block copolymers can be prepared for example from the above monomers of formula VI or its subformulae, wherein one of the reactive groups is halogen and the other reactive group is a boronic acid, boronic acid derivative group or and alkylstannane. The synthesis of statistical, alternating and block
• copolymers is described in detail for example in WO 03/048225 A2 or WO
• fullerene mixture in a formulation according to the present invention, including solvents, is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
• concentration of the fullerene derivatives of this invention in a fullerene mixture is preferably from 10 to 90 % by weight, very preferably from 33 % to 80 % by weight.
• Another aspect of the present invention relates to a formulation comprising one or more fullerene derivatives of this invention, or a fullerene mixture as described above, and further comprising one or more solvents, preferably selected from organic solvents.
• Such a formulation is preferably used as a carrier for the preparation of a semiconducting layer of an OE device, like an OPV or OPD device, wherein the fullerene derivative or fullerene mixture is for example used in the
• the formulation further comprises one or more binders to adjust the rheological properties, as described for example in WO 2005/055248 A1.
• the formulations according to the present invention preferably form a solution.
• the invention additionally provides an electronic device comprising a fullerene derivative of this invention or fullerene mixture, or a semiconducting layer comprising it, as described above and below.
• Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices,
• electrophotographic recording devices organic memory devices, sensor devices, charge injection. layers, Schottky diodes, planarising layers, antistatic films, conducting substrates and conducting patterns.
• Especially preferred electronic device are OFETs, OLEDs, OPV and OPD devices, in particular bulk heterojunction (BHJ) OPV devices and OPD
• the active semiconductor channel between the drain and source may comprise the layer of the invention.
• the charge (hole or electron) injection or transport layer may comprise the layer of the invention.
• a fullerene mixture is used that contains a p-type (electron donor) semiconductor and an n-type (electron acceptor) semiconductor.
• the p-type semiconductor is for example a
• n-type semiconductor is a fullerene derivative of this invention, a mixture of two or more fullerenes, at least one of which is a fullerene derivative of this invention.
• the device preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi-transparent substrate on one side of the active layer, and a second metallic or semi-transparent electrode on the other side of the active layer.
• the active layer according to the present invention is further blended with additional organic and inorganic compounds to enhance the device properties.
• metal particles such as Au or Ag
• nanoparticules or Au or Ag nanoprism for enhancements in light harvesting due to near-field effects (i.e. plasmonic effect) as described, for example in Adv. Mater. 2013, 25 (17), 2385-2396 and Adv. Ener. Mater.
• a molecular dopant such as 2,3,5,6-tetrafluoro- 7,7,8,8-tetracyanoquinodimethane for enhancement in photoconductivity as described, for example in Adv. Mater.
• a stabilising agent consisting of a UV absorption agent and/or anti-radical agent and/or antioxidant agent such as 2-hydroxybenzophenone, 2- hydroxyphenylbenzotriazole, oxalic acid anilides, hydroxyphenyl triazines, merocyanines, hindered phenol, N-aryl-thiomorpholine, N-aryl-thiomorpholine- 1 -oxide, N-aryl-thiomorpholine-1 ,1 -dioxide, N-aryl-thiazolidine, N-aryl- thiazolidine-1 -oxide, N-aryl-thiazolidine-1 ,1 -dioxide and 1 ,4- diazabicyclo[2.2.2]octane as described, for example, in WO2012095796 A1 and in WO2013021971 A1.
• a UV absorption agent and/or anti-radical agent and/or antioxidant agent such as 2-hydroxybenzophenone, 2- hydroxypheny
• the device preferably may further comprise a UV to visible photo-conversion layer such as described, for example, in J. Mater. Chem. 2011 , 27, 12331 or a NIR to visible or IR to NIR photo-conversion layer such as described, for example, in J. Appl. Phys. 2013, 773, 124509.
• a UV to visible photo-conversion layer such as described, for example, in J. Mater. Chem. 2011 , 27, 12331
• a NIR to visible or IR to NIR photo-conversion layer such as described, for example, in J. Appl. Phys. 2013, 773, 124509.
• the OPV or OPD device comprises, between the active layer and the first or second electrode, one or more additional buffer layers acting as hole transporting layer and/or electron blocking layer, which comprise a material such as metal oxides, like for example, ZTO, MoO x , NiO x , a doped conjugated polymer, like for example PEDOTPSS and polypyrrole- polystyrene sulfonate (PPy:PSS), a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example substituted triaryl amine derivatives such as 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), graphene based materials, wherein
• crosslinked N-containing compound derivatives or an organic compound like for example tris(8-quinolinolato)-aluminium(lll) (Alq 3 ), phenanthroline
• the ratio polymenfullerene derivative is preferably from 5:1 to 1 :5 by weight, more preferably from 1 :1 to 1 :3 by weight, most preferably 1 :1 to 1 :2 by weight.
• a polymeric binder may also be included, from 5 to 95% by weight. Examples of binder include polystyrene (PS), polypropylene (PP) and polymethylmethacrylate (PMMA).
• a fullerene derivative, fullerene mixture or formulation 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.
• 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.
• area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like.
• a suitable solvent should selected so as to ensure full dissolution of both the p-type and the n-type component, and to take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.
• Organic solvents are generally used for this purpose.
• Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents.
• Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof.
• Examples include, but are not limited to dichloromethane, trichloromethane, tetrachloromethane, chlorobenzene, o-dichlorobenzene, 1 ,2,4-trichlorobenzene, 1 ,2-dichloroethane, 1 ,1 ,1-trichloroethane, 1 ,1 ,2,2- tetrachloroethane, 1 ,8-diiodooctane, 1-chloronaphthalene, 1 ,8-octane-dithiol, anisole, 2-methylanisole, phenetol, 4-methyl-anisole, 3-methylanisole, 2,6- dimethylanisole, 2,5-di-methylanisole, 2,4-dimethylanisole, 3,5-dimethyl- anisole, 4-fluoroanisole, 3-fluoro-anisole, 3-trifluoro-methylanisole, 4-fluoro-3- methylanisole, 2-fluoro
• solvents selected from aliphatic or aromatic hydrocarbons, or mixtures thereof, which are non-chlorinated.
• solvents selected from non-chlorinated aliphatic or aromatic hydrocarbons, or mixtures thereof, which contain less than 5% of halogenated but non-chlorinated (e.g. fluorinated, brominated or iodinated) aliphatic or aromatic hydrocarbons, like e.g. 1 ,8-diiodooctane.
• halogenated but non-chlorinated e.g. fluorinated, brominated or iodinated
• solvents selected from non-chlorinated aliphatic or aromatic hydrocarbons, or mixtures thereof, which contain less than 5% of halogenated but non-chlorinated (e.g. fluorinated, brominated or iodinated) aliphatic or aromatic hydrocarbons, like e.g. 1 ,8-diiodooctane.
• Preferred solvents of this type are selected from 1 ,2,4-trimethylbenzene, 1 ,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2,6-lutidine, N,N- dimethylformamide, 2,3-dimethylpyrazine, 2-methylanisole, phenetol, 4- methyl-anisole, 3-methylanisole, 2,5-dimethyl-anisole, 2,4-dimethylanisole, 3,5-dimethyl-anisole, ⁇ , ⁇ -dimethylaniline, ethyl benzoate, 1- methylnaphthalene, 2-methylnaphthalene, N-methylpyrrolidinone, dioxane, 4- isopropylbiphenyl, phenyl ether, pyridine, 1 ,8-octanedit
• the OPV device can be of any OPV device type known from the literature (see e.g. Waldauf et a/., Appl. Phys. Lett, 2006, 89, 233517).
• a first preferred OPV device comprises the following layers (in the sequence from bottom to top):
• a high work function electrode preferably comprising a metal oxide, like for example ITO, serving as anode or a conducting grid
• PEDOT:PSS poly(3,4-ethylenedioxythiophene): poly(styrene-sulfonate), substituted triaryl amine derivatives, for example.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),
• PEDOT:PSS poly(3,4-ethylenedioxythiophene): poly(styrene-sulfonate
• substituted triaryl amine derivatives for example.TBD (N,N'-dyphenyl-N-N'-bis(3- methylphenyl)-1 ,1'biphenyl-4,4'-diamine) or NBD (N,N'-d
• 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
• a low work function electrode preferably comprising a metal like for
• At least one of the electrodes preferably the anode, is at least partially transparent to visible light
• n-type semiconductor is a fullerene derivative of this invention.
• a second preferred OPV device 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, or a conducting grid
• a layer having hole blocking properties preferably comprising a metal oxide like TiO x or ZnO x , or comprising an organic compound such as polymer like poly(ethyleneimine) or crosslinked nitrogen containing compound
• 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, for example of
• PEDOT:PSS or substituted triaryl amine derivatives for example, TBD or NBD,
• 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 at least partially transparent to visible light
• n-type semiconductor is a fullerene derivative of this invention.
• semiconductor materials are preferably selected from the materials, like the 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. Func. Mater, 2004, 14(10), 1005.
• An optional annealing step may be then necessary to optimize blend morpohology and consequently OPV device performance.
• Another method to optimize device performance is to prepare formulations for the fabrication of OPV(BHJ) devices that may include additives with variable boiling points to promote phase separation in the right way.
• fullerene derivatives, fullerene mixtures and semiconducting layers of the present invention are also suitable for use as n-type semiconductor in other
• 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 fullerene derivative of this invention, a fullerene mixture or an organic semiconducting layer according to the present invention as n-type semiconductor.
• 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 fullerene derivative of this invention, a fullerene mixture or an organic semiconducting layer according to the present invention as n-type semiconductor.
• Other features of the OFET are well known to those skilled in the art.
• OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode are generally known, and are described for example in US 5,892,244, US 5,998,804, US 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT displays and security applications.
• the gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
• An OFET device preferably comprises:
• the semiconductor layer comprises a fullerene derivative of this invention or a fullerene mixture as described above and below.
• the OFET device can be a top gate device or a bottom gate device. Suitable structures and manufacturing methods of an OFET device are known to the skilled in the art and are described in the literature, for example in US
• 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.
• fluorosolvents fluoro atoms
• a suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380).
• 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).
• OFETs and other devices with semiconducting materials according to the present invention can be used for RFID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with monetry value, like stamps, tickets, shares, cheques etc.
• the fullerene derivatives, fullerene mixtures, and semiconducting layers according to the invention can be used in OLEDs, for example in the buffer layer, ETL or HBL of an OLED.
• the OLED device can be used for example as the active display layer in a flat panel display device, or as the backlight of a flat panel display like for example 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.
• the fullerene derivatives, fullerene mixture or semiconducting layer according to the present invention may be employed in one or more of the ETL, HBL or buffer layer, especially their water-soluble derivatives (for example with polar or ionic side groups) or ionically doped forms.
• the processing of such layers, comprising a semiconductor material of the present invention, for the use in OLEDs is generally known by a person skilled in the art, see, e.g., Muller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124- 7128, O'Malley et al, Adv. Energy Mater. 2012, 2, 82-86 and the literature cited therein.
• the fullerene derivatives, fullerene mixtures, and materials according to this invention especially those showing
• photoluminescent properties may be employed as materials of light sources, e.g. in display devices, as described in EP 0 889 350 A1 or by C. Weder et al., Science, 1998, 279, 835-837.
• a further aspect of the invention relates to both the oxidised and reduced form of a fullerene derivative according to this invention. Either loss or gain of electrons results in formation of a highly delocalised 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 delocalised ionic centres in the material, with the corresponding counterions derived from the applied dopants.
• Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion- implantantion of the dopant into the semiconductor material.
• suitable dopants are for example halogens (e.g., I 2) Cl 2 , Br 2 , ICI, ICI 3 , IBr and IF), Lewis acids (e.g., PF 5 , AsF 5 , SbF 5 , BF 3 , BCI 3 , SbCI 5 , BBr 3 and SO 3 ), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HNO 3 , H 2 SO 4 , HCIO 4 , FSO3H and CISO 3 H), transition metal compounds (e.g., FeCI 3 , FeOCI, Fe(CIO 4 ) 3 , Fe(4-CH 3 C 6 H 4 SO3) 3 , TiCI 4 , ZrCI 4 , HfCI , NbF 5> NbCI 5 , TaCI 5 , MoF 5> MoCI 5 , WF 5 , WCI 6 , UF 6 and LnCI 3 (wherein L
• examples of dopants are cations (e.g., H ⁇ Li + , Na + , K + , Rb + and Cs + ), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O 2 , XeOF 4 , (NO 2 + ) (SbF 6 " ), (NO 2 + ) (SbCI 6 -), (NO 2 + ) (BF 4 " ), AgCIO 4 , H 2 lrCI 6 , La(NO 3 ) 3 6H 2 O, FSO 2 OOSO 2 F, Eu, acetylcholine, R N ⁇ (R is an alkyl group), R 4 P + (R is an alkyl group), R 6 As + (R is an alkyl group), and R 3 S + (R is an alkyl group).
• the conducting form of a fullerene derivative of the present invention can be used as an organic "metal" in applications including, but not limited to, charge injection layers and ITO planarising layers in OLED applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers.
• the fullerene derivatives and fullerene mixtures 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
• photoisomerisable compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913 A1.
• fullerene derivatives, fullerene mixtures, and materials according to the present invention can be employed as chemical sensors or materials for detecting and discriminating DNA sequences.
• water-soluble derivatives for example with polar or ionic side groups
• ionically doped forms can be employed as chemical sensors or materials for detecting and discriminating DNA sequences.
• reaction is quenched with water (100 cm 3 ) and an organic layer separated.
• aqueous layer is extracted with hexanes (3 x 50 cm 3 ) and the combined organic extracts are dried with anhydrous Na 2 SO 4 and concentrated by rotary evaporation to give colorless oil.
• This oil is directly used for next step without further purification. (8.7 g, 75%).
• 2,5-bis(trimethylsilyl)thiophene (30 mmol, 6.96 g) is dissolved in 600 cm 3 of dry methylene chloride, and m-MCPA (90 mmol, 20.17 g, 77% purity) is added stepwise. The mixture is stirred at 21 °C for 24 hours and filtered and washed first with 10% NaHCO 3 and then with distilled water. The aqueous layer is extracted with methylene chloride (3 x 50 cm 3 ) and the combined organic extracts are dried with anhydrous Na 2 SO 4 and concentrated by rotary evaporation to give colorless oil. The oil obtained in this way is
• triphenylarsine (AsPh 3 )(3.00 mmol, 919 mg) are dissolved in 30 cm 3 of anhydrous toluene, and the solution is stirred for 30 min. Then a toluene solution containing 1.84 g (5.00 mmol) of 2,5-diiodothiophene-1 ,1 -dioxide and 15 mmol (6.0 g) of 2-ethyl-5-tri-n-butylstannyl thiophene is added, and the mixture is refluxed for other 12 hours.
• Tris(dibenzylideneacetone)dipalladium(0) (0.750 mmol, 687 mg) and triphenylarsine (AsPh 3 )(3.00 mmol, 919 mg) are dissolved in 30 cm 3 of anhydrous toluene, and the solution is stirred for 30 minutes. Then a toluene solution containing 1.84 g (5.00 mmol) of 2, 5-Diiodothiophene-1 ,1 -dioxide and 15 mmol (6.9 g) of 2-hexyl-5-tri-n-butylstannyl thiophene is added, and the mixture is refluxed for other 12 hours.
• anhydrous DMF (6.4 cm 3 ) are added by syringe.
• the reaction is lowered into an oil bath at 120°C and allowed to stir overnight. After one night the reaction is yellow with black precipitate.
• the reaction mixture is cooled, pulled through a silica plug with generous DCM and the solvent is removed using reduced pressure in the presence of silica gel.
• the crude material is purified by column chromatography using silica and hexane followed by hexane and 1 % ethyl acetate. Material is carried directly on to the next reaction.
• the crude material is purified by HPLC using a column with cosmosil buckyprep material as the stationary phase (from Nacalai Tesque; pyrenylpropyl group bonded silica) and toluene as the mobile phase. Fractions containing pure product are combined and solvent removed using rotary evaporation. The sample is left in an oven overnight at 70°C under reduced pressure to remove residual solvent. The product is isolated (183 mg, 37.5%) as a brown crystalline solid.
• the crude reaction mixture is filtered to remove potassium carbonate. Water is added to the filtrate, which is extracted with diethyl ether twice. The ether extractions are then dried with magnesium sulfate which is subsequently removed by filtration The solvent is removed at reduced pressure and the crude material is purified by chromatography using silica and hexanes to give 13.96 g (93.9% yield) of the title product as a clear liquid showing the correct molecular ion by GCMS.
• the crude material is purified by flash chromatography using a normal silica and 1 :1 ODCB:Hexane as eluent.
• the sample is left in an oven overnight at 70°C under reduced pressure to remove residual solvent.
• the product is isolated (677 mg, 64.1 %) as a brown crystalline solid.
• the reaction is allowed to reflux and stir for 2 days at which point it is cooled and the solvent is removed under reduced pressure.
• the crude material is purified by HPLC using a column with cosmosil buckyprep material as the stationary phase (from Nacalai Tesque; pyrenylpropyl group bonded silica) and toluene as the mobile phase. Fractions containing pure product are combined and solvent removed using rotary evaporation. The sample is left in an oven overnight at 70°C under reduced pressure to remove residual solvent. The product is isolated (90 mg, 16.6%) as a brown crystalline solid.
• Example 5.1 is prepared similarly to example 3.1 to give 13.71 g (97.6% yield) as a clear oil.
• Example 5.2 is prepared similarly to example 3.2 to give 5.79 g (96.6% yield) as a white solid.
• saturated ammonium chloride solution is added slowly to the completed and cooled, crude reaction mixture. A strong precipitation is observed. This is followed quickly by a phase separation of the water and THF and subsequent, significant resolvation of the precipitate.
• Example 5.3 is prepared similarly to example 3.3 to give 4.48 g (quantitative yield) as a pale yellow shiny solid.
• Example 5.4 is prepared similarly to example 3.4 to give 392 mg (9% yield) as a yellow solid.
• Example 5.5 is prepared similarly to example 3.5 to give 294 mg (30.1 % yield) as a brown crystalline solid. Purity is confirmed by HPLC at 99.29%.
• Example 6.1 is prepared similarly to example 3.1 to give 15.85 g (quantitative yield) as a clear oil.
• Example 6.2 is prepared similarly to example 3.2 to give ⁇ 7 g (quantitative yield) as a white solid.
• saturated ammonium chloride solution is added slowly to the completed and cooled, crude reaction mixture. A strong precipitation is observed. This is followed quickly by a phase separation of the water and THF and subsequent, significant resolvation of the precipitate. Addition of a small, extra quantity of water resulted in complete solvation of all solids.
• the THF layer is removed and the water is washed twice with diethyl ether.
• the combined THF and diethyl ether phases are washed with brine, dried with magnesium sulfate, filtered, and the solvents are removed by rotary evaporation. Product is used in the next reaction without further purification.
• Example 6.3 is prepared similarly to example 3.3 to give 5.87 g (94.4% yield) as a pale grey shiny solid.
• Example 6.4 is prepared similarly to example 3.4 to give 1.51 g (28% yield) as a yellow solid.
• Example 6.5 is prepared similarly to example 3.5 to give 757 mg (65% yield) as a brown crystalline solid. Purity is confirmed by HPLC at 99.73%.
• Example B1 Bulk heteroiunction organic photovoltaic devices (OPVs) from fullerenes C1. C2. 1-6
• Organic photovoltaic (OPV) devices are fabricated on pre-patterned ITO-glass substrates (13Q/sq.) purchased from LUMTEC Corporation. Substrates are cleaned using common solvents (acetone, iso-propanol, deionized-water) in an ultrasonic bath. A conducting polymer poly(ethylene dioxythiophene) doped with poly(styrene sulfonic acid) [Clevios VPAI 4083 (H.C. Starck)] is mixed in a 1 :1 ratio with deionized-water. This solution is filtered using a 0.45 ⁇ filter before spin-coating to achieve a thickness of 20 nm.
• Substrates are exposed to ozone prior to the spin-coating process to ensure good wetting properties. Films are then annealed at 140 °C for 30 minutes in a nitrogen atmosphere where they are kept for the remainder of the process. Active material solutions (i.e. polymer + fullerene) are prepared to fully dissolve the solutes. Thin films are either spin-coated or blade-coated in a nitrogen atmosphere to achieve active layer thicknesses between 50 and 500 nm as measured using a profilometer. A short drying period follows to ensure removal of any residual solvent. Typically, blade-coated films are dried at 70 °C for 2 minutes on a hotplate.
• Ca (30 nm) / Al (100 nm) cathodes are thermally evaporated through a shadow mask to define the cells.
• Current- voltage characteristics are measured using a Keithley 2400 SMU while the solar cells are illuminated by a Newport Solar Simulator at 100 mW.crrf 2 white light.
• the solar simulator is equipped with AM1.5G filters.
• the illumination intensity is calibrated using a Si photodiode. All the device preparation and characterization is done in a dry-nitrogen atmosphere.
• OPV devices are prepared wherein the photoactive layer contains a blend of a polymer and a fullerene derivative of Examples 1 to 5, respectively, which is coated from a o-dichlorobenzene solution at a total solid concentration as shown in Table 1 below.
• the OPV device characteristics are shown in Table 1.
• Polymer 1 and its preparation are disclosed in WO 2011/131280.
• example 2 which has limited solubility in common organic solvent, prohibits the formation of the suitable morphology to achieve good performance in an OPV device, compared to fullerenes 1-6 according to the invention which show significantly better performance.

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