WO2019161748A1 - Composés semi-conducteurs organiques - Google Patents

Composés semi-conducteurs organiques Download PDF

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WO2019161748A1
WO2019161748A1 PCT/CN2019/074960 CN2019074960W WO2019161748A1 WO 2019161748 A1 WO2019161748 A1 WO 2019161748A1 CN 2019074960 W CN2019074960 W CN 2019074960W WO 2019161748 A1 WO2019161748 A1 WO 2019161748A1
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atoms
groups
optionally
organic
group
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PCT/CN2019/074960
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Xiaowei Zhan
Jiayu Wang
Jingshuai ZHU
Tengfei Li
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Peking University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—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 four or more hetero rings

Definitions

  • the invention relates to novel organic semiconducting compounds containing a polycyclic unit, to methods for their preparation and educts or intermediates used therein, to compositions, polymer blends and formulations containing them, to the use of the compounds, compositions and polymer blends 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 compounds, compositions or polymer blends.
  • OOV organic photovoltaic
  • PSC perovskite-based solar cell
  • OPD organic photo-detectors
  • OFET organic field effect transistors
  • OLED organic light emitting diodes
  • organic semiconducting (OSC) materials in order to produce more versatile, lower cost electronic devices.
  • Such materials find application in a wide range of devices or apparatus, including organic field effect transistors (OFETs) , organic light emitting diodes (OLEDs) , organic photodetectors (OPDs) , organic photovoltaic (OPV) cells, perovskite-based solar cell (PSC) devices, sensors, memory elements and logic circuits to name just a few.
  • OFETs organic field effect transistors
  • OLEDs organic light emitting diodes
  • OPDs organic photodetectors
  • OCV organic photovoltaic
  • PSC perovskite-based solar cell
  • 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.
  • OCV organic photovoltaics
  • Conjugated polymers have found use in OPVs as they allow devices to be manufactured by solution-processing techniques such as spin casting, dip coating or ink jet printing. Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices.
  • solution-processing techniques such as spin casting, dip coating or ink jet printing.
  • Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices.
  • polymer based photovoltaic devices are achieving efficiencies above 10%.
  • OFETs Another particular area of importance is OFETs.
  • the performance of OFET devices is principally based upon the charge carrier mobility of the semiconducting material and the current on/off ratio, so the ideal semiconductor should have a low conductivity in the off state, combined with high charge carrier mobility (> 1 x 10 -3 cm 2 V -1 s -1 ) .
  • the semiconducting material is stable to oxidation i.e. it has a high ionisation potential, as oxidation leads to reduced device performance.
  • Further requirements for the semiconducting material are good processibility, especially for large-scale production of thin layers and desired patterns, and high stability, film uniformity and integrity of the organic semiconductor layer.
  • OPDs Organic photodetectors
  • the photosensitive layer in an OPV or OPD device is usually composed of at least two materials, a p-type semiconductor, which is typically a conjugated polymer, an oligomer or a defined molecular unit, and an n-type semiconductor, which is typically a fullerene or substituted fullerene, graphene, a metal oxide, or quantum dots.
  • a p-type semiconductor which is typically a conjugated polymer, an oligomer or a defined molecular unit
  • an n-type semiconductor which is typically a fullerene or substituted fullerene, graphene, a metal oxide, or quantum dots.
  • OSC materials disclosed in prior art for use in OE devices have several drawbacks. They are often difficult to synthesize or purify (fullerenes) , and/or do not absorb light strongly in the near IR spectrum >700nm. In addition, other OSC materials do not often form a favourable morphology and/or donor phase miscibility for use in organic photovoltaics or organic photodetectors.
  • OSC materials for use in OE devices like OPVs, PSCs, OPDs and OFETs, which have advantageous properties, in particular good processability, a high solubility in organic solvents, good structural organization and film-forming properties.
  • the OSC materials should be easy to synthesize, especially by methods suitable for mass production.
  • the OSC materials should especially have a low bandgap, which enables improved light harvesting by the photoactive layer and can lead to higher cell efficiencies, high stability and long lifetime.
  • the OSC materials should especially have high charge-carrier mobility, high on/off ratio in transistor devices, high oxidative stability and long lifetime.
  • Another aim of the invention was to extend the pool of OSC materials and n-type OSCs available to the expert. Other aims of the present invention are immediately evident to the expert from the following detailed description.
  • IDT indaceno-type polycyclic core as shown in formula I, wherein an N atom is located in at least two of the spiro positions, and further comprise one or two terminal groups which are electron withdrawing relative to the central polycyclic core, and do optionally further comprise one or more aromatic or heteroaromatic spacer groups which are located between the polycyclic core and the terminal groups and which can be electron withdrawing or electron donating relative to the polycyclic core.
  • IDT indaceno-type
  • N atom is located in at least two of the spiro positions
  • terminal groups which are electron withdrawing relative to the central polycyclic core
  • aromatic or heteroaromatic spacer groups which are located between the polycyclic core and the terminal groups and which can be electron withdrawing or electron donating relative to the polycyclic core.
  • A-D-A acceptor-donor-acceptor
  • A-D-A compounds comprising the aforementioned structural features can be used as n-type OSCs which show advantageous properties as described above.
  • OSC small molecules comprising an IDT core that is flanked by two terminal 2- (3-oxo-2, 3-dihydroinden-1-ylidene) malononitrile withdrawing groups have been reported for use as non-fullerene n-type OSCs in OPV devices, for example 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.
  • CN105906636 A discloses the following compound and its use as red emitter in OLEDs
  • WO 2015/190762 A2 discloses the following compound and its use as p-type OSC
  • the invention relates to a compound of formula I
  • Ar 1 , Ar 2 arylene or heteroarylene which has from 5 to 20 ring atoms, which is mono-or polycyclic, which optionally contains fused rings, and which is unsubstituted or substituted by one or more identical or different groups L,
  • R 1 and R 2 together with the C or Si 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,
  • R W an electron withdrawing group, which preferably has one of the meanings given for an electron withdrawing group R T1 ,
  • R 0 , R 00 H or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12, C atoms that is optionally fluorinated,
  • X 0 halogen preferably F or Cl
  • the invention further relates to novel synthesis methods for preparing compounds of formula I, and novel intermediates used therein.
  • the invention further relates to the use of compounds of formula I as semiconductor, preferably as electron acceptor or n-type semiconductor, preferably in a semiconducting material, an electronic or optoelectronic device, or a component of an electronic or optoelectronic device.
  • the invention further relates to the use of compounds of formula I as dyes or pigments.
  • the invention further relates to a composition comprising one or more compounds of formula I, and further comprising one or more compounds having one or more of a semiconducting, hole or electron transport, hole or electron blocking, insulating, binding, electrically conducting, photoconducting, photoactive or light emitting property.
  • the invention further relates to a composition comprising one or more compounds of formula I, and further comprising a binder, preferably an electrically inert binder, very preferably an electrically inert polymeric binder.
  • the invention further relates to a composition comprising a compound of formula I, and further comprising one or more electron donors or p-type semiconductors, preferably selected from conjugated polymers.
  • the invention further relates to a composition comprising one or more n-type semiconductors, at least one of which is a compound of formula I, and further comprising one or more p-type semiconductors.
  • the invention further relates to a composition
  • a composition comprising one or more n-type semiconductors, at least one of which is a compound of formula I, and at least one other of which is a fullerene or fullerene derivative, and further comprising one or more p-type semiconductors, preferably selected from conjugated polymers.
  • the invention further relates to a bulk heterojunction (BHJ) formed from a composition comprising a compound of formula I as electron acceptor or n-type semiconductor, and one or more compounds which are electron donor or p-type semiconductors, and are preferably selected from conjugated polymers.
  • BHJ bulk heterojunction
  • the invention further relates to the use of a compound of formula I or a composition as described above and below, as semiconducting, charge transporting, electrically conducting, photoconducting, photoactive or light emitting material.
  • the invention further relates to the use of a compound of formula I or a composition as described above and below, in an electronic or optoelectronic device, or in a component of such a device or in an assembly comprising such a device.
  • the invention further relates to a semiconducting, charge transporting, electrically conducting, photoconducting, photoactive or light emitting material, comprising a compound of formula I or a composition as described above and below.
  • the invention further relates to an electronic or optoelectronic device, or a component thereof, or an assembly comprising it, which comprises a compound of formula I or a composition as described above and below.
  • the invention further relates to an electronic or optoelectronic device, or a component thereof, or an assembly comprising it, which comprises a semiconducting, charge transporting, electrically conducting, photoconducting or light emitting material as described above and below.
  • the invention further relates to a formulation comprising one or more compounds of formula I, or comprising a composition or semiconducting material as described above and below, and further comprising one or more solvents, preferably selected from organic solvents.
  • the invention further relates to the use of a formulation as described above and below for the preparation of an electronic or optoelectronic device or a component thereof.
  • the invention further relates to an electronic or optoelectronic device or a component thereof, which is obtained through the use of a formulation as described above and below.
  • the electronic or optoelectronic device includes, without limitation, organic field effect transistors (OFET) , organic thin film transistors (OTFT) , organic light emitting diodes (OLED) , organic light emitting transistors (OLET) , organic light emitting electrochemical cell (OLEC) , organic photovoltaic devices (OPV) , organic photodetectors (OPD) , organic solar cells, dye-sensitized solar cells (DSSC) , organic photoelectrochemical cells (OPEC) , perovskite-based solar cells (PSC) , laser diodes, Schottky diodes, photoconductors, photodetectors and thermoelectric devices.
  • OFET organic field effect transistors
  • OFT organic thin film transistors
  • OLET organic light emitting diodes
  • OLET organic light emitting electrochemical cell
  • OPD organic photovoltaic devices
  • OPD organic photodetectors
  • organic solar cells dye-sensitized solar cells
  • DSSC dye
  • Preferred devices are OFETs, OTFTs, OPVs, PSCs, OPDs and OLEDs, in particular OPDs and BHJ OPVs or inverted BHJ OPVs.
  • the component of the electronic or optoelectronic device includes, without limitation, charge injection layers, charge transport layers, interlayers, planarizing layers, antistatic films, polymer electrolyte membranes (PEM) , conducting substrates and conducting patterns.
  • charge injection layers charge transport layers
  • interlayers interlayers
  • planarizing layers antistatic films
  • PEM polymer electrolyte membranes
  • the assembly comprising an electronic or optoelectronic device includes, without limitation, 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.
  • IC integrated circuits
  • RFID radio frequency identification
  • the electron withdrawing groups like R T1 and R T2 , are understood to be electron withdrawing relative to the polycyclic core.
  • 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.
  • 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 polymerization reaction, like for example a group having the meaning of R 31 or R 32 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 alkyl-or arylhalide, an alkyl-or arylstannane or an alkyl-or arylboronate.
  • 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.
  • 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.
  • 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. Chem., 1994, 66, 1134) .
  • 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.
  • 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, trichloromethane (TCM, chloroform) , chlorobenzene or 1, 2, 4-trichloro-benzene. Unless stated otherwise, chlorobenzene is used as solvent.
  • GPC gel permeation chromatography
  • 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 B, N, O, 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, P, Si, Se, As, Te or Ge.
  • hetero atom will be understood to mean an atom in an organic compound that is not a H-or C-atom, and preferably will be understood to mean 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, O, S, P, Si, Se, As, Te and Ge.
  • carbyl and hydrocarbyl group include for example: a C 1 -C 40 alkyl group, a C 1 -C 40 fluoroalkyl group, a C 1 -C 40 alkoxy or oxaalkyl group, a C 2 -C 40 alkenyl group, a C 2 -C 40 alkynyl group, a C 3 -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 C 6 -C 18 aryl group, a C 6 -C 40 alkylaryl group, a C 6 -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 C 3 -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 C 6 -C 12 aryl group, and a C 4 -C 20 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. 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 (O) 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 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 - (CH 2 ) a -aryl or - (CH 2 ) 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, 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,
  • An alkyl group or an alkoxy group i.e., where the terminal CH 2 group is replaced by -O-, 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 C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl, C 5 -C 7 -4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl and C 5 -C 7 -4-alkenyl.
  • alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
  • An oxaalkyl group i.e., where one CH 2 group is replaced by -O-, can be straight-chain.
  • radicals together form a carbonyloxy group -C (O) -O-or an oxycarbonyl group -O-C (O) -.
  • this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonyl,
  • a fluoroalkyl group can be perfluoroalkyl C i F 2i+1 , 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 11 , C 6 F 13 , C 7 F 15 or C 8 F 17 , very preferably C 6 F 13 , 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 perfluorinated) alkyl group.
  • 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 1-3 each denote L as defined above and below and where at least, preferably all, of RSub 1-3 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 RSub 1-3 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 substituted by an F atom.
  • 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 compounds of 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 compounds of formula I are especially suitable as (electron) acceptor or n-type semiconductor, and for the preparation of blends of n-type and p-type semiconductors which are suitable for use in OPD or BHJ OPV devices.
  • the compounds of formula I are further suitable to replace the fullerene compounds that have hitherto been used as n-type semiconductor in OPV or OPD devices.
  • a first preferred embodiment of the present invention relates to compounds of formula I wherein at least one, preferably all, indaceno groups have trans-configuration, i.e. wherein one of the two groups U 1 , or one of the two groups U 2 respectively, which are attached to the same benzene ring, is a single bond and the other is different from a single bond, as exemplarily illustrated below.
  • Preferred compounds of formula I according to this first preferred embodiment are selected from the following subformulae
  • Preferred compounds of formula I2 are those wherein all of the groups U 1 and U 2 denote NR 1 .
  • a second preferred embodiment of the present invention relates to compounds of formula I wherein at least one, preferably all, indaceno groups have cis-configuration, i.e. wherein both groups U 1 , or both U 2 respectively, which are attached to the same benzene ring, are a single bond, as exemplarily illustrated below.
  • Preferred compounds of formula I according to this second preferred embodiment are selected from the following subformulae
  • Preferred compounds of formula I4 are those wherein all groups U 1 denote NR 1 .
  • Preferred compounds of formula I5 are those wherein all groups U 1 and U 2 denote NR 1 .
  • Preferred groups Ar 1 in formula I, I1-I5 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
  • Preferred groups Ar 1 are those of formula A1a, A1b, A1d, A1e, A1g and A1h, especially those of formula A1a and A1b.
  • R 3-7 are as defined above and below.
  • Preferred groups Ar 2 in formula I, I1-I5 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
  • V 1 , W 1 , W 2 , W 3 and R 5-9 have the meanings given above.
  • Preferred groups Ar 2 are those of formula A2a, A2b, A2d, A2e, A2g and A2h, especially those of formula A2a and A2b.
  • R 3-7 are as defined above and below.
  • Preferred groups Ar 3 and Ar 4 in formula I, I1-I5 and their subformulae are each independently and on each occurrence identically or differently selected from arylene or heteroarylene which has from 5 to 20 ring atoms, which is mono-or polycyclic, which optionally contains fused rings, and which is unsubstituted or substituted by one or more identical or different groups L.
  • Ar 3 and Ar 4 in formula I, I1-I5 and their subformulae are each independently and on each occurrence identically or differently selected from the following formulae and their mirror images:
  • V 2 is CR 4 or N
  • R 4 has one of the meanings given for R 3
  • V 1 , W 1 , W 2 , W 4 , R 0 , R 5-8 are as defined above and below.
  • Ar 3 and Ar 4 in formula I, I1-I5 and their subformulae are each independently, and on each occurrence identically or differently, selected from the following formulae and their mirror images
  • Preferred formulae AR1-1 to AR6-1 are those containing at least one, preferably one, two or four substituents X 1-4 selected from F and Cl, very preferably F.
  • Preferred groups Ar 3 and Ar 4 are selected from formulae AR1, AR2, AR3 and AR5.
  • Very preferred groups Ar 4-7 are selected from formulae AR1-1, AR1-2, AR2-1, AR3-1, AR3-2 and AR5-1, most preferably from formulae AR1-1, AR1-2, AR2-1, AR2-2 and AR3-1.
  • R a , R b aryl or heteroaryl each having from 4 to 30, preferably from 5 to 20, ring atoms, optionally containing fused rings and being unsubstituted or substituted with one or more groups L, or one of the meanings given for L,
  • X 0 halogen preferably F or Cl
  • R T1 and R T2 denotes an electron withdrawing group
  • Preferred compounds of formula I are those wherein both of R T1 and R T2 denote an electron withdrawing group.
  • R T1 and R T2 are each independently selected from formulae T3, T10, T31, T36, T37, T38, T39, T47, T52, T53 and T54, wherein preferably L'is H, R a and R b denote H or C 1 -C 12 -alkyl, r is 0 and s is 0.
  • R 1 and R 2 are preferably 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 are preferably selected from mono-or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula IA 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.
  • the compounds of formula I, I1-I5 and their subformulae R 3-9 when being different from H, are each independently selected from F, Cl, CN 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, without being perfluorinated.
  • I1-I5 and their subformulae R 3-9 when being different from H, are each independently selected from 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.
  • Preferred aryl and heteroaryl groups R 1-9 when being different from H, are each independently selected from the following formulae
  • R 11-17 independently of each other, and on each occurrence identically or differently, denote H or have one of the meanings given for L in formula I or one of its preferred meanings as given above and below.
  • Very preferred aryl and heteroaryl groups R 1-9 when being different from H, are each independently selected from the following formulae
  • R 11-15 are as defined above.
  • Most preferred 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 CH 2 or CH 3 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 .
  • 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-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 R 1-9 .
  • any one of the groups R 1 ', R 2 ', R 3 'and R 4 ' (if they replace a CH 3 group) can denote a link to the respective group R 1-10
  • two neighbored groups R 1 ', R 2 ', R 3 'or R 4 ' (if they replace a CH 2 group) 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.
  • - a is 1 or 2, preferably 1,
  • - b is 1 or 2, preferably 1,
  • - c is 1 or 2, preferably 1,
  • - a is 2 or 3 and in at least one, preferably all, benzene rings of formula I one of the two groups U 1 attached to the same benzene ring is a single bond and the other is different from a single bond,
  • U 1 and U 2 are a single bond and the other is CR 1 R 2 , SiR 1 R 2 or NR 1 ,
  • W 1 , W 2 and W 3 are S or Se, preferably S,
  • V 1 is CR 3 and V 2 is CR 4 ,
  • V 1 is CR 3 and V 2 is N
  • V 1 and V 2 are N
  • Ar 1 is selected from formulae A1a, A1b, A1d, A1e, A1g and A1h, very preferably from formulae A1a and A1b,
  • Ar 2 is selected from formulae A2a, A2b, A2d, A2e, A2g and A2h, especially those of formula A2a and A2b,
  • Ar 3 and Ar 4 are selected from formulae AR1, AR2, AR3 and AR5,
  • Ar 3 and Ar 4 are selected from formulae AR1-1, AR1-2, AR2-1, AR3-1, AR3-2 and AR5-1, most preferably from formulae AR1-1, AR1-2, AR2-1, AR2-2 and AR3-1,
  • Ar 3 and Ar 4 denote 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 or thiadiazole [3, 4-c] pyridine, which are substituted by X 1 , X 2 , X 3 and X 4 as defined above,
  • Ar 4 and Ar 5 denote 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 or thiadiazole [3, 4-c] pyridine, wherein X 1 , X 2 , X 3 and X 4 are H,
  • Ar 4 and Ar 5 denote thiophene, thiazole, thieno [3, 2-b] thiophene, thiazolothiazole, benzene, 2, 1, 3-benzothiadiazole, 1, 2, 3-benzothiadiazole, thieno [3, 4-b] thiophene, benzotriazole or thiadiazole [3, 4-c] pyridine, wherein one or more of X 1 , X 2 , X 3 and X 4 are different from H,
  • R 1 and R 2 when being different from H, 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, without being perfluorinated, or alkyl or alkoxy having 1 to 12 C atoms that is optionally fluorinated,
  • R 1 and R 2 are different from H, and 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-dialkoxyphen
  • L denote F, Cl, CN, NO 2 , or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated,
  • L is F, Cl, CN, NO 2 , or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated,
  • L is F, Cl, CN, NO 2 , or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated,
  • L is F, Cl, CN, NO 2 , or alkyl or alkoxy with 1 to 16 C atoms that is optionally fluorinated,
  • R 5 , R 6 , R 7 , R 8 and R 9 are H
  • R 5 , R 6 , R 7 , R 8 and R 9 is different from H
  • R 3-9 when being different from H, 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,
  • R 3-9 when being different from H, 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,
  • R T1 and R T2 are selected from the formulae T3, T10, T31, T36, T37, T38, T39, T47, T52, T53 and T54, wherein preferably L'is H, R a and R b denote H or C 1 -C 12 -alkyl, r is 0 and s is 0.
  • Preferred compounds of formula I and I1-I5 are selected from the following subformulae
  • Ar 3 , Ar 4 , R T1 , R T2 , R 1 , a and b have the meanings given above and below.
  • R 1 and R 5 are as defined above and below.
  • the conjugated polymer used in the said composition comprises at least one electron donating unit ( "donor unit” ) and at least one electron accepting unit ( “acceptor unit” ) , and optionally at least one spacer unit separating a donor unit from an acceptor unit, wherein each donor and acceptor units is directly connected to another donor or acceptor unit or to a spacer unit, and wherein all of the donor, acceptor and spacer units are each independently selected from arylene or heteroarylene that has from 5 to 20 ring atoms, is mono-or polycyclic, optionally contains fused rings, are is unsubstituted or substituted by one or more identical or different groups L as defined above.
  • the spacer units are located between the donor and acceptor units such that a donor unit and an acceptor unit are not directly connected to each other.
  • Preferred conjugated polymers comprise, very preferably consist of, one or more units selected from formula U1, U2 and U3, and/or one or more units selected from formula U4, U5, U6 and U7
  • D denotes a donor unit
  • A denotes an acceptor unit
  • Sp denotes a spacer unit, all of which are selected, independently of each other and on each occurrence identically or differently, from arylene or heteroarylene that has from 5 to 20 ring atoms, is mono-or polycyclic, optionally contains fused rings, are is unsubstituted or substituted by one or more identical or different groups L as defined above.
  • R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L as defined above, and wherein preferably at least one of R 11 , R 12 , R 13 and R 14 is different from H and in formula D147 preferably R 12 and R 13 are F and R 11 and R 14 are H or C1-C30 alkyl.
  • R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L as defined above.
  • R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L as defined above.
  • R 11 and R 12 are H.
  • R 11-14 are H or F.
  • the conjugated polymer contains, preferably consists of
  • acceptor units selected from the group consisting of the formulae A1, A2, A5, A15, A16, A20, A74, A88, A92, A94 and A98, A99, A100 and
  • spacer units if present, are preferably located between the donor and acceptor units such that a donor unit and an acceptor unit are not directly connected to each other.
  • the conjugated polymer comprises, preferably consists of
  • the conjugated polymer according to this second preferred embodiment contains from one to six, very preferably one, two, three or four distinct units D and from one to six, very preferably one, two, three or four distinct units A, wherein d1, d2, d3, d4, d5 and d6 denote the molar ratio of each distinct unit D, and a1, a2, a3, a4, a5 and a6 denote the molar ratio of each distinct unit A, and
  • each of d1, d2, d3, d4, d5 and d6 is from 0 to 0.6, and d1+d2+d3+d4+d5+d6 is from 0.2 to 0.8, preferably from 0.3 to 0.7, and
  • each of a1, a2, a3, a4, a5 and a6 is from 0 to 0.6, and a1+a2+a3+a4+a5+d6 is from 0.2 to 0.8, preferably from 0.3 to 0.7, and d1+d2+d3+d4+d5+d6+a1+a2+a3+a4+a5+a6 is from 0.8 to 1, preferably 1.
  • conjugated polymer according to this second preferred embodiment contains, preferably consists of
  • acceptor units selected from the group consisting of the formulae A1, A2, A5, A15, A16, A20, A74, A88, A92, A94, A98, A99 and A100.
  • 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 conjugated polymers are preferably statistical or random copolymers.
  • polymers comprising one of the formulae P1-P54 as one or more repeating unit.
  • x and y are preferably from 0.1 to 0.9, very preferably from 0.25 to 0.75, most preferably from 0.4 to 0.6.
  • x, y and z are preferably from 0.1 to 0.8, very preferably from 0.2 to 0.6, most preferably from 0.25 to 0.4.
  • X 1 , X 2 , X 3 and X 4 denote F
  • X 1 , X 2 , X 3 and X 4 denote F
  • X 1 and X 2 denote H
  • X 3 and X 4 denote F
  • R 11 and R 12 are H. Further preferably R 11 and R 12 , when being different from H, denote straight-chain or branched alkyl with 1 to 30, preferably 1 to 20, C atoms that is optionally fluorinated.
  • R 15 and R 16 are H, and R 13 and R 14 are different from H.
  • R 17 and R 18 are F. Further preferably in formula P54 one or both of R 11 and R 12 are C1-C30 alkyl.
  • R 13 , R 14 , R 15 and R 16 when being different from H, are each independently selected from the following groups:
  • R 17 and R 18 when being different from H, are each independently selected from the following groups:
  • conjugated polymers selected of formula PT
  • Preferred endcap groups R 31 and R 32 are H, C 1-20 alkyl, or optionally substituted C 6-12 aryl or C 2-10 heteroaryl, very preferably H, phenyl or thiophene.
  • the compounds of formula IA, IB and their subformulaeand the conjugated polymers of formula Pi-viii, P1-P54 and PT 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 compounds of the present invention can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling.
  • aryl-aryl coupling reactions such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling.
  • the educts can be prepared according to methods which are known to the person skilled in the art.
  • 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.
  • Yamamoto 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.
  • 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.
  • Yamamoto coupling educts having two reactive halide groups are preferably used.
  • Suzuki coupling educts having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used.
  • edcuts 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 (II) 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 (ortho-tolyl) phosphine, i.e. Pd (o-Tol 3 P) 4 .
  • Preferred Pd (II) 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 (0) , or Pd (II) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris (ortho-tolyl) phosphine or tri (tert-butyl) phosphine.
  • a Pd (0) dibenzylideneacetone complex for example tris (dibenzyl-ideneacetone) dipalladium (0) , bis(dibenzylideneacetone) palladium (0) , or Pd (II) salts e.g. palladium acetate
  • a phosphine ligand for example triphenylphosphine, tris (
  • 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.
  • 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) .
  • leaving groups of formula -O-SO 2 Z 0 can be used wherein Z 0 is an alkyl or aryl group, preferably C 1-10 alkyl or C 6-12 aryl. Particular examples of such leaving groups are tosylate, mesylate and triflate.
  • Novel methods of preparing compounds of formula I as described above and below are another aspect of the invention.
  • the compounds of formula I 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 compounds of formula I 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.
  • compositions blends 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 compounds of formula I 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. Additional solvents which can be used include 1, 2, 4-trimethylbenzene, 1, 2, 3, 4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2, 6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, N, N-dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2, 3-dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro-methylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3-methylanisole, 4-fluoro-3-
  • 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, tetraline, 2-methylthiophene, 3-methylthiophene, decaline, indane, methyl benzo
  • 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, J.W.Jr., Journal of Paint Technology, 1966, 38 (496) , 296 ".
  • Solvent blends may also be used and can be identified as described in "Solvents, W. H. Ellis, Federation of Societies for Coatings Technology, p9-10, 1986". Such a procedure may lead to a blend of ‘non’ solvents that will dissolve both the polymers of the present invention, although it is desirable to have at least one true solvent in a blend.
  • the compounds of formula I 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.
  • 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.
  • 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.
  • the compounds or polymers should be first dissolved in a suitable solvent.
  • Solvents must fulfil the requirements stated above and must not have any detrimental effect on the chosen print head. Additionally, solvents should have boiling points >100°C, preferably >140°C and more preferably >150°C in order to prevent operability problems caused by the solution drying out inside the print head.
  • suitable solvents include substituted and non-substituted xylene derivatives, di-C 1-2 -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 N, N-di-C 1-2 -alkylanilines and other fluorinated or chlorinated aromatics.
  • a preferred solvent for depositing a compound of formula I by ink jet printing comprises a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three.
  • the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total.
  • Such a solvent enables an ink jet fluid to be formed comprising the solvent with the compound or polymer, which reduces or prevents clogging of the jets and separation of the components during spraying.
  • the solvent (s) may include those selected from the following list of examples: dodecylbenzene, 1-methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, 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.
  • 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 compounds according to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices.
  • the compounds of the present invention are typically applied as thin layers or films.
  • the present invention also provides the use of the semiconducting compound or composition or layer in an electronic device.
  • the compound or composition may be used as a high mobility semiconducting material in various devices and apparatus.
  • the compound 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 compound 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 invention additionally provides an electronic device comprising compound or composition or organic semiconducting layer according to the present invention.
  • Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, 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.
  • Especially preferred electronic device are OFETs, OLEDs, OPV, PSC and OPD devices, in particular OPD, PSC and bulk heterojunction (BHJ) OPV devices.
  • the active semiconductor channel between the drain and source may comprise the compound or composition of the invention.
  • the charge (hole or electron) injection or transport layer may comprise the compound or composition of the invention.
  • the compounds according to the present invention are preferably used in a composition that comprises or contains, more preferably consists of, one or more p-type (electron donor) semiconductors and one or more n-type (electron acceptor) semiconductors.
  • At least one of the n-type semiconductors is a compound of formula I.
  • the p-type semiconductor is preferably a conjugated polymer as defined above.
  • the composition can also comprise a compound of formula I as n-type semiconductor, a p-type semiiconductor like a conjugated polymer, and a second n-type semiconductor, which is preferably a fullerene or substituted fullerene.
  • the fullerene is for example an indene-C 60 -fullerene bisadduct like ICBA, or a (6, 6) -phenyl-butyric acid methyl ester derivatized methano C 60 fullerene, also known as "PCBM-C 60 " or "C 60 PCBM” , 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.
  • 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
  • C n denotes a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside,
  • 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
  • l 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 60-Ih ) [5, 6] fullerene, (C 70-D5h ) [5, 6] fullerene, (C 76-D2* ) [5, 6] fullerene, (C 84- D2* ) [5, 6] fullerene, (C 84-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, La@C 60 , La@C 82 , Y@C 82 , Sc 3 N@C 80 , Y 3 N@C 80 , Sc 3 C 2 @C 80 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.
  • Adduct1 Primary and secondary adducts, named "Adduct1" and “Adduct 2" in formula Full-I and its subformulae, are each preferably selected from the following formulae
  • 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,
  • R S1 , R S2 , R S3 , R S4 and R S5 independently of each other denote H, CN or have one of the meanings of L as defined above and below,
  • 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:
  • 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, oQDM-C60 (1', 4'-dihydro-naphtho [2', 3': 1, 9] [5, 6] fullerene-C60-Ih) , or bis-oQDM-C60.
  • the 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 PEDOT: PSS, 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 a
  • the ratio polymer: compound of formula I 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) 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.
  • 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.
  • 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 compound, like that of formula I, 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 ⁇ -methylstyrene and ⁇ -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.
  • 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.
  • 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 ( ⁇ -methylstyrene) , poly ( ⁇ -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 ( ⁇ - ⁇ - ⁇ ’- ⁇ ’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) ,
  • Preferred insulating binders to be used in the formulations as described before are polystryrene, poly ( ⁇ -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 (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) .
  • compositions and 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.
  • area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like.
  • Suitable solutions or formulations containing the mixture of a compound of formula I and a polymer must be prepared.
  • suitable solvent must be selected to ensure full dissolution of both component, p-type and n-type and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.
  • Organic solvents are generally used for this purpose.
  • Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents. Examples include, but are not limited to chlorobenzene, 1, 2-dichlorobenzene, chloroform, 1, 2-dichloroethane, dichloromethane, carbon tetrachloride, toluene, cyclohexanone, ethylacetate, tetrahydrofuran, anisole, 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
  • the OPV device can for example be of any type known from the literature (see e.g. Waldauf et al., 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 PEDOT: PSS (poly (3, 4-ethylenedioxythiophene) : poly (styrene-sulfonate) , or TBD (N, N’ -dyphenyl-N-N’ -bis (3-methylphenyl) -1, 1’ biphenyl-4, 4’ -diamine) or NBD (N, N’ -dyphenyl-N-N’ -bis (1-napthylphenyl) -1, 1’ biphenyl-4, 4’ -diamine) ,
  • PEDOT PEDOT: PSS (poly (3, 4-ethylenedioxythiophene) : poly (styrene-sulfonate)
  • TBD N, N’ -dyphenyl-N-N’ -bis (3-methylphenyl) -1, 1’ biphenyl-4, 4’ -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,
  • 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 compound of formula I.
  • 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
  • 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 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 PEDOT: PSS, 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 compound of formula I.
  • the p-type and n-type semiconductor materials are preferably selected from the materials, like the compound/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.
  • OPV OPV
  • BHJ OPV
  • 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 Fréchet et al. J. Am. Chem. Soc., 2010, 132, 7595-7597.
  • Another preferred embodiment of the present invention relates to the use of a compound 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 compound or composition according to the present invention.
  • a compound 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)
  • PSC perovskite-based solar cell
  • 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 WO2013171520A1
  • a preferred OE device 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) , Sb 2 S 3 (stibnite) , Sb 2 (S x Se (x-1) ) 3, PbS x Se (x-1) , CdS x Se (x-1) , ZnTe, CdTe, ZnS x Se (x-1) , InP, FeS, FeS 2 , Fe 2 S 3 , Fe 2 SiS 4 , Fe 2 GeS 4 , Cu 2 S, CuInGa, CuIn (Se x S (1-x) ) 2 , Cu 3 Sb x Bi (x-1) , (S y Se (y-1) ) 3 , Cu 2 SnS 3 , SnS x Se (x-1) , Ag 2 S, AgBiS 2
  • chalcopyrite e.g. CuIn x Ga (1-x) (S y Se (1-y) ) 2
  • kesterite e.g. Cu 2 ZnSnS 4 , Cu 2 ZnSn (Se x S (1-x) ) 4, Cu 2 Zn (Sn 1-x Ge x ) S 4
  • metal oxide e.g. CuO, Cu 2 O
  • 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 ABX 3 , 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
  • 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 CsSnI 3 , CH 3 NH 3 Pb (I 1- x Cl x ) 3 , CH 3 NH 3 PbI 3, CH 3 NH 3 Pb (I 1-x Br x ) 3 , CH 3 NH 3 Pb (I 1-x (BF 4 ) x ) 3 , CH 3 NH 3 Sn (I 1-x Cl x ) 3 , CH 3 NH 3 SnI 3 or CH 3 NH 3 Sn (I 1-x Br x ) 3 wherein 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.
  • the invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the compound of formula I 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 compound of formula I 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 compound of formula I is employed as electron transport material (ETM) or as hole blocking material as part of the electron selective layer.
  • ETM electron transport material
  • hole blocking material as part of the electron selective layer.
  • the compound of formula I is employed as electron transport material (ETM) .
  • the compound of formula I 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 compound of formula I, 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 TiO 2 , ZnO 2 , SnO 2 , Y 2 O 5 , Ga 2 O 3 , SrTiO 3 , BaTiO 3 or combinations thereof;
  • porous scaffold which can be conducting, semi-conducting or insulating, and which preferably comprises a metal oxide such as TiO 2 , ZnO 2 , SnO 2 , Y 2 O 5 , Ga 2 O 3 , SrTiO 3 , BaTiO 3 , Al 2 O 3 , ZrO 2 , SiO 2 or combinations thereof, and which is preferably composed of nanoparticles, nanorods, nanoflakes, nanotubes or nanocolumns;
  • a metal oxide such as TiO 2 , ZnO 2 , SnO 2 , Y 2 O 5 , Ga 2 O 3 , SrTiO 3 , BaTiO 3 , Al 2 O 3 , ZrO 2 , SiO 2 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;
  • 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 (III) tris (bis (trifluoromethylsulfonyl) imide) ) , which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
  • 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
  • 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;
  • 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 (III) tris (bis (trifluoromethylsulfonyl) imide) ) , which can enhance the properties of the hole selective layer, for example the electrical conductivity, and/or facilitate its processing;
  • 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
  • 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 compound of formula I 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 TiO 2 , ZnO 2 , SnO 2 , Y 2 O 5 , Ga 2 O 3 , SrTiO 3 , BaTiO 3 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;
  • 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 compounds of formula I 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 compounds of formula I 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.
  • 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 compounds of formula I 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 compound of formula I 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 compound of formula I 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 precursor of a binder for example a liquid monomer, oligomer or crosslinkable polymer, optionally in the presence of a solvent
  • 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 compound formula I 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 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.
  • additives that can enhance the electrical conductivity are for example halogens (e.g. I 2 , Cl 2 , Br 2 , ICl, ICl 3 , IBr and IF) , Lewis acids (e.g. PF 5 , AsF 5 , SbF 5 , BF 3 , BCl 3 , SbCl 5 , BBr 3 and SO 3 ) , protonic acids, organic acids, or amino acids (e.g. HF, HCl, HNO 3 , H 2 SO 4 , HClO 4 , FSO 3 H and ClSO 3 H) , transition metal compounds (e.g.
  • halogens e.g. I 2 , Cl 2 , Br 2 , ICl, ICl 3 , IBr and IF
  • Lewis acids e.g. PF 5 , AsF 5 , SbF 5 , BF 3 , BCl 3 , SbCl 5 , BBr 3 and SO 3
  • FeCl 3 FeOCl, Fe (ClO 4 ) 3 , Fe (4-CH 3 C 6 H 4 SO 3 ) 3 , TiCl 4 , ZrCl 4 , HfCl 4 , NbF 5 , NbCl 5 , TaCl 5 , MoF 5 , MoCl 5 , WF 5 , WCl 6 , UF 6 and LnCl 3 (wherein Ln is a lanthanoid) ) , anions (e.g.
  • WO 3 , Re 2 O 7 and MoO 3 metal-organic complexes of cobalt, iron, bismuth and molybdenum, (p-BrC 6 H 4 ) 3 NSbCl 6 , bismuth (III) tris (trifluoroacetate) , FSO 2 OOSO 2 F, acetylcholine, R 4 N + , (R is an alkyl group) , R 4 P + (R is a straight-chain or branched alkyl group 1 to 20) , R 6 As + (R is an alkyl group) , R 3 S + (R is an alkyl group) and ionic liquids (e.g.
  • 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 compound formula I 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 compound formula 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 compound of formula I, 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 TiO 2 .
  • Suitable device structures for PSCs comprising a compounds of formula 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) 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 compounds and compositions of 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 compounds 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 compound and compositions according to the present invention.
  • an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a compound and compositions according to the present invention.
  • Other features of the OFET are well known to those skilled in the art.
  • OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode are generally known, and are described for example in US 5,892,244, US 5,998,804, US 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these 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 preferably comprises:
  • the semiconductor layer preferably comprises a compound of formula I.
  • 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 or Cytop (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. (available from Acros, catalogue number 12380) .
  • fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon 1600 or 2400 (from DuPont) or (from Cytonix) or the perfluorosolvent FC (Acros, No. 12377) .
  • 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.
  • 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 compounds 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.
  • 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., Müller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128 and the literature cited therein.
  • 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 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.
  • suitable dopants are for example halogens (e.g., I 2 , Cl 2 , Br 2 , ICl, ICl 3 , IBr and IF) , Lewis acids (e.g., PF 5 , AsF 5 , SbF 5 , BF 3 , BCl 3 , SbCl 5 , BBr 3 and SO 3 ) , protonic acids, organic acids, or amino acids (e.g., HF, HCl, HNO 3 , H 2 SO 4 , HClO 4 , FSO 3 H and ClSO 3 H) , transition metal compounds (e.g., FeCl 3 , FeOCl, Fe (ClO 4 ) 3 , Fe (4-CH 3 C 6 H 4 SO 3 ) 3 , TiCl 4 , ZrCl 4 , HfCl 4 , NbF 5 , NbCl 5 , TaCl 5 , MoF 5 , MoCl 5
  • Lewis acids e.
  • 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 + ) (SbCl 6 - ) , (NO 2 + ) (BF 4 - ) , AgClO 4 , H 2 IrCl 6 , La (NO 3 ) 3 .
  • dopants are cations (e.g., H + , Li + , Na + , K + , Rb + and Cs + ) , alkali metals (e.g., Li, Na, K, Rb, and Cs) , alkaline-earth metal
  • 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.
  • 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 described above, which are especially useful as alignment layers to induce or enhance alignment in a liquid crystal medium provided onto said anisotropic film.
  • the materials according to the present invention 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne des composés semi-conducteurs organiques contenant une unité polycyclique, des procédés associés à leur préparation et des produits de départ ou produits intermédiaires utilisés à cet effet, des compositions, des mélanges de polymères et des formulations les contenant, l'utilisation des composés, des compositions et des mélanges de polymères en tant que semi-conducteurs organiques dans, ou pour la préparation de dispositifs électroniques organiques (OE), notamment des dispositifs photovoltaïques organiques (OPV), des dispositifs de cellules solaires de type pérovskite (PSC), des photodétecteurs organiques (OPD), des transistors à effet de champ organiques (OFET) et des diodes électroluminescentes organiques (OLED), ainsi que des dispositifs OE, OPV, PSC, OPD, OFET et OLED.
PCT/CN2019/074960 2018-02-23 2019-02-13 Composés semi-conducteurs organiques WO2019161748A1 (fr)

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