WO2013030325A1 - Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers - Google Patents

Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers Download PDF

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WO2013030325A1
WO2013030325A1 PCT/EP2012/066941 EP2012066941W WO2013030325A1 WO 2013030325 A1 WO2013030325 A1 WO 2013030325A1 EP 2012066941 W EP2012066941 W EP 2012066941W WO 2013030325 A1 WO2013030325 A1 WO 2013030325A1
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group
formula
independently
compound
substituted
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PCT/EP2012/066941
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French (fr)
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Pascal Hayoz
Natalia Chebotareva
Yves Henri GEERTS
Sara STAS
Jean-Yves Balandier
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Basf Se
Université Libre de Bruxelles
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Priority to KR1020147008274A priority Critical patent/KR102030859B1/en
Priority to CN201280053536.9A priority patent/CN104094435B/en
Priority to US14/241,769 priority patent/US9209412B2/en
Priority to EP12751539.3A priority patent/EP2751855B1/en
Priority to JP2014527669A priority patent/JP6296980B2/en
Publication of WO2013030325A1 publication Critical patent/WO2013030325A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • Diketopyrrolopyrrole Oligomers and Compositions comprising Diketopyrrolopyrrole Oligomers
  • the present invention relates to compositions, comprising (a) a compound of the formula I, and (b) a polymeric material, to specific oligomers of the formula I, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and pho- todiodes, or in a device containing a diode and/or an organic field effect transistor.
  • organic devices especially in organic photovoltaics (solar cells) and pho- todiodes, or in a device containing a diode and/or an organic field effect transistor.
  • High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the compositions, or oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
  • WO2010/049321 WO2010/049323, WO2010/108873, WO2010/1 15767, WO2010/136353, WO2010/136352 and WO201 1/144566:
  • WO05/049695 discloses diketopyrrolopyrrole (DPP) based polymers and their use in PLEDs, organic integrated circuits (O-ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (O-SCs), or organic laser diodes, but fails to disclose DPP oligomers.
  • DPP diketopyrrolopyrrole
  • EP2034537A2 discloses polymers of formula , wherein each R is independently selected from hydrogen, an optionally substituted hydrocarbon, and a hetero-containing group; each Ar is independently selected from optionally substituted aryl and heteroaryl groups; each M is an optional, conjugated moiety; a represents a number that is at least 1 ; b represents a number from 0 to 20; and n represents a number that is at least 1 , but fails to disclose DPP oligomers.
  • oligomers which are prepared by a stepwise sequence of suzuki couplings using brominated 1 ,4-dioxo-3,6- diphenylpyrrolo[3,4c]pyrrole (DPP derivatives) and 1 ,4-dibromo-2,5-di-n-hexylbenzene as the monomers.
  • the resulting oligomers contained three, five and seven DPP units, respectively.
  • WO2003048268 relates to an organic electroluminescent device comprising a perylene uch as, for example,
  • WO06/061343 discloses fluorescent diketopyrrolopyrroles of the formula
  • R 1 and R 2 may be the same or different and are selected from a Ci-C2salkyl group, an allyl group, which can be substituted one to three times with Ci-C3alkyl, a cycloalkyl group, which can optionally be substituted one to three times with d-Csalkyl and/or Ci- Cealkoxy, a cycloalkyl group, which is condensed one or two times by phenyl which can be substituted one to three times with Ci-C4-alkyl, halogen, nitro, or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, a heterocyclic group, haloalkyl, haloalkenyl, haloal- kynyl, a heterocyclic group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group
  • R 101 to R 123 may be the same or different and are selected from hydrogen, Ci- C25alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR 27 R 28 , wherein R 27 and R 28 are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R 115 to R 121
  • R 124 and R 125 may be the same or different and are selected from Ci-Cisalkyl; Ci-Cisalkoxy, A 3 , C6-Ci8aryl; C7-Cisaralkyl; or R 124 and R 125 together form a ring especially a five-, six- or seven-membered ring, which can optionally be substituted by Ci-CsalkyI, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with d-Cs-alkyl, d-Cs-alkoxy, halogen and cyano; or
  • R 131 to R 152 may be the same or different and are selected from hydrogen, Ci- C25alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR 27 R 28 , wherein R 27 and R 28 are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group,
  • R 153 is a hydrogen atom, a Ci-C25alkyl group, which might be interrupted by -O-, a cycloal- kyl group, an aralkyl group, an aryl group, or a heterocyclic group, and
  • a 6 is cycloalkyl, arylene, or heteroarylene, which are optionally substituted one to three times with d-Cs-alkyl, or d-Cs-alkoxy; and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, in solid dye lasers, EL lasers and electroluminescent devices.
  • JP2006310538 discloses fluorescent diketopyrrolopyrroles of the formula wherein Ar 6 may be aryl, or heteroryl, and its use in light emitting elements.
  • inks the prepn. of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color12 filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, dye lasers and electroluminescent devices.
  • US2010/0326525 relates to optoelectronic devices, such as photovoltaic devices, comprising:
  • the electron donor material comprises a compound of Formula (I): I)
  • X is oxygen or sulfur
  • Ai and A2 are independently selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual Ai within the (Ai)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group;
  • Bi is independently selected from substituted and unsubstituted aryl or heteroaryl groups; m is independently selected from 1 , 2, 3, 4, 5, 6, 7, 8, or 9;
  • n is independently selected from 1 , 2, 3, 4, 5, 6, 7, 8, or 9;
  • p is independently selected from 0 or 1 ;
  • Ei and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group;
  • Ri, R2, R3, and R 4 are independently selected from H, C1-C12 alkyl, and -C(-0)-0-Ci-Ci2 alkyl.
  • the monomers were copolymerized with benzothiadiazole, dioctyloxybenzene and fluorene through fluoride-mediated Suzuki polymerization to give copolymers with low content of DPP (1 mol%).
  • the copolymers were used as the emitting layers in the light-emitting diodes.
  • the compounds are tested as electron acceptors in combination with poly(3-hexylthiophene) (P3HT) as the donor material.
  • P3HT poly(3-hexylthiophene)
  • Working photovoltaic devices are obtained that show a photoresponse in the wavelength region where the DPP molecules absorb.
  • the best device shows a power conversion efficiency of 0.31 % in simulated solar light, with a photon-to-electron conversion efficiency of ca. 10% up to 700 nm.
  • compositions comprising
  • a 1 and A 2 are independently of each other a group of formula
  • R 5 , A 3 , A 4 and A 5 are independently of each other a group of formula
  • -Ar- -Ar- -Ar- -Ar- -Ar- a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
  • R 1 , R 2 , R 1' , R 2' , R 1 " , R 2' , R 1* and R 2* may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, C6-d 4 aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR 39 -, -COO-, -CO- or -OCO-,
  • Ci- dalkyl Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C2 4 aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR 39 -, -COO-, -CO- or -OCO-,
  • Ci- dalkyl Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C2 4 aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR 39 -, -COO-, -CO- or -OCO-,
  • Ci- dalkyl a C3-Ci2cycloalkyl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C2 4 aryl, d- doheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR 39 -, -COO-, -CO- or -OCO-,
  • a C6-C2 4 aryl group which can optionally be substituted one or more times with d-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C2 4 sryl, d- doheteroaryl, s silyl group or s siloxsnyl group,
  • a d-doheteroaryl group which can optionally be substituted one or more times with Ci- dalkyl, d-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-d 4 sryl, d- doheterosryl, s silyl group or s siloxsnyl group,
  • R 3 is hydrogen, halogen, cyano, d-dsalkyl, d-dsalkyl which is substituted one or more
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a bivalent group of formula
  • R 10 and R 11 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C25arylalkyl, Ci-Cisalkanoyl,
  • R 12 and R 13 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C6-C2 4 aryl, C2-C2oheteroaryl, or R 12 and R 13 together represent oxo, r form a five or six membered ring, which is unsubstituted or substituted by Ci- C-iealkyl and/or Ci-Cisalkoxy;
  • R 14 and R 15 are independently of each other hydrogen, Ci-Cisalkyl, C6-C2 4 aryl, C2-
  • R 16 and R 17 are independently of each other hydrogen, halogen, Ci-C2salkyl, Ci-C2salkoxy,
  • R x is a Ci-Csalkyl group, or a tri(Ci-Cealkyl)silyl group,
  • R 18 and R 19 are independently of each other hydrogen, Ci-Cisalkyl, C7-C2sarylalkyl, or a phenyl group, which optionally can be substituted one to three times with Ci-Csalkyl and/or C-i-Cealkoxy,
  • R 20 and R 21 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2-
  • C25alkyl which is interrupted by one or more -O- or -S-, COOR 50 , cyano, Ci-Cisalkoxy, Ce- C2 4 aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl, or R 20 and R 21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (het- ero)aromatic residue and which may both have up to 4 carbon atoms,
  • R 30 to R 38 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2- C25alkyl which is interrupted by one or more -O- or -S-, COOR 50 , cyano, Ci-Cisalkoxy, C6- C2 4 aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl,
  • R 40 and R 41 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2- C25alkyl which is interrupted by one or more -O- or -S-, COOR 50 , cyano, Ci-Cisalkoxy, C6- C2 4 aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl,
  • R 50 is Ci-C25alkyl, Ci-C2shaloalkyl, C7-C2sarylalkyl, C6-C2 4 aryl or C2-C2oheteroaryl;
  • R60 to R68 represent independently of each other H, halogen, cyano, Ci-C2salkyl, Ci- C25alkyl which is substituted by E and/or interrupted by D, C6-C2 4 aryl, C6-C2 4 aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C3- Ci2cycloalkyl, C3-Ci2cycloalkyl, which is substituted by G, C2-Cisalkenyl, C2-Cisalkynyl, Ci- Cisalkoxy, Ci-Cisalkoxy which is substituted by E and/or interrupted by D, C7-C2saralkyl, or C7-C25aralkyl, which is substituted by G,
  • E is Ci-C 8 thioalkoxy, COO-Ci-Ci 8 alkyl, Ci-C 8 alkoxy, CN, -NR 39 R 39' , -CONR 39 R 39' , or halo- gen,
  • G is E, or Ci-Cisalkyl
  • R 39 and R 39' are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C25arylalkyl, or Ci-Cisalkanoyl. If the polymeric material is a dik PP) polymer it comprises at least 5
  • DPP repeating units of formula wherein each R 101 and R 102 have meaning of R 1 .
  • the quotient of the weight average molecular weight of the polymer and the molecular weight of the repeating unit of the polymer is at least 5.
  • the quotient is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
  • compositions of the present invention may provide improved charge mobility in elec- tronic devices as well as improved stability and integrity of the organic semiconductor layer.
  • an oligomer may be used to extend the effective absorption breath of a polymer bulk heterojunction solar cell. Phase seperation may be controlled and the device morphology may be optimized.
  • a is 1 or 2; b is 0, or 1 ; c is 0, or 1 , more preferably a is 1 , b is 1 and c is 1 , even more preferably a is 1 , b is 1 and c is 0, most preferably a is 1 , b and c are 0.
  • k is 0, or 1 ; I is 1 or 2; r is 0, or 1 ; z is 0 or 1.
  • k+l+r+z is an integer smaller than 4, more preferably k+l+r+z is 1 or 3.
  • R 1 , R 2 , R 1' , R 2' , R 1" , R 2" , R * and R 2* may be the same or different and are selected from hydrogen, a Ci-C36alkyl group which can optionally be substituted one or more times with Ci-Csalkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2- C2oheteroaryl, and/or can optionally be interrupted by -0-, -S-, -COO- or -OCO-, a C2-C36alkenyl group which can optionally be substituted one or more times with Ci- Cealkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-
  • a C3-C36alkinyl group which can optionally be substituted one or more times with Ci- CsalkyI, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-, -COO- or -OCO-,
  • a C3-Ci2cycloalkyl group which can optionally be substituted one or more times with Ci- Cealkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-, -COO- or -OCO-,
  • Ci-Csalkyl Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2-C2oheteroaryl,
  • Ci- Cealkyl Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C2 4 aryl, C2-C2oheteroaryl and -CO-Ci-Ci 8 alkyl, -CO-C 5 -Ci 2 cycloalkyl, -COO-Ci-Ci 8 alkyl.
  • R 1 , R 2 , R 1' , R 2' , R 1" , R 2' , R 1* and R 2* may be the same or different and are selected from hydrogen, a Ci-C36alkyl group, a C2-C36alkenyl group, a C3-C36alkinyl group which can optionally be interrupted one or more times by -0-, -S- or COO and a phenyl group which can optionally be substituted one or more times by d-Csalkyl, d-Csalkoxy, halogen or cyano.
  • R 1 , R 2 , R 1 ' , R 2' , R 1" , R 2" , R 1* and R 2* may be the same or different and are selected from hydrogen and a Ci-C36alkyl group. Most preferred R 1 , R 2 , R 1' , R 2' , R 1 " , R 2" , R 1* and R 2* may be the same or different and are selected from a Cg-C36alkyl group. In one particularly preferred embodiment of the present invention R 1 , R 2 , R 1 ' , R 2' , R 1 " , R 2" , R 1* and R 2* may be the same or different and are selected from a Ci3-C24alkyl group.
  • R is R 2
  • R ' is R 2'
  • R " is R 2"
  • R * is R 2* .
  • R , R 2 , R ' , R 2' , R " R 2" , R 1* and R 2* have all the same meaning.
  • R 1 , R 2 , R 1' , R 2' , R 1" , R 2" , R 1* and R 2* are Ci3-C24alkyl, especially Ci6-C24alkyl.
  • R 1 ' and R 2' can be represented by formula
  • Chiral side chains such as R 1' and R 2' , can either be homochiral, or racemic, which can influence the morphology of the polymers.
  • R 3 is hydrogen, halogen, cyano, C1-C25 alkyl,
  • Ci-Ci8thioalkoxy Ci-Cisalkoxy, or is R 5 or R 6 ;
  • R 3 is hydrogen, halogen, cyano, C1-C25 alkyl, , Ci-
  • Ar 1 , Ar 2 and Ar 3 are independently ent group of formu-
  • Ar 1 , Ar 2 and Ar 3 are independently of each other a bivalent group of formu- la Ar 4 , Ar 5 , Ar 6 and Ar 7 are preferably independently of each other a bivalent group of formula
  • X is is -S-, -NR -, -Si(R 8 )(R 19 )-
  • X is -NRTM-, -C(R 2 )(R1 3 ). or
  • R 10 and R 11 are independently of each other Ci-Cisalkyl, or Ci-Cisalkanoyl. Most preferably R 10 and R 11 are independently of each other Ci-Cisalkyl.
  • R 12 and R 13 dently of each other hydrogen, Ci-Cisalkyl, or R 12 and
  • R 13 together represent More preferably R 12 and R 13 are independently of each other hydrogen, or Ci-Cisalkyl. Most preferably R 12 and R 13 are independently of each other Ci-Cisalkyl.
  • R 14 and R 15 are independently of each other hydrogen, Ci-Cisalkyl, C6-C2 4 aryl, C2-C2oheteroaryl, -CN. or COOR 50 . More preferably R 14 and R 15 are independently of each other hydrogen, Ci-Cisalkyl, -CN or COOR 50 . Most preferably R 14 and R 15 are independently of each other hydrogen, -CN or COOR 50 ; especially -CN.
  • R 16 and R 17 are independently of each other hydrogen, Ci-C2salkyl, Ci-
  • R x is a C-i-Cealkyl group, or a tri(Ci-Cealkyl)silyl group. More preferably R 16 and R 17 are independently of each other Ci-C2salkyl or ⁇ R x , wherein
  • R x is a tri(Ci-C8alkyl)silyl group. Most preferably R 16 and R 17 are independently of each other , wherein R x is a tri(Ci-C8alkyl)silyl group,
  • R 18 and R 19 are independently of each other Ci-Cisalkyl, a phenyl group, which optionally can be substituted one to three times with d-Csalkyl and/or d-Csalkoxy. Most preferably R 18 and R 19 are independently of each other Ci-Cisalkyl.
  • R 20 and R 21 are independently of each other hydrogen, Ci-C25alkyl, C2-C2salkyl which is interrupted by one or more -O- or -S-, COOR 50 , cyano, Ci-Cisalkoxy, fluoro or R 20 and R 21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which may both have up to 4 carbon atoms. More preferably R 20 and R 21 are independently of each other hydrogen, Ci-C2salkyl, or cyano. Even more preferably R 20 and R 21 are independently of each other hydrogen, or Ci-C25alkyl. Most preferably R 20 and R 21 are hydrogen.
  • R 30 to R 38 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkyl which is interrupted by one or more -O- or -S-, COOR 50 , cyano, Ci-Cisalkoxy, or fluoro. More preferably R 30 to R 38 are independently of each other hydrogen, Ci-C2salkyl, or Ci- Cisalkoxy. Most preferably R 30 to R 38 are independently of each other hydrogen, or Ci- C25alkyl; especially hydrogen.
  • R 40 and R 41 are independently of each other hydrogen, Ci-C2salkyl, or cyano. More preferably R 40 and R 41 are independently of each other hydrogen, or Ci-C2salkyl. Most preferably R 40 and R 41 are independently of each other Ci-C2salkyl, Preferably R 50 is Ci-C 2 5alkyl, C 6 -C 2 4aryl or C 2 -C 2 oheteroaryl. Most preferably R 50 is Ci- C25alkyl,
  • R 60 to R 68 represent independently of each other H, fluoro, cyano, Ci-C2salkyl, or Ci-C25alkyl which is substituted by E and/or interrupted by D, Ci-Cisalkoxy. More preferably R 60 to R 68 represent independently of each other H, fluoro, cyano, Ci-C2salkyl, or Ci- C25haloalkyl. Even more preferably R 60 to R 68 represent independently of each other H, cyano, or Ci-C2salkyl. Most preferably R 60 to R 68 represent hydrogen.
  • compounds of formula I are preferred, wherein R 3 , R 20 , R21 , Rso to R 38 and R 60 to R 68 are hydrogen .
  • E is Ci-Csthioalkoxy, COO-Ci-Cisalkyl, Ci-Csalkoxy, CN or fluoro. More preferably E is Ci-Csalkoxy, CN, or fluoro. Even more preferably E is Ci- Cealkoxy, or fluoro. Most preferably E is Ci-Csalkoxy.
  • G is E, or Ci-Ci8alkyl.
  • R 39 and R 39' are independently of each other Ci-Cisalkyl, Ci-Cishaloalkyl, or Ci- Ciealkanoyl. More preferably R 39 and R 39' are independently of each other Ci-Cisalkyl, or Ci-Cishaloalkyl. Most preferably R 39 and R 39' are independently of each other Ci-Cisalkyl.
  • Examples of compounds of the formula I are compounds A-1 to A-27 and B-1. Reference is made to claim 9.
  • the polymeric material b) is preferably selected from nonconductive or semiconductive material, more preferably semiconductive material, such as, for example,
  • ⁇ ' is usually in the range of 10 to 1000, especially 10 to 200; very especially 10 to 150
  • polymers containing diketopyrrolopyrrole (DPP) repeating units which are, for example, described in US6451459, WO2005/049695, WO2008/000664, WO2009/047104, WO2010/049321 , WO2010/049323, WO2010/108873, WO2010/115767, WO2010/136353, WO201 1/144566, European patent application no. 11 192316.5,
  • the polymeric material is preferably p-type semiconductive.
  • the polymeric material is a polymer comprisi , especially a polymer represented by
  • each R 101 and R 102 have the meaning of R 1 ; each A 6 and A 7 is independently selected from optionally substituted aryl and heteroaryl groups; each M is an optional, conjugated moiety; s represents a number from 1 to 4; t represents a number from 1 to 4; u represents a number that is at least 1 , especially 1 ; v represents a number from 0 to 20, especially 1 to 5; and n repre- sents a number that is at least 5.
  • a 6 , A 7 and M may independently of each other have the meaning of Ar 1 . The same preferences apply for A 6 , A 7 and M as for Ar 1 .
  • v is an integer of 1 to 5, especially 1 ;
  • t is an integer of 1 to 3, especially 1 ;
  • s is an integer of 1 to 3, especially 1 ; the sum of v, t and s is equal, or smaller than 7,
  • a 6 , A 7 and M are independently of each other a group of formula , or , and R 101 and R 102 are the same and are a Ci-C36alkyl group, n is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
  • Ri * may be the same or different.
  • R 2 , R 2 ', R 2 ', or R 2* may be the same or different.
  • the polymeric material is a DPP polymer it comprises at least 5, especially at least 10
  • the quotient of the weight average molecular weight of the DPP polymer and the molecular weight of the repeating unit of the polymer is at least 5.
  • the quotient is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
  • n a preferred n the composition comprises a compound
  • a 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 2 , R 1' , R 2' , R 1" , R 2' , R * and R 2* are as defined above.
  • the weight% (w%ong) of one, or a mixture of more than one oligomer of formula (I) in the composition of the present invention is 0.1 % to 99.9%.
  • the weight% (w%p 0 i) of one, or a mixture of more than one polymers in the composition of the present invention is 0.1 % to 99.9%.
  • the sum of w%oii g and w%p 0 i adds up to 100.
  • compositions according to the present invention are mixtures of compounds in Example 1 of WO2010/049321 :
  • the present invention is also directed to a formulation, comprising
  • the formulation can be used for the production of the organic layer, especially an organic semiconducting (OSC) layer.
  • OSC organic semiconducting
  • the OSC layer can be used in an organic semiconductor device.
  • the formulation and the OSC layer according to the present invention may be prepared by a process which comprises:
  • the mixing comprises mixing the components together in a solvent or solvent mixture,
  • the solvent may be a single solvent, or the compound(s) of formula I and polymeric materials(s) may each be dissolved in a separate solvent followed by mixing the two resultant solutions.
  • the polymeric materials(s) may be dissolved together with the compound(s) of formula I in a suitable solvent, and the solution deposited for example by dipping, spraying, painting or printing it on a substrate to form a liquid layer and then removing the solvent to leave a solid layer. It will be appreciated that solvents are chosen which are able to dissolve both the compound(s) of formula I and polymeric materials(s), and which upon evaporation from 0 the solution blend give a coherent defect free layer.
  • suitable and preferred organic solvents include, without limitation, dichloro- methane, trichloromethane, monochlorobenzene, o- dichlorobenzene, 1 ,2,4- trichlorbenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p- 5 xylene, 1 ,4-dioxane, acetone, methylethylketone, 1 ,2-dichloroethane, 1 ,1 ,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, dimethyla- cetamide, dimethylsulfoxide, tetralin, decalin, indane, mesitylene, 1-methylnaphthalene and/or mixtures thereof. 0 It is desirable to be
  • Liquid coating of organic electronic devices is more desirable 5 than vacuum deposition techniques.
  • the formulations of the present invention enable the use of a number of liquid coating techniques.
  • the organic semiconductor layer may be incorporated into the final device structure by, for example, and without limitation, dip coating, spin coating, ink jet printing, letter-press printing, screen printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, flexographic printing, web printing, spray coating, slot-die coating, brush coating or pad printing.
  • the OSC formulation according to the present invention can additionally comprise one or more further components like for example surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive or non-reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles, furthermore, especially in case crosslinkable binders are used, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents or co- reacting monomers.
  • further components like for example surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive or non-reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles, furthermore, especially in case crosslinkable binders are used, catalyst
  • R 103 2-hexyldecyl and y is 3, or 4, are excluded.
  • the compound of the formula II is more preferably a compound of the formula
  • a 2 , A 3 , A 4 , A 5 , R 1 , R2, R i' , R 2' , R i" , R 2" , R i* and R 2* are as defined above.
  • Compounds of the formula Ma are preferred.
  • the preferences for A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 2 , R 1 ' , R 2' , R 1 ' , R 2' , R 1* and R 2* are the same as specified above for the compounds of formula I.
  • a 1 and A 2 are independently of each other a group of formula
  • a 3 is a group of formula
  • R 1 , R 2 , R 1' , R 2' , R 3 and R 5 are as defined above;
  • Ar 1 , Ar 2 and Ar 3 are independently of each other a bivalent group of formula
  • Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a bivalent group of formula
  • R 105 is 2-ethylhexyl
  • Compounds of formula III are preferred, wherein the (hetero)arylgroups Ar 1 and Ar 4 to Ar 7 , which are directly linked to the diketopyrrolopyrrole basic structure, are different from a six- membered ring.
  • R 3 , R 2 o, R 21 , R3o t 0 R38 and R 60 to R 68 are hydrogen .
  • R 1 , R 2 , R 1' , R 2' , R 1 ' , R 2' , R * and R 2* are C13- C2 4 alkyl, especially Ci6-C2 4 alkyl.
  • a is 1 or 2; b is 0, or 1 ; c is 0, or 1 , more preferably a is 1 , b is 1 and c is 1 , even more preferably a is 1 , b is 1 and c is 0, most preferably a is 1 , b and c are 0.
  • k is 0, or 1 ; I is 1 or 2; r is 0, or 1 ; z is 0 or 1.
  • k+l+r+z is an integer smaller than 4, more preferably k+l+r+z is 1 or 3.
  • compound (III) is different from . More preferably Ar 1 is different from
  • R 20 and R 21 have the meaning as described for compound (I).
  • the preferences for a, b, c, k, I, r, z, R 3 , R 5 , R 6 , R 1 , R 2 , R 1* and R 2* are, in principal, the same as specified above for the compounds of formula I.
  • the present invention is directed to compounds of formula III, wherein R 1 , R 2 , R 1* and R 2* may be the same or different and are selected from a C13- C2 4 alkyl group.
  • Ar 1 , Ar 2 , Ar 3 are independently of each other a bivalent group of formula
  • Ar 1 , Ar 2 and Ar 3 are independently of each other a bivalent group of formula
  • Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a bivalent rou of formula
  • a moiety selected from Ar 1 , Ar 5 or Ar 7 is linked via a single bond to the DPP basis skeleton, preferably the substituents in ortho position to this linking bond are hydrogen.
  • R 3 is R 5 .
  • a 1 and A 2 have the meaning of R 5 .
  • a 1 and A 2 are as defined above, g 1 to 4, especially 1 ; R 1 , R 2 , R 1*
  • R 2* are a Ci-C3salkyl group and Ar 5 is (h is 1 , 2, or 3, especially 1 , or 3, very especially 1), , wherein X, R «>, R12. RI3. RIB. RI7. R2O, 21 ANC
  • R 35 are as defined above.
  • R2 R 1* and R 2* are a Ci-C38alkyl group, especially a Ci3-C24alkyl group, and Ar 4 and Ar 6 are independently of each other , X, R10, R12, R13. R16. R17. R20, R21 anc
  • Examples of compounds of the formula III are compounds A-1 to A-27. Reference is made to claim 9. Among the compounds A-1 to A-27 compounds A-1 , A-4, A-10, A-11 , A-13, A- 14, A-22 to A-27 are preferred.
  • R 2 is R 1* , comprises
  • R 200 and R 200' are independently of each other a Ci-Csalkyl group, or a benzyl group) with 1 mole of a di-nitrile compound of the for-
  • step (a) tained in step (a) with a compound R 2 -X 16 (X 16 is halogen, especially J, or Br) under basic conditions (preferably K2CO3) in a dry solvent such as e.g. dimethylformamide, wherein A 1 , A 2 , A 3 , R 1 , R2, R i* and R 2* are as defined above.
  • a dry solvent such as e.g. dimethylformamide, wherein A 1 , A 2 , A 3 , R 1 , R2, R i* and R 2* are as defined above.
  • the oligomers of formula (II) and (III) are present in pure form. They are not present in form of a mixture with further oligomers and/or polymers.
  • step a) obtained in step a) with a bromide of the formula R 1 -X 16 (X 16 is halogen, especially Br, or I) in the presence of a suitable base, like potassium carbonate, in a suitable solvent, like N-methyl-pyrrolidone, R 1 , R 1 ' , R 2' , A 1 , A 3 and A 4 are as defined above.
  • a suitable base like potassium carbonate
  • a suitable solvent like N-methyl-pyrrolidone
  • the disuccinates to be used in the process according to the invention include dialkyi, diaryl or monoalkyl-monoaryl succinates.
  • the dialkyi and diaryl succinates may also be asymmetrical. However, it is preferred to use symmetrical disuccinates, most preferably symmetrical dialkyi succinates, most preferably symmetrical dialkyi succinates.
  • aryl denotes preferably phenyl which is unsub- stituted or substituted by halogen such as chlorine, Ci-6-alkyl such as ethyl, methyl, isopro- pyl or tert-butyl, or Ci-6-alkoxy such as methoxy or ethoxy.
  • halogen such as chlorine
  • Ci-6-alkyl such as ethyl, methyl, isopro- pyl or tert-butyl
  • Ci-6-alkoxy such as methoxy or ethoxy.
  • the preferred meaning of aryl is unsubstituted phenyl.
  • alkyl may be unbranched or branched, preferably branched, and may contain preferably 1 to 18, in particular 1 to 12, more particularly 1 to 8 and more preferably 1 to 5, carbon atoms.
  • Branched alkyl is preferably sec- or tert-alkyl, for example, isopropyl, sec-butyl, tert-butyl, tert-amyl and cyclohexyl.
  • disuccinates are dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, dihexyl succinate, diheptyl succinate, dioctyl succinate, diisopropyl succinate, di-sec-butyl succinate, di-tert-butyl succinate, di-tert-amyl suc- cinate, di-[1 ,1-dimethylbutyl] succinate, di-[1 ,1 ,3,3-tetramethylbutyl] succinate, di-[1 ,1- dimethylpentyl] succinate, di-[1-methyl-ethylbutyl] succinate, di-[1 , 1 -diethylpropyl] succinate, diphenyl succinate, di-[4-methylphenyl] succinate, di-[4-chlorophenyl] succinate, mo- noethyl-monophenyl succinate
  • the disuccinates are known compounds and may be prepared by known methods.
  • the nitriles and the disuccinate are used in stoichiometric proportions. It can be advantageous to use the nitriles to be reacted with the disuccinate in more than only stoi- chiometric proportions. An excess of disuccinate over the nitrile can often have a positive influence on the yield, in which case the excess may be up to twice the stoichiometrically required amount of disuccinate.
  • the reaction of the disuccinate with the nitriles is carried out in an organic solvent.
  • suitable solvents are primary, secondary or tertiary alcohols containing 1 to 10 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- butanol, tert-butanol, n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3- pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, 2,4,4-trimethyl-2-pentanol, or glycols such as ethylene glycol or diethylene glycol; and also ethers such as tetrahydrofuran or dioxan, or glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or diethylene glycol
  • an alcohol as solvent, in particular a secondary or tertiary alcohol.
  • Preferred tertiary alcohols are tert-butanol and tert-amyl alcohol. Mixtures of these preferred solvents with aromatic hydrocarbons such as toluene or xylene, or halogen-substituted benzene such as chlorobenzene, are also useful.
  • Suitable strong bases are in particular the alkali metals themselves such as lithium, sodium or potassium, or alkali metal amides such as lithium amide, sodium amide or potassium amide, or alkali metal hydrides such as lithium, sodium or potassium hydride, or alkaline earth metal alcoholates or alkali metal alcoholates which are derived preferably from primary, secondary or tertiary aliphatic alcohols containing from 1 to 10 carbon atoms, for exam- pie, lithium methylate, sodium methylate or potassium methylate, or lithium, sodium or potassium ethylate, lithium, sodium or potassium n-propylate, lithium, sodium or potassium iso-propylate, lithium, sodium or potassium n-butylate, lithium, sodium or potassium sec- butylate, lithium, sodium or potassium tert-butylate, lithium, sodium or potassium 2-methyl- 2-butylate, lithium, sodium or potassium 2-methyl-2-pentylate, lithium, sodium or potassium 3-methyl
  • the preferred strong base is an alkali metal alcoholate, the alkali metals being preferably sodium or potassium and the alcoholate being preferably derived from a secondary or tertiary alcohol.
  • Particularly preferred strong bases are therefore, for example, sodium or potassium isopropylate, sodium or potassium sec-butylate, sodium or potassium tert-butylate and sodium or potassium tert-amylate.
  • the alkali metal alcoholates may be prepared in situ by reacting the appropriate alcohol with the alkali metal, alkali metal hydride or alkali metal amide.
  • the strong base is employed in an amount of preferably from about 0.1 to about 10 moles, most preferably from about 1.9 to about 4.0 moles, based on one mole of the disuccinate. Although a stoichiometric amount of base may suffice, an excess of base has been found to have an advantageo
  • X 14 is halogen, such as, for example, Br, or I
  • copper(l)cyanide is carried out in a suitable solvent, like dimethylforamide (DMF) and is carried out at a temperature from about room temperature to about 180°C, preferably from about 100 °C to about 170 °C, e.g. at 130 °C.
  • a suitable solvent like dimethylforamide (DMF)
  • DMF dimethylforamide
  • X 16 is halogen, especially J, or Br
  • basic conditions preferably K2CO3
  • a dry sol- vent such as e.g. dimethylformamide
  • a 1 , A 2 , A 3 , R , R 2 , R ' , R 2' , R * and R 2* are as defined above.
  • X 15 is a halogen atom, especially Br, or 1. 1 and z are independently of each other 1 , or 2. k is 0, 1 or 2. r is 0, or 1. R , R 2 , R 1* , R 2* , A 1 and A 2 are as defined above.
  • step (a) tained in step (a) with a compound R 2 -X 16 (X 16 is halogen, especially J, or Br) under basic conditions (preferably K2CO3) in a dry solvent such as e.g. dimethylformamide.
  • a dry solvent such as e.g. dimethylformamide.
  • the compounds of formula XV and XV can be synthesized, for example, in analogy to the methods described in C. Morton et al., Tetrahedron 58 (2002) 5547-5565, or Tetrahedron 62 (2006) 6018-6028.
  • Ar 4 is Ar 7 , k is 1 , or 2, z is 1 , or 2) may be prepared
  • X16' is -B(OH) 2 , -B(OH) 3 -, -BF 3 , -B(OY ) 2 , and X 16 is halogen, such as, for example, Br, or I.
  • the Suzuki reaction is typically conducted at about 0 °C to 180 °C in an aromatic hydrocarbon solvent such as toluene, xylene.
  • aromatic hydrocarbon solvent such as toluene, xylene.
  • Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon.
  • An aqueous base preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger.
  • a condensation reaction may take 0.2 to 100 hours.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example TBAB
  • Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.
  • the compounds of the present invention can also be sythesized by the Stille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 1 1-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508).
  • Stille coupling see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 1 1-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508.
  • inert organic solvents are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200°C, preferably from 30 to 170°C for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours.
  • the halogen X 16 on the halogenated reaction partner can be replaced with the X 16' moiety and at the same time the X 16' moiety of the other reaction partner is replaced by X 16 .
  • R 1 , R 2 , R 1' , R 2' , R 1 " , R 2" , R 1* and/or R 2* are hydrogen
  • a protecting group which can be removed after synthesis of the precursor compound
  • Conversion of the precursor compound into the desired final compound is carried out by means of fragmentation under known conditions, for example thermally, optionally in the presence of an additional catalyst, for example the catalysts described in WO00/36210.
  • Z 4 and Z 8 are independently of each other Ci-C6alkyl, Ci-C6alkyl interrupted by oxygen, sulfur or N(Z 12 )2, or unsubstituted or Ci-C6alkyl-, Ci-C6alkoxy-, halo-, cyano- or nitro- substituted phenyl or biphenyl,
  • Z 5 , Z 6 and Z 7 are independently of each other hydrogen or Ci-C6alkyl
  • Z 9 is hydrogen, Ci-C6alkyl or a group of formula or
  • Z 10 and Z 11 are each independently of the other hydrogen, Ci-C6alkyl, Ci-C6alkoxy, halogen, cyano, nitro, N(Z 12 )2, or unsubstituted or halo-, cyano-, nitro-, Ci-C6alkyl- or
  • Z 12 and Z 13 are Ci-Cealkyl
  • Z 14 is hydrogen or Ci-Cealkyl
  • Z 15 is hydrogen, Ci-Cealkyl, or unsubstituted or Ci-C6alkyl-substituted phenyl
  • Q is p,q-C2-C6alkylene unsubstituted or mono- or poly-substituted by Ci-C6alkoxy
  • Ci-C6alkylthio or C2-Ci2dialkylamino wherein p and q are different position numbers
  • X is a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, m' being the number 0 when X is oxygen or sulfur and m being the number 1 when X is nitrogen, and
  • L 1 and L 2 are independently of each other unsubstituted or mono- or poly-Ci-Csalkoxy-, -Ci-Cealkylthio-, -C2-C24dialkylamino-, -C6-Ci2aryloxy-, -C6-Ci2arylthio-,
  • Most preferred L is a
  • (X) are intermediates in the production of polymers and form a further subject of the present invention.
  • a 1 ' and A 2' are independently of each other a group of formula
  • R 3' is independently in each occurrence ZnX 2 , -SnR 07 R 08 R 209 , wherein R 207 , R 208 and R209 are identical or different and are H or Ci-C6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched;
  • X 12 is a halogen atom, very especially I, or Br; -OS(0)2CF3, -OS(0)2-aryl, especially -OS(0) 2 CH 3 , -B(OH) 2 , -B(OH) 3 -, -BF 3 , -B(OY ) 2 , or
  • Y 1 is independently in each occurrence a Ci-Csalkyl group and Y 2 is independently in each occurrence a C2-Cioalkylene group, such as -CY 3 Y 4 -CY 5 Y 6 -, or - CY Y8.CY9Y10- CY11Y1 2 -, wherein Y 3 , Y 4 , Ys, ⁇ ⁇ , Y 7 , ⁇ ⁇ _ ⁇ ⁇ .
  • ⁇ and Yi 2 are independently of each other hydrogen, or a Ci-Csalkyl group, especially -C(CH3)2C(CH3)2-, or -C(CH3)2CH 2 C(CH 3 )2-, -CH 2 C(CH 3 ) 2 CH 2 -, and Y 13 and Y 14 are independently of each other hydrogen, or a Ci-C 8 alkyl group; a, b, c, p, q, R , R 2 , R ' , R 2' , R " , R 2" , R * , R 2* , Ar , Ar 2 , Ar 3 , A 3 , A 4 and A 5 are as defined above.
  • An example of a compound of formula X is compound A-16 as depicted in claim 9.
  • Compounds of formula X can be obtained in analogy to known procedures, which are, for example, described in US6451459, WO2005/049695, WO2008/000664, WO2009/047104, WO2010/049321 , WO2010/049323, WO2010/108873, WO2010/115767, WO2010/136353, EP2033983 and EP2034537.
  • the compounds of formula X can be used to prepare polymers. Accordingly, the present invention is also directed to polymers comprising repeating unit(s) of formula R ,1' ' O R" O R ' O O
  • the polymers of the present invention may be used in the production of semiconductor devices. Accordingly, the present invention is also directed to semiconductor devices comprising a polymer of the present invention.
  • Halogen is fluorine, chlorine, bromine and iodine.
  • Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-non
  • d-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl.
  • Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl.
  • a haloalkyi group is an alkyl group, wherein one, or more than one hydrogen atoms are repled by halogen atoms.
  • a haloalkyi group is an alkyl group, wherein one, or more than one hydrogen atoms are repled by halogen atoms.
  • C2-C25alkenyl (C2-Cisalkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4- dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
  • alkenyl groups such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4- dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,
  • C2-25alkynyl is straight-chain or branched and preferably C2-salkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn- 4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6- yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.
  • Ci-C25alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.
  • Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2- dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1 ,1 ,3,3-tetramethylbutoxy and 2- ethylhexoxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, iso- propoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy.
  • alkylthio group means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.
  • Ci-Ci8perfluoroalkyl is a branched or unbranched radical such as for example -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CF 3 ) 3 .
  • carrier group is typically a Ci-i8carbamoyl radical, preferably d-scarbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcar- bamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.
  • alkanoyl represents an alkyl group attached to the parent molecular group through a carbonyl group and is exemplified by formyl, acetyl, propionyl, and butanoyl.
  • sil group means a group of formula -SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are independently of each other a d-Csalkyl group, in particular a C1-C4 alkyl group, a C6- C 2 4aryl group, or a C7-Ci 2 aralkylgroup, such as a trimethylsilyl group.
  • siloxanyl group means a group of formula -0-SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are as defined above, such as a trimethylsiloxanyl group.
  • Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are d-Csalkoxy or d-Csalkylthio groups as exemplified further below.
  • the term "aliphatic group" comprises also alkyl groups wherein certain non-adjacent carbon atoms are re- placed by oxygen, like -CH 2 -0-CH 2 -CH 2 -0-CH 3 . The latter group can be regarded as methyl substituted by -0-CH 2 -CH 2 -0-CH 3 .
  • An aliphatic hydrocarbon group having up to 25 carbon atoms is a linear or branched alkyl, alkenyl or alkynyl (also spelled alkinyl) group having up to 25 carbon atoms as exemplified above.
  • Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) free valencies, e.g. tri- methylene or tetramethylene.
  • Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are d-Csalkoxy or d-Csalkylthio groups as exemplified further below.
  • the term "aliphatic group" comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like -CH2-O-CH2-CH2-O-CH3. The latter group can be regarded as methyl substituted by -O-CH2-CH2-O-CH3.
  • a cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl group which may be substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups.
  • a cycloaliphatic-aliphatic group is an aliphatic group substituted by a cycloaliphatic group, wherein the terms "cycloaliphatic” and “aliphatic” have the meanings given herein and wherein the free valency extends from the aliphatic moiety.
  • a cycloaliphatic- aliphatic group is for example a cycloalkyl-alkyl group.
  • a cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkyl group, e.g. cyclohex- yl-methyl.
  • a "cycloalkenyl group” means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups and/or condensed with phenyl groups.
  • a bivalent group of the formula (X 1 is , S, Se, or NR 10 ) wherein R 20 and R 21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, is e.g. a group of the formula
  • A represents linear or branched alkylene having up to 25 carbon atoms, preferably ethylene or propylene which may be substituted by one or more alkyl groups
  • Y represents oxygen or sulphur.
  • the bivalent group of the formula -Y-A-O- represents -O-CH2-CH2-O- or -O-CH2-CH2-CH2-O- .
  • a cycloalkyl group is typically C3-Ci2cycloalkyl (especially C5-Ci2cycloalkyl), such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloun- decyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
  • the cycloalkyl group, or cycloalkenyl group, in particular a cyclohexyl group can be condensed one or two times by phenyl which can be substituted one to three times with Ci-C4-alkyl, halogen and cyano. Examples of such condensed
  • R 155 and R 156 are independently of each other d-Cs-alkyl, d-Cs-alkoxy, halogen and cy- ano, in particular hydrogen.
  • C6-C2 4 aryl is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, as- indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted.
  • C6-Ci2aryl examples include phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted.
  • C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ro,co-dimethyl-co-phenyl-butyl, o-phenyl-dodecyl, co-phenyl-octadecyl, co-phenyl-eicosyl or co-phenyl-docosyl, preferably Cz-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, co-phenyl-dodecyl or co-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such
  • Heteroaryl is typically C2-C2oheteroaryl, i.e.
  • Possible substituents of the above-mentioned groups are d-Csalkyl, a hydroxyl group, a mercapto group, d-Csalkoxy, d-Csalkylthio, halogen, halo-d-Csalkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially d-Csalkyl, d-Csalkoxy, d- Cealkylthio, halogen, halo-d-Csalkyl, or a cyano group.
  • Ci-dsalkyl (Ci-Cisalkyl) interrupted by one or more O is, for example, (CH2CH20)i-9-R x , where R* is H or d-doalkyl, CH2-CH(ORy')-CH 2 -0-Ry, where Ry is Ci-dsalkyl (Ci- Ci8alkyl), and Ry' embraces the same definitions as Ry or is H.
  • a substituent such as, for example R 3 , occurs more than one time in a group, it can be different in each occurrence.
  • compositions, or compounds of the present invention, or an organic semiconductor material, layer or component, comprising the compositions, or compounds of the present invention can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
  • OFET organic field effect transistor
  • the compounds of the present invention can show p-type transistor behavior and can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to a semiconductor device comprising as a semiconducting effective means a compound of the present invention.
  • the invention relates especially to a semiconductor device comprising as as a semiconducting effective means a composition, or a compound of the present invention.
  • a composition or a compound of the present invention.
  • the compounds are especially selected from compounds A-1 to A-27 and B-1 , respectively, which are depicted in claim 9.
  • said semiconductor device is a diode, a photodiode, a sensor, an organic field effect transistor (OFET), a transistor for flexible displays, or a solar cell, or a device containing a diode and/or an organic field effect transistor, and/or a solar cell.
  • OFET organic field effect transistor
  • semiconductor devices Common to all is the presence of one or more semiconductor materials. Semiconductor devices have been described, for example, by S. M. Sze in Physics of Semiconductor Devices, 2 nd edition, John Wiley and Sons, New York (1981 ).
  • Such devices include rectifiers, transistors (of which there are many types, including p-n-p, n-p-n, and thin-film transistors), light emitting semiconductor devices (for example, organic light emitting diodes in display applications or backlight in e.g. liquid crystal displays), pho- toconductors, current limiters, solar cells, thermistors, p-n junctions, field-effect diodes, Schottky diodes, and so forth.
  • the semiconductor material is combined with one or more metals and/or insulators to form the device.
  • Semiconductor devices can be prepared or manufactured by known methods such as, for example, those described by Peter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill, New York (2000).
  • organic electronic components can be manufactured as described by D.R. Gamota et al. in Printed Organic and Molecular Electronics, Kluver Academic Publ., Boston, 2004.
  • a particularly useful type of transistor device, the thin-film transistor (TFT) generally includes a gate electrode, a gate dielectric on the gate electrode, a source electrode and a drain electrode adjacent to the gate dielectric, and a semiconductor layer adjacent to the gate dielectric and adjacent to the source and drain electrodes (see, for example, S. M. Sze, Physics of Semiconductor Devices, 2 nd edition, John Wiley and Sons, page 492, New York (1981)).
  • These components can be assembled in a variety of configurations. More specifically, an organic thin-film transistor (OTFT) has an organic semiconductor layer.
  • a substrate supports the OTFT during manufacturing, testing, and/or use.
  • the substrate can provide an electrical function for the OTFT.
  • Useful substrate ma- terials include organic and inorganic materials.
  • the substrate can comprise silicon materials inclusive of various appropriate forms of silicon, inorganic glasses, ceramic foils, polymeric materials (for example, acrylics, polyester, epoxies, polyamides, polycarbonates, polyimides, polyketones, poly(oxy-1 ,4-phenyleneoxy-1 ,4-phenylenecarbonyl-1 ,4- phenylene) (sometimes referred to as poly(ether ether ketone) or PEEK), polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalenedicarboxylate) (PEN), poly(ethylene ter- ephthalate) (PET), poly(phenylene sulfide) (PPS)), filled polymeric materials (for example, fiber-reinforced plastics (FRP)), and coated metallic
  • the gate electrode can be any useful conductive material.
  • the gate electrode can comprise doped silicon, or a metal, such as aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, and titanium.
  • Conductive oxides such as indium tin oxide (ITO), or conducting inks/pastes comprised of carbon black/graphite or colloidal silver dis- persions, optionally containing polymer binders can also be used.
  • Conductive polymers also can be used, for example polyaniline or poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS).
  • PEDOT:PSS poly(styrene sulfonate)
  • alloys, combinations, and multilayers of these materials can be useful.
  • the same material can provide the gate electrode function and also provide the support function of the substrate.
  • doped silicon can function as the gate electrode and support the OTFT.
  • the gate dielectric is generally provided on the gate electrode. This gate dielectric electrically insulates the gate electrode from the balance of the OTFT device.
  • Useful materials for the gate dielectric can comprise, for example, an inorganic electrically insulating material.
  • the gate dielectric (insulator) can be a material, such as, an oxide, nitride, or it can be a material selected from the family of ferroelectric insulators (e.g. organic materials such as poly(vinylidene fluoride/trifluoroethylene or poly(m-xylylene adipamide)), or it can be an organic polymeric insulator (e.g. poly(methacrylate)s, poly(acrylate)s, polyimides, benzocy- clobutenes (BCBs), parylenes, polyvinylalcohol, polyvinylphenol (PVP), polystyrenes, poly- ester, polycarbonates) as for example described in J. Veres et al. Chem.
  • ferroelectric insulators e.g. organic materials such as poly(vinylidene fluoride/trifluoroethylene or poly(m-xylylene adipamide)
  • organic polymeric insulator e.g. poly(
  • Examples of materials useful for the gate dielectric include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, and zinc sulphide, including but not limited to PbZr x Tii-x0 3 (PZT), Bi 4 Ti 3 0i 2 , BaMgF 4 , Ba(Zri- x Tix)0 3 (BZT).
  • alloys, hybride materials e.g.
  • the thickness of the dielectric layer is, for example, from about 10 to 1000 nm, with a more specific thickness being about 100 to 500 nm, providing a capacitance in the range of 0.1 - 100 nanofarads (nF).
  • the source electrode and drain electrode are separated from the gate electrode by the gate dielectric, while the organic semiconductor layer can be over or under the source electrode and drain electrode.
  • the source and drain electrodes can be any useful conductive material favourably providing a low resistance ohmic contact to the semiconductor layer.
  • Useful materials include most of those materials described above for the gate electrode, for example, aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof, combinations thereof, and multilayers thereof. Some of these materials are appropriate for use with n- type semiconductor materials and others are appropriate for use with p-type semiconductor materials, as is known in the art.
  • the thin film electrodes can be provided by any useful means such as physical vapor deposition (for example, thermal evaporation or sputtering) or (ink jet) printing methods.
  • the patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.
  • the present invention further provides a thin film transistor device comprising
  • a gate insulator layer disposed on said electrically conducting gate electrodes
  • the present invention further provides a process for preparing a thin film transistor device comprising the steps of:
  • the ratio of the compound of formula I to the polymeric material can vary from 5 to 95 percent based on the amount of the compound of formula I and the polymeric material.
  • the polymeric material may be a semi-conducting polymer, or a polymeric binder.
  • the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).
  • PS polystyrene
  • HDPE high-density polyethylene
  • PP polypropylene
  • PMMA polymethylmethacrylate
  • the above-mentioned layer comprising a compound of the present invention may additionally comprise at least another material.
  • the other material can be, but is not restricted to another compound of the present invention, a semi-conducting polymer, a polymeric bind- er, organic small molecules different from a compound of the present invention, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.).
  • Any suitable substrate can be used to prepare the thin films of the compositions, or compounds of the present invention.
  • the substrate used to prepare the above thin films is a metal, silicon, plastic, paper, coated paper, fabric, glass or coated glass.
  • a TFT is fabricated, for example, by solution deposition, or vacuum deposition of a composition, or compound of the present invention on a highly doped silicon substrate covered with a thermally grown oxide layer followed by vacuum deposition and patterning of source and drain electrodes.
  • a TFT is fabricated by deposition of source and drain electrodes on a highly doped silicon substrate covered with a thermally grown oxide and then solution deposition of a composition, or compound of the present invention to form a thin film.
  • the gate electrode could also be a patterned metal gate electrode on a substrate or a conducting material such as a conducting polymer, which is then coated with an insulator ap- plied either by solution coating or by vacuum deposition on the patterned gate electrodes.
  • Suitable or- ganic solvents for processing the semiconductors of the invention include, but are not lim- ited to, aromatic or aliphatic hydrocarbons, halogenated such as chlorinated or fluorinated hydrocarbons, esters, ethers amides, such as chloroform, tetrachloroethane, tetrahydrofu- ran, toluene, tetraline, anisole, xylene, ethyl acetate, methyl ethyl ketone, dimethyl forma- mide, dichlorobenzene, trichlorobenzene, propylene glycol monomethyl ether acetate (PGMEA) and mixtures thereof.
  • PGMEA propylene glycol monomethyl ether acetate
  • the solution, and/or dispersion is then applied by a method, such as, spin-coating, dip-coating, screen printing, microcontact printing, doctor blading or other solution application techniques known in the art on the substrate to obtain thin films of the semiconducting material.
  • a method such as, spin-coating, dip-coating, screen printing, microcontact printing, doctor blading or other solution application techniques known in the art on the substrate to obtain thin films of the semiconducting material.
  • dispenser covers any composition comprising a composition, or compound of the present invention, which is not fully dissolved in a solvent.
  • the dispersion can be done selecting a composition including at least a compound of formula I, or a mixture containing a compound of formula I, and a solvent, wherein the oligomer and/or polymer exhibits lower solubility in the solvent at room temperature but exhibits greater solubility in the solvent at an elevated temperature, wherein the composition gels when the elevated temperature is lowered to a first lower temperature without agitation;
  • the dispersion can also be constituted of (a) a continuous phase comprising a solvent, a binder resin, and optionally a dispersing agent, and (b) a disperse phase comprising a compound of formula I, or a mixture containing a compound of formula I of the present invention.
  • the degree of solubility of the compound of formula I in the solvent may vary for example from 0.5 % to about 20 % solubility, particularly from 1 % to about 5 % solubility.
  • the thickness of the organic semiconductor layer is in the range of from about 5 to about 1000 nm, especially the thickness is in the range of from about 10 to about 100 nm.
  • the compositions, or compounds of the present invention can be used alone as the organic semiconductor layer of the semiconductor device.
  • the layer can be provided by any useful means, such as, for example, vapor deposition and printing techniques.
  • the compositions, or compounds of the present invention, which are sufficiently soluble in organic solvents can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).
  • compositions, or compounds of the present invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles.
  • Such articles in- elude, for example, radio-frequency identification (RFID) tags, backplanes for flexible dis- plays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like. Due to its ambi-polarity the material can also be used in Organic Light Emitting Transistors (OLET).
  • OFID Radio-frequency identification
  • OLET Organic Light Emitting Transistors
  • the invention provides organic photovoltaic (PV) devices (solar cells) comprising a composition, or a compound of the present invention.
  • PV organic photovoltaic
  • the structure of organic photovoltaic devices (solar cells) is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
  • the PV device comprise in this order:
  • transition layer such as an alkali halogenide, especially lithium fluoride
  • the photoactive layer comprises the compositions, or compounds of the present invention.
  • the photoactive layer is made of a composition, or a compound of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor.
  • fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule).
  • the term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene ⁇ Ceo) and the related "spherical" fullerenes as well as carbon nanotubes.
  • Fullerenes may be selected from those known in the art ranging from, for example, C20-C1000.
  • the fullerene is selected from the range of Ceo to C 9 6.
  • the fullerene is Ceo or C70, such as [60]PCBM, or [70]PCBM.
  • the acceptor material can also be a material selected from the group consisting of another compound of formula I or any semi-conducting polymer provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.).
  • the active layer comprises preferably a mixture of a compound of the present invention and a fullerene, such as
  • PCBM 6,6-phenyl-C 6 i-butyric acid methyl ester
  • PCBM 6,6-phenyl-C 6 i-butyric acid methyl ester
  • PCBM Methanofullerene Phenyl-Cei-Butyric-Acid-Methyl-Ester
  • the electrodes are preferably composed of metals or "metal substitutes".
  • metal is used to embrace both materials composed of an elementally pure metal, e.g., Mg, and also metal alloys which are materials composed of two or more elementally pure metals, e.g., Mg and Ag together, denoted Mg:Ag.
  • metal substitute refers to a material that is not a metal within the normal definition, but which has the metal-like properties that are desired in certain appropriate applications.
  • metal substitutes for electrodes and charge transfer layers would include doped wide-bandgap semiconductors, for example, transparent conducting oxides such as indium tin oxide (ITO), gallium indium tin oxide (GITO), and zinc indium tin oxide (ZITO).
  • transparent conducting oxides such as indium tin oxide (ITO), gallium indium tin oxide (GITO), and zinc indium tin oxide (ZITO).
  • ITO indium tin oxide
  • GITO gallium indium tin oxide
  • ZITO zinc indium tin oxide
  • Another suitable metal substitute is the transparent conductive polymer polyanaline (PANI) and its chemical relatives, or PEDOT:PSS.
  • Metal substitutes may be further selected from a wide range of non- metallic materials, wherein the term "non-metallic" is meant to embrace a wide range of materials provided that the material is free of metal in its chemically uncombined form.
  • the substrate can be, for example, a plastic (flexible substrate), or glass substrate.
  • a smoothing layer is situated between the anode and the photoactive layer.
  • a preferred material for this smoothing layer comprises a film of 3,4-polyethylenedioxythiophene (PEDOT), or 3,4-polyethylenedioxy- thiophene:polystyrene-sulfonate (PEDOT:PSS).
  • the photovoltaic cell comprises, as described for example, in US-B-6,933,436 a transparent glass carrier, onto which an electrode layer made of indium/tin oxide (ITO) is applied.
  • ITO indium/tin oxide
  • This electrode layer generally has a comparatively rough surface structure, so that it is covered with a smoothing layer made of a polymer, typically PEDOT, which is made electrically conductive through doping.
  • the photoactive layer is made of two components, has a layer thickness of, for example, 100 nm to a few ⁇ depending on the application method, and is applied onto this smoothing layer.
  • the photoactive layer is made of a compound of the formula I, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-
  • Blodgett (“LB") method, the ink jet printing method and the dripping method.
  • a squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer.
  • a dispersion agent such as chlorobenzene is preferably used as a solvent.
  • the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.
  • the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, ⁇ , ⁇ -dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
  • an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, ⁇ , ⁇ -dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
  • this transition layer is made of an alkali halogenide, namely a lithium fluoride, which is vapor deposited in a vacuum of 2 ⁇ 10- 6 torr at a rate of 0.2 nm/minute.
  • ITO is used as a hole-collecting electrode
  • aluminum which is vapor deposited onto the electrically insulating transition layer, is used as an electron-collecting electrode.
  • the electric insulation properties of the transition layer obviously prevent influences which hinder the crossing of the charge carrier from being effective, particularly in the transition region from the photoactive layer to the transition layer.
  • one or more of the layers may be treated with plasma prior to depositing the next layer. It is particularly advantageous that prior to the deposition of the PEDOT SS layer the anode material is subjected to a mild plasma treatment.
  • PEDOT SS As an alternative to PEDOT SS a crosslinkable hole-transport material based on triaryla- mines as referenced in Macromol. Rapid Commun. 20, 224-228 (1999) can be used.
  • the layer can also include an electron acceptor to improve electron transport.
  • an electron acceptor to improve electron transport.
  • the electron acceptor material is soluble in one or more organic solvents.
  • the electron acceptor material is present in the range fo 0.5 to 20 % by weight of the triarylamine material.
  • the photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum.
  • Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
  • a so called 'tandem solar cell' comprise in this order:
  • a transition layer such as an alkali halogenide, especially lithium fluoride
  • a photoactive layer such as an alkali halogenide, especially lithium fluoride
  • a middle electrode such as Au, Al, ZnO, T1O2 etc.
  • a transition layer such as an alkali halogenide, especially lithium fluoride
  • a photoactive layer optionally a smoothing layer
  • the PV device can also be processed on a fiber as described, for example, in
  • the materials or films comprising the compounds of the formula I, especially I la, lib and III can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.
  • [1143585-17-4] a) 4g of compound [1143585-17-4] are dissolved in 100ml chloroform and the mixture is cooled to -5°C. Then 20mg perchloric acid (70%) are added, followed by the addition of 630mg of N-bromo-succinic acid (NBS). The mixture is stirred for 1 hour at -5°C, and then washed with water. The organic phase is dried and evaporated. The compound of formula 27 is obtained after chromatography over silica gel.
  • BGBC Bottom Gate Bottom Contact
  • FETs Field-Effect Transistors
  • the substrates are prepared by standard cleaning in acetone and i-propanol followed by oxygen plasma treatment for 30 minutes and are then transferred in a glove box and treated with octyltrichlorosilane (OTS) to achieve a hydrophobic monolayer.
  • OTS octyltrichlorosilane
  • oligomer film The semiconductor is dissolved in a proper solvent (see Table 1) in a concentration of 0.75 % by weight at elevated temperature and is spin-coated at 1500 rounds per minute (rpm) for 60 seconds onto the silicon dioxide/silicon substrate.
  • a proper solvent see Table 1
  • oligomer/polymer film The oligomer and polymer are separately dissolved in dry toluene (0.75 % by weight) at 80°C for 4h, then mixed to achieve the desired ratio and spin-coated at 1500 rpm for 60 seconds onto the silicon dioxide/silicon substrate.
  • PET substrates with lithographically patterned gold contacts (50 nm) covered with a photoresist are used as substrates.
  • the substrates are prepared by cleaning in acetone and eth- anol and dried at 60°C for 30 min.
  • the oligomer and polymer are separately dissolved in dry toluene (0.75 wt%) at 80°C for 4 h and then mixed to achieve the desired ratio, filtered through a 0.45 ⁇ filter, spin-coated to achieve a 50 nm semiconductor layer and dried at 80°C for 30 seconds.
  • the solar cell has the following structure: Al electrode/LiF layer/organic layer, comprising a compound of the present invention and [60]PCBM /[poly(3,4-ethylenedioxy-thiophene)
  • PEDOT poly(styrenesulfonic acid)
  • PSS poly(styrenesulfonic acid)
  • ITO electrode/glass substrate The solar cells are made by spin coating a layer of the PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1 :1 mixture of the compound of the present invention (1 % by weight) : [60]PCBM (a substituted Ceo fullerene) is spin coated from ortho-dichlorobenzene (DCB). (organic layer). LiF and Al are sublimed under high vacuum through a shadow- mask.
  • PCBM a substituted Ceo fullerene
  • the solar cell is measured under Aescusoft solar light simulator with halogen light source.
  • the current is estimated under AM 1.5 conditions using the External Quantum Efficiency (EQE) graph.
  • oligomer A-4 up to 10%

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Abstract

The present invention relates to compositions, comprising (a) a compound of the formula (I), and (b) a polymeric material, to specific oligomers of the formula I, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the compositions, or oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

Description

Diketopyrrolopyrrole Oligomers and Compositions, comprising Diketopyrrolopyrrole Oligomers
The present invention relates to compositions, comprising (a) a compound of the formula I, and (b) a polymeric material, to specific oligomers of the formula I, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and pho- todiodes, or in a device containing a diode and/or an organic field effect transistor. High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the compositions, or oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
Examples of DPP polymers and their synthesis are, for example, described in
US6451459B1 , WO05/049695, WO2008/000664, EP2034537A2, EP2075274A1 ,
WO2010/049321 , WO2010/049323, WO2010/108873, WO2010/1 15767, WO2010/136353, WO2010/136352 and WO201 1/144566:
WO05/049695 discloses diketopyrrolopyrrole (DPP) based polymers and their use in PLEDs, organic integrated circuits (O-ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (O-SCs), or organic laser diodes, but fails to disclose DPP oligomers.
Figure imgf000002_0001
EP2034537A2 discloses polymers of formula , wherein each R is independently selected from hydrogen, an optionally substituted hydrocarbon, and a hetero-containing group; each Ar is independently selected from optionally substituted aryl and heteroaryl groups; each M is an optional, conjugated moiety; a represents a number that is at least 1 ; b represents a number from 0 to 20; and n represents a number that is at least 1 , but fails to disclose DPP oligomers.
M. Smet et al., Tetrahedron Letters 42 (2001) 6257-6530 describes oligomers, which are prepared by a stepwise sequence of suzuki couplings using brominated 1 ,4-dioxo-3,6- diphenylpyrrolo[3,4c]pyrrole (DPP derivatives) and 1 ,4-dibromo-2,5-di-n-hexylbenzene as the monomers. The resulting oligomers contained three, five and seven DPP units, respectively.
Matthias Horn et al., Eur. Polymer J. 38 (2002) 2197-2205 describes the synthesis and characterisation of thermomesogenic polysiloxanes with 2,5-dihydropyrrolo[3,4-c]pyrrole units in the main chain.
Figure imgf000003_0001
WO2003048268 relates to an organic electroluminescent device comprising a perylene uch as, for example,
Figure imgf000003_0002
WO06/061343 discloses fluorescent diketopyrrolopyrroles of the formula
Figure imgf000003_0003
wherein R1 and R2 may be the same or different and are selected from a Ci-C2salkyl group, an allyl group, which can be substituted one to three times with Ci-C3alkyl, a cycloalkyl group, which can optionally be substituted one to three times with d-Csalkyl and/or Ci- Cealkoxy, a cycloalkyl group, which is condensed one or two times by phenyl which can be substituted one to three times with Ci-C4-alkyl, halogen, nitro, or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, a heterocyclic group, haloalkyl, haloalkenyl, haloal- kynyl, a heterocyclic group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, aryl, heteroaryl, or -CR3R4-(CH2)m-A3 wherein R3 and R4 independently from each other stand for hydrogen or Ci-C4alkyl, or phenyl which can be substituted one to three times with Ci-C3alkyl, A3 stands for aryl, or heteroaryl, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with d-Csalkyl and/or d-Csalkoxy, and m stands for 0, 1 , 2, 3 or 4,
A4 and A5 independently of each other stands for
Figure imgf000003_0004
Figure imgf000004_0001
wherein R101 to R123 may be the same or different and are selected from hydrogen, Ci- C25alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR27R28, wherein R27 and R28 are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group, or at least two adjacent substituents R115 to R121 form an aromatic, heteroaromatic or aliphatic fused ring system,
R124 and R125 may be the same or different and are selected from Ci-Cisalkyl; Ci-Cisalkoxy, A3, C6-Ci8aryl; C7-Cisaralkyl; or R124 and R125 together form a ring especially a five-, six- or seven-membered ring, which can optionally be substituted by Ci-CsalkyI, or which can optionally be condensed one or two times by phenyl which can be substituted one to three times with d-Cs-alkyl, d-Cs-alkoxy, halogen and cyano; or
Figure imgf000004_0002
wherein R131 to R152 may be the same or different and are selected from hydrogen, Ci- C25alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ether group, an aryl thioether group, aryl, a heterocyclic group, halogen, haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, a group NR27R28, wherein R27 and R28 are as defined above, a nitro group, a silyl group, a siloxanyl group, a substituted or unsubstituted vinyl group,
R153 is a hydrogen atom, a Ci-C25alkyl group, which might be interrupted by -O-, a cycloal- kyl group, an aralkyl group, an aryl group, or a heterocyclic group, and
A6 is cycloalkyl, arylene, or heteroarylene, which are optionally substituted one to three times with d-Cs-alkyl, or d-Cs-alkoxy; and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, in solid dye lasers, EL lasers and electroluminescent devices.
The following compounds are explicitly mentioned in WO06/061343:
Figure imgf000005_0001
JP2006310538 discloses fluorescent diketopyrrolopyrroles of the formula
Figure imgf000006_0001
wherein Ar6 may be aryl, or heteroryl, and its use in light emitting elements.
Figure imgf000006_0002
the prepn. of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color12 filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, dye lasers and electroluminescent devices.
US2010/0326525 relates to optoelectronic devices, such as photovoltaic devices, comprising:
a) a first hole-collecting electrode;
b) an optional hole-transporting layer;
c) a layer comprising a mixture of an electron donor material and an electron acceptor material; and
d) a second electron-collecting electrode,
wherein the electron donor material comprises a compound of Formula (I): I)
Figure imgf000006_0003
wherein X is oxygen or sulfur Ai and A2 are independently selected from substituted and unsubstituted aryl or heteroaryl groups, wherein each individual Ai within the (Ai)m moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group, and each individual A2 within the (A2)n moiety can be independently selected from a substituted or unsubstituted aryl or heteroaryl group;
Bi is independently selected from substituted and unsubstituted aryl or heteroaryl groups; m is independently selected from 1 , 2, 3, 4, 5, 6, 7, 8, or 9;
n is independently selected from 1 , 2, 3, 4, 5, 6, 7, 8, or 9;
p is independently selected from 0 or 1 ;
Ei and E2 are independently selected from a nonentity, H, or a substituted or unsubstituted aryl or heteroaryl group or a C1-C12 alkyl group; and
Ri, R2, R3, and R4 are independently selected from H, C1-C12 alkyl, and -C(-0)-0-Ci-Ci2 alkyl.
The following dimeric DPP compound is explicitly disclosed:
Figure imgf000007_0001
Y. Xu et al., Synthetic
containing oligomers:
Figure imgf000007_0002
and
Figure imgf000007_0003
The monomers were copolymerized with benzothiadiazole, dioctyloxybenzene and fluorene through fluoride-mediated Suzuki polymerization to give copolymers with low content of DPP (1 mol%). The copolymers were used as the emitting layers in the light-emitting diodes.
R. A. J. Janssen et al., Macromol. Chem. Phys. 2011 , 212, 515-520 disclose diketo- pyrrolopyrrole-based oligomers of formula
Figure imgf000008_0001
(R = 2-hexyldecyl; n = 1 to 4), which of mono- and
Figure imgf000008_0002
). Monodisperse oligomers were obtained from the resulting mixture by separation of the oligomers using recycling GPC. Their optical and electrochemical properties were investigated. For all properties, measured in solution, no clear change was observed upon increase of the chain length, leading to the conclusion that conjugation in this system is only very limited.
Stephen Loser et al., J. Am. Chem. Soc. 133 (2011) 8142-8145 (DOI: 10.1021/ja202791 n Publication Date (Web): 05 May 2011 ) describes the synthesis, characterization, and first implementation of a naphtho[2,3-b:6,7-b']dithiophene (NDT)-based donor molecule in high ly efficient organic photovoltaics (OPVs). When NDT(TDPP)2 (TDPP = thiophene-capped d
Figure imgf000008_0003
(R = 2-ethylhexyl)) is combined with the electron acceptor PC61 BM, a power conversion efficiency (PCE) of 4.06±0.06% is achieved.
T.-Q. Nguyen et al., Applied Physics Letters 93 (2008) 163306 reports the incoporation of a soluble oligothiophene with a diketopyrrolopyrrole core into a polymer(poly(3- hexylthiophen)/fullerene bulk heteroju notion (BHJ) solar cell. R. A. J. Janssen et al., Ma 31 (2010) 1554-1559 disclose small
Figure imgf000009_0001
and
Figure imgf000009_0002
). The compounds are tested as electron acceptors in combination with poly(3-hexylthiophene) (P3HT) as the donor material. Working photovoltaic devices are obtained that show a photoresponse in the wavelength region where the DPP molecules absorb. The best device shows a power conversion efficiency of 0.31 % in simulated solar light, with a photon-to-electron conversion efficiency of ca. 10% up to 700 nm.
It is the object of the present invention to provide compounds, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
It has surprisingly been found that certain dimeric, trimeric and quatermeric diketo- pyrrolopyrrol derivatives can be used alone, or in admixture with polymers as organic semiconductors. Alone, or in admixture with polymers, they are especially suitable as semiconductors for the application in field effect transistors. Said derivatives have excellent solubility in non-halogenated organic solvents (allowing easy handling).
Accordingly, the present invention relates to compositions, comprising
Figure imgf000009_0003
(I), and
(b) a polymeric material, wherein
p is 0, or 1 , q is 0, or 1 ,
A1 and A2 are independently of each other a group of formula
-Ar- -Ar- -Ar R3
J b
, or have the meaning of R5, A3, A4 and A5 are independently of each other a group of formula
-Ar- -Ar- -Ar- -Ar- a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
k is 0, 1 , or 2; I is 1 , 2, or 3; r is 0, or 1 ; z is 0, 1 or 2;
R1, R2, R1', R2', R1 ", R2', R1* and R2* may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, C6-d4aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR39-, -COO-, -CO- or -OCO-,
a C2-Ciooalkenyl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C24aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR39-, -COO-, -CO- or -OCO-,
a C3-Ciooalkinyl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C24aryl, d- C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR39-, -COO-, -CO- or -OCO-,
a C3-Ci2cycloalkyl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C24aryl, d- doheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -NR39-, -COO-, -CO- or -OCO-,
a C6-C24aryl group which can optionally be substituted one or more times with d-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-C24sryl, d- doheteroaryl, s silyl group or s siloxsnyl group,
a d-doheteroaryl group which can optionally be substituted one or more times with Ci- dalkyl, d-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , C6-d4sryl, d- doheterosryl, s silyl group or s siloxsnyl group,
-CO-Ci-Ci8alkyl, -CO-C5-Ci2cycloalkyl, -COO-Ci-Cisalkyl;
R3 is hydrogen, halogen, cyano, d-dsalkyl, d-dsalkyl which is substituted one or more
Figure imgf000010_0001
times by E and/or interrupted one or more times by D, , COO-Ci-Cisalkyl, d-
Ci2cycloalkyl, C3-Ci2cycloalkyl, which is substituted by G, d-dsalkenyl, d-dsalkynyl, Ci- dsthioalkoxy, Ci-Cisalkoxy, Ci-Cisalkoxy which is substituted by E and/or interrupted by D, d-d ning of R5, or R6;
R5 is
Figure imgf000010_0002
Figure imgf000011_0001
Ar1, Ar2, Ar3, Ar4, Ar5, Ar6 and Ar7 are independently of each other a bivalent group of formula
Figure imgf000011_0002
Figure imgf000012_0001
or ;
R10 and R11 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C25arylalkyl, Ci-Cisalkanoyl,
R12 and R13 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C6-C24aryl, C2-C2oheteroaryl, or R12 and R13 together represent oxo,
Figure imgf000013_0001
r form a five or six membered ring, which is unsubstituted or substituted by Ci- C-iealkyl and/or Ci-Cisalkoxy;
R14 and R15 are independently of each other hydrogen, Ci-Cisalkyl, C6-C24aryl, C2-
C2oheteroaryl, -CN or COOR50;
R16 and R17 are independently of each other hydrogen, halogen, Ci-C2salkyl, Ci-C2salkoxy,
— x
C7-C25arylalkyl, or ^ , Rx is a Ci-Csalkyl group, or a tri(Ci-Cealkyl)silyl group,
R18 and R19 are independently of each other hydrogen, Ci-Cisalkyl, C7-C2sarylalkyl, or a phenyl group, which optionally can be substituted one to three times with Ci-Csalkyl and/or C-i-Cealkoxy,
R20 and R21 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2-
C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci-Cisalkoxy, Ce- C24aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl, or R20 and R21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (het- ero)aromatic residue and which may both have up to 4 carbon atoms,
R30 to R38 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2- C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci-Cisalkoxy, C6- C24aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl,
R40 and R41 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2- C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci-Cisalkoxy, C6- C24aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl,
R50 is Ci-C25alkyl, Ci-C2shaloalkyl, C7-C2sarylalkyl, C6-C24aryl or C2-C2oheteroaryl;
R60 to R68 represent independently of each other H, halogen, cyano, Ci-C2salkyl, Ci- C25alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C3- Ci2cycloalkyl, C3-Ci2cycloalkyl, which is substituted by G, C2-Cisalkenyl, C2-Cisalkynyl, Ci- Cisalkoxy, Ci-Cisalkoxy which is substituted by E and/or interrupted by D, C7-C2saralkyl, or C7-C25aralkyl, which is substituted by G,
D is -CO-, -COO-, -S-, -0-, -NR39-, or -C(=0)NR39-,
E is Ci-C8thioalkoxy, COO-Ci-Ci8alkyl, Ci-C8alkoxy, CN, -NR39R39', -CONR39R39', or halo- gen,
G is E, or Ci-Cisalkyl, and
R39 and R39' are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7- C25arylalkyl, or Ci-Cisalkanoyl. If the polymeric material is a dik PP) polymer it comprises at least 5
DPP repeating units of formula
Figure imgf000014_0001
, wherein each R101 and R102 have meaning of R1. The quotient of the weight average molecular weight of the polymer and the molecular weight of the repeating unit of the polymer is at least 5. The quotient is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
The compositions of the present invention may provide improved charge mobility in elec- tronic devices as well as improved stability and integrity of the organic semiconductor layer.
In addition, an oligomer may be used to extend the effective absorption breath of a polymer bulk heterojunction solar cell. Phase seperation may be controlled and the device morphology may be optimized.
Preferably a is 1 or 2; b is 0, or 1 ; c is 0, or 1 , more preferably a is 1 , b is 1 and c is 1 , even more preferably a is 1 , b is 1 and c is 0, most preferably a is 1 , b and c are 0.
Preferably k is 0, or 1 ; I is 1 or 2; r is 0, or 1 ; z is 0 or 1. Preferably k+l+r+z is an integer smaller than 4, more preferably k+l+r+z is 1 or 3.
Preferably R1, R2, R1', R2', R1", R2", R * and R2* may be the same or different and are selected from hydrogen, a Ci-C36alkyl group which can optionally be substituted one or more times with Ci-Csalkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2- C2oheteroaryl, and/or can optionally be interrupted by -0-, -S-, -COO- or -OCO-, a C2-C36alkenyl group which can optionally be substituted one or more times with Ci- Cealkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-, -COO- or -OCO-,
a C3-C36alkinyl group which can optionally be substituted one or more times with Ci- CsalkyI, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-, -COO- or -OCO-,
a C3-Ci2cycloalkyl group which can optionally be substituted one or more times with Ci- Cealkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2-C2oheteroaryl, and/or can optionally be interrupted by -O-, -S-, -COO- or -OCO-,
a C6-C24aryl group which can optionally be substituted one or more times with Ci-Csalkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2-C2oheteroaryl,
a C2-C2oheteroaryl group which can optionally be substituted one or more times with Ci- Cealkyl, Ci-Csalkoxy, halogen, C5-Ci2cycloalkyl, cyano, C6-C24aryl, C2-C2oheteroaryl and -CO-Ci-Ci8alkyl, -CO-C5-Ci2cycloalkyl, -COO-Ci-Ci8alkyl. More preferably R1, R2, R1', R2', R1", R2', R1* and R2* may be the same or different and are selected from hydrogen, a Ci-C36alkyl group, a C2-C36alkenyl group, a C3-C36alkinyl group which can optionally be interrupted one or more times by -0-, -S- or COO and a phenyl group which can optionally be substituted one or more times by d-Csalkyl, d-Csalkoxy, halogen or cyano. Even more preferably R1, R2, R1 ', R2', R1", R2", R1* and R2* may be the same or different and are selected from hydrogen and a Ci-C36alkyl group. Most preferred R1, R2, R1', R2', R1 ", R2", R1* and R2* may be the same or different and are selected from a Cg-C36alkyl group. In one particularly preferred embodiment of the present invention R1, R2, R1 ', R2', R1 ", R2", R1* and R2* may be the same or different and are selected from a Ci3-C24alkyl group.
Preferably R is R2, R ' is R2', R " is R2" and R * is R2*. Most preferably R , R2, R ', R2', R " R2", R1* and R2* have all the same meaning.
In a preferred embodiment of the present invention R1, R2, R1', R2', R1", R2", R1* and R2* are Ci3-C24alkyl, especially Ci6-C24alkyl.
Figure imgf000015_0001
Advantageously, the groups R1 ' and R2' can be represented by formula
wherein ml = n1 + 2 and ml + n1 < 24. Chiral side chains, such as R1' and R2', can either be homochiral, or racemic, which can influence the morphology of the polymers.
R14
Preferably R3 is hydrogen, halogen, cyano, C1-C25 alkyl,
Ci-Ci8thioalkoxy, Ci-Cisalkoxy, or is R5 or R6;
Figure imgf000015_0002
More preferably R3 is hydrogen, halogen, cyano, C1-C25 alkyl, , Ci-
Ciethioalkoxy, Ci-Cisalkoxy, or is R5 or R6. Even more preferably R3 is hydrogen, cyano, Ci-C25alkyl, Ci-Cisalkoxy, or is R5, or R6. Most preferably R3 is hydrogen.
of formula
, more preferably a group of formula
Figure imgf000016_0001
Figure imgf000016_0002
, more preferably a group of formula
Compounds of formula I are preferred, wherein the (hetero)arylgroups Ar1 and Ar4 to Ar7, which are directly linked to the diketopyrrolopyrrole basic structure, are different from a six- membered ring. Preferably Ar1, Ar2 and Ar3 are independently of each other a bivalent group of formula
Figure imgf000016_0003
. especially
Figure imgf000016_0004
Figure imgf000017_0001
ore preferably Ar1, Ar2 and Ar3 are independently ent group of formu-
Figure imgf000017_0002
Most preferably Ar1, Ar2 and Ar3 are independently of each other a bivalent group of formu- la
Figure imgf000017_0003
Ar4, Ar5, Ar6 and Ar7 are preferably independently of each other a bivalent group of formula
Figure imgf000018_0001
Figure imgf000019_0001
r5,
Figure imgf000019_0002
Ar4, Ar5,
Figure imgf000019_0003
(R 8)(R19)-, -C(R 2)(R13)-,
X is is -S-, -NR -, -Si(R 8)(R19)-
Figure imgf000020_0001
33
R3^ R
Most preferably X is is -NR™-, -C(R 2)(R13). or
Preferably R10 and R11 are independently of each other Ci-Cisalkyl, or Ci-Cisalkanoyl. Most preferably R10 and R11 are independently of each other Ci-Cisalkyl.
Preferably R12 and R13 dently of each other hydrogen, Ci-Cisalkyl, or R12 and
R13 together represent
Figure imgf000020_0002
More preferably R12 and R13 are independently of each other hydrogen, or Ci-Cisalkyl. Most preferably R12 and R13 are independently of each other Ci-Cisalkyl.
Preferably R14 and R15 are independently of each other hydrogen, Ci-Cisalkyl, C6-C24aryl, C2-C2oheteroaryl, -CN. or COOR50. More preferably R14 and R15 are independently of each other hydrogen, Ci-Cisalkyl, -CN or COOR50. Most preferably R14 and R15 are independently of each other hydrogen, -CN or COOR50; especially -CN.
Preferably R16 and R17 are independently of each other hydrogen, Ci-C2salkyl, Ci-
C25alkoxy or -R , Rx is a C-i-Cealkyl group, or a tri(Ci-Cealkyl)silyl group. More preferably R16 and R17 are independently of each other Ci-C2salkyl or ^^Rx , wherein
Rx is a tri(Ci-C8alkyl)silyl group. Most preferably R16 and R17 are independently of each other , wherein Rx is a tri(Ci-C8alkyl)silyl group,
Preferably R18 and R19 are independently of each other Ci-Cisalkyl, a phenyl group, which optionally can be substituted one to three times with d-Csalkyl and/or d-Csalkoxy. Most preferably R18 and R19 are independently of each other Ci-Cisalkyl. Preferably R20 and R21 are independently of each other hydrogen, Ci-C25alkyl, C2-C2salkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci-Cisalkoxy, fluoro or R20 and R21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which may both have up to 4 carbon atoms. More preferably R20 and R21 are independently of each other hydrogen, Ci-C2salkyl, or cyano. Even more preferably R20 and R21 are independently of each other hydrogen, or Ci-C25alkyl. Most preferably R20 and R21 are hydrogen. Preferably R30 to R38 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci-Cisalkoxy, or fluoro. More preferably R30 to R38 are independently of each other hydrogen, Ci-C2salkyl, or Ci- Cisalkoxy. Most preferably R30 to R38 are independently of each other hydrogen, or Ci- C25alkyl; especially hydrogen.
Preferably R40 and R41 are independently of each other hydrogen, Ci-C2salkyl, or cyano. More preferably R40 and R41 are independently of each other hydrogen, or Ci-C2salkyl. Most preferably R40 and R41 are independently of each other Ci-C2salkyl, Preferably R50 is Ci-C25alkyl, C6-C24aryl or C2-C2oheteroaryl. Most preferably R50 is Ci- C25alkyl,
Preferably R60 to R68 represent independently of each other H, fluoro, cyano, Ci-C2salkyl, or Ci-C25alkyl which is substituted by E and/or interrupted by D, Ci-Cisalkoxy. More preferably R60 to R68 represent independently of each other H, fluoro, cyano, Ci-C2salkyl, or Ci- C25haloalkyl. Even more preferably R60 to R68 represent independently of each other H, cyano, or Ci-C2salkyl. Most preferably R60 to R68 represent hydrogen.
In an embodiment of the present invention, compounds of formula I are preferred, wherein R3, R20, R21 , Rso to R38 and R60 to R68 are hydrogen .
Preferably D is -COO-, -S-, -O- or -C(=0)NR39-. More preferably D is -S-, or -O-. Most preferably D is -0-. Preferably E is Ci-Csthioalkoxy, COO-Ci-Cisalkyl, Ci-Csalkoxy, CN or fluoro. More preferably E is Ci-Csalkoxy, CN, or fluoro. Even more preferably E is Ci- Cealkoxy, or fluoro. Most preferably E is Ci-Csalkoxy. G is E, or Ci-Ci8alkyl.
Preferably R39 and R39' are independently of each other Ci-Cisalkyl, Ci-Cishaloalkyl, or Ci- Ciealkanoyl. More preferably R39 and R39' are independently of each other Ci-Cisalkyl, or Ci-Cishaloalkyl. Most preferably R39 and R39' are independently of each other Ci-Cisalkyl.
Examples of compounds of the formula I are compounds A-1 to A-27 and B-1. Reference is made to claim 9.
The polymeric material b) is preferably selected from nonconductive or semiconductive material, more preferably semiconductive material, such as, for example,
Figure imgf000022_0001
(η' is usually in the range of 10 to 1000, especially 10 to 200; very especially 10 to 150) and polymers containing diketopyrrolopyrrole (DPP) repeating units, which are, for example, described in US6451459, WO2005/049695, WO2008/000664, WO2009/047104, WO2010/049321 , WO2010/049323, WO2010/108873, WO2010/115767, WO2010/136353, WO201 1/144566, European patent application no. 11 192316.5,
EP2033983 and EP2034537. The polymeric material is preferably p-type semiconductive.
In a preferred embodiment of the present invention the polymeric material is a polymer comprisi , especially a polymer represented by
formula:
Figure imgf000022_0002
(VII), wherein each R101 and R102 have the meaning of R1; each A6 and A7 is independently selected from optionally substituted aryl and heteroaryl groups; each M is an optional, conjugated moiety; s represents a number from 1 to 4; t represents a number from 1 to 4; u represents a number that is at least 1 , especially 1 ; v represents a number from 0 to 20, especially 1 to 5; and n repre- sents a number that is at least 5. A6, A7 and M may independently of each other have the meaning of Ar1. The same preferences apply for A6, A7 and M as for Ar1.
In said embodiment polymers of the formula
Figure imgf000022_0003
are preferred, wherein v is an integer of 1 to 5, especially 1 ; t is an integer of 1 to 3, especially 1 ;
s is an integer of 1 to 3, especially 1 ; the sum of v, t and s is equal, or smaller than 7,
A6, A7 and M are independently of each other a group of formula
Figure imgf000022_0004
, or
Figure imgf000022_0005
, and R101 and R102 are the same and are a Ci-C36alkyl group, n is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
T nits:
Figure imgf000022_0006
and , respectively. Ri Ri' Ri" anc| Ri* may be the same or different. R2, R2', R2', or R2* may be the same or different.
If the polymeric material is a DPP polymer it comprises at least 5, especially at least 10
DPP repeating units of formula
Figure imgf000023_0001
, wherein each R101 and R102 have the meaning of R1.
The quotient of the weight average molecular weight of the DPP polymer and the molecular weight of the repeating unit of the polymer is at least 5. The quotient is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150.
Examples of preferred polymers are shown below:
Figure imgf000023_0002
(j is an integer from 0 to 3, especially 1 , or 2, very especially 1);
Figure imgf000023_0003
is usually in the range of 5 to 1000, especially 10 to 200, very especially 10 to 150 and R101 and R102 are a Ci-C38alkyl group). n a preferred n the composition comprises a compound
Figure imgf000024_0001
wherein A1, A2, A3, A4, A5, R1, R2, R1', R2', R1", R2', R * and R2* are as defined above.
The weight% (w%ong) of one, or a mixture of more than one oligomer of formula (I) in the composition of the present invention is 0.1 % to 99.9%. The weight% (w%p0i) of one, or a mixture of more than one polymers in the composition of the present invention is 0.1 % to 99.9%. The sum of w%oiig and w%p0i adds up to 100.
Examples of compositions according to the present invention are mixtures of compounds in Example 1 of WO2010/049321 :
Figure imgf000024_0002
(Mw = 39'500, Polydispersity = 2.2
(measured by HT-GPC)). In addition, the present invention is also directed to a formulation, comprising
(a) a compound of formula I as defined above,
(b) a polymeric material as defined above, and
5 (c) a solvent, or solvent mixture.
The formulation can be used for the production of the organic layer, especially an organic semiconducting (OSC) layer. The OSC layer can be used in an organic semiconductor device.
10
The formulation and the OSC layer according to the present invention may be prepared by a process which comprises:
(i) first mixing the compound(s) of formula I and the polymeric material(s) . Preferably the mixing comprises mixing the components together in a solvent or solvent mixture,
15 (ii) applying the solvent(s) containing the compound(s) of formula I and the polymeric materials) to a substrate; and optionally evaporating the solvent(s) to form a solid OSC layer according to the present invention, and
(iii) optionally removing the solid OSC layer from the substrate or the substrate from the solid layer.
0
In step (i) the solvent may be a single solvent, or the compound(s) of formula I and polymeric materials(s) may each be dissolved in a separate solvent followed by mixing the two resultant solutions. 5 The polymeric materials(s) may be dissolved together with the compound(s) of formula I in a suitable solvent, and the solution deposited for example by dipping, spraying, painting or printing it on a substrate to form a liquid layer and then removing the solvent to leave a solid layer. It will be appreciated that solvents are chosen which are able to dissolve both the compound(s) of formula I and polymeric materials(s), and which upon evaporation from 0 the solution blend give a coherent defect free layer.
Examples of suitable and preferred organic solvents include, without limitation, dichloro- methane, trichloromethane, monochlorobenzene, o- dichlorobenzene, 1 ,2,4- trichlorbenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p- 5 xylene, 1 ,4-dioxane, acetone, methylethylketone, 1 ,2-dichloroethane, 1 ,1 ,1-trichloroethane, 1 ,1 ,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, dimethyla- cetamide, dimethylsulfoxide, tetralin, decalin, indane, mesitylene, 1-methylnaphthalene and/or mixtures thereof. 0 It is desirable to generate small structures in modern microelectronics to reduce cost (more devices/unit area), and power consumption. Patterning of the layer of the invention may be carried out by photolithography, electron beam lithography or laser patterning.
Liquid coating of organic electronic devices such as field effect transistors is more desirable 5 than vacuum deposition techniques. The formulations of the present invention enable the use of a number of liquid coating techniques. The organic semiconductor layer may be incorporated into the final device structure by, for example, and without limitation, dip coating, spin coating, ink jet printing, letter-press printing, screen printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, flexographic printing, web printing, spray coating, slot-die coating, brush coating or pad printing.
The OSC formulation according to the present invention can additionally comprise one or more further components like for example surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive or non-reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles, furthermore, especially in case crosslinkable binders are used, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents or co- reacting monomers.
Figure imgf000026_0001
wherein R103 = 2-hexyldecyl and y is 3, or 4, are excluded.
The compound of the formula II is more preferably a compound of the formula
Figure imgf000027_0001
(lib), wherein Ai
A2, A3, A4, A5, R1, R2, Ri', R2', Ri", R2", Ri* and R2* are as defined above. Compounds of the formula Ma are preferred. The preferences for A1, A2, A3, A4, A5, R1, R2, R1 ', R2', R1 ', R2', R1* and R2* are the same as specified above for the compounds of formula I.
In a further preferred embodiment the present invention is directed to compounds of the
formula
Figure imgf000027_0002
(III), wherein
A1 and A2 are independently of each other a group of formula
+Ar1- -Ar^- -ArJ R3
Figure imgf000027_0003
-Ar- -Ar- -Ar- -Ar-
A3 is a group of formula
a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
k is 0, 1 , or 2; I is 1 , 2, or 3; r is 0, or 1 ; z is 0, 1 or 2;
R1, R2, R1', R2', R3 and R5 are as defined above;
Ar1, Ar2 and Ar3 are independently of each other a bivalent group of formula
Figure imgf000027_0004
Figure imgf000028_0001
Ar4, Ar5, Ar6 and Ar7 are independently of each other a bivalent group of formula
Figure imgf000029_0001
Figure imgf000030_0001
, wherein X, R10, R 2, R13, RM RIS_ RI6_ R20, R2i to R37, R40 and R41 are as defined for compound (I), with the proviso that Ar1, Ar4, Ar5, Ar7 does not represent a six membered ring, which is attached directly to the diketo- pyrrolopyrrole moiety, and that
Figure imgf000030_0002
(R1°4 is 2-hexyldecyl), and
Figure imgf000030_0003
(R105 is 2-ethylhexyl) are excluded. Compounds of formula III are preferred, wherein the (hetero)arylgroups Ar1 and Ar4 to Ar7, which are directly linked to the diketopyrrolopyrrole basic structure, are different from a six- membered ring.
Compounds of formula III are preferred, wherein R3, R2o, R21, R3o t0 R38 and R60 to R68 are hydrogen .
Compounds of formula III are preferred, where R1, R2, R1', R2', R1 ', R2', R * and R2* are C13- C24alkyl, especially Ci6-C24alkyl.
Preferably a is 1 or 2; b is 0, or 1 ; c is 0, or 1 , more preferably a is 1 , b is 1 and c is 1 , even more preferably a is 1 , b is 1 and c is 0, most preferably a is 1 , b and c are 0. Preferably k is 0, or 1 ; I is 1 or 2; r is 0, or 1 ; z is 0 or 1. Preferably k+l+r+z is an integer smaller than 4, more preferably k+l+r+z is 1 or 3.
In one preferred embodiment of the present invention at least one of Ar1, Ar5 or Ar7 in
compound (III) is different from
Figure imgf000031_0001
. More preferably Ar1 is different from
. Even more preferably Ar5
Figure imgf000031_0002
Ar7 are different from . Most preferably Ar1, Ar5 and Ar7 in compound (III)
are different from
Figure imgf000031_0003
. R20 and R21 have the meaning as described for compound (I). The preferences for a, b, c, k, I, r, z, R3, R5, R6, R1, R2, R1* and R2* are, in principal, the same as specified above for the compounds of formula I.
In a preferred embodiment the present invention is directed to compounds of formula III, wherein R1, R2, R1* and R2* may be the same or different and are selected from a C13- C24alkyl group.
Preferably Ar1, Ar2, Ar3 are independently of each other a bivalent group of formula
Figure imgf000031_0004
-
Figure imgf000032_0001
Ar1, Ar2 and Ar3 are independently of each other a bivalent group of formula
Figure imgf000032_0002
Figure imgf000033_0001
More preferably Ar4, Ar5, Ar6 and Ar7 are independently of each other a bivalent rou of formula
Figure imgf000033_0002
Figure imgf000033_0003
especially , or
Figure imgf000034_0001
Ar7 are independently of each other a bivalent group of formula
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0003
. The preferences for X, R10, R11 R12, R13, R1 , R15. R16. R17. R18. R19_ R20i R21 _ R30 R38, R 0_ R41 _ R60 t0 R68, D, E and G are the same as specified above for the compounds of formula I.
If a moiety selected from Ar1, Ar5 or Ar7 is linked via a single bond to the DPP basis skeleton, preferably the substituents in ortho position to this linking bond are hydrogen.
In a preferred embodiment R3 is R5. In another preferred embodiment A1 and A2 have the meaning of R5.
In another preferred embodiment the compound of formula III is a compound of formula
Figure imgf000035_0004
wherein A1 and A2 are as defined above, g 1 to 4, especially 1 ; R1, R2, R1*
Figure imgf000035_0005
and R2* are a Ci-C3salkyl group and Ar5 is (h is 1 , 2, or 3, especially 1 , or 3, very especially 1),
Figure imgf000036_0001
, wherein X, R«>, R12. RI3. RIB. RI7. R2O, 21 ANC| RSO t0
R35 are as defined above.
the present invention is directed to compounds of formula
Figure imgf000036_0002
(lllc), wherein Ar5, A1 and A2 are as defined above, R1 ,
R2, R1* and R2* are a Ci-C38alkyl group, especially a Ci3-C24alkyl group, and Ar4 and Ar6 are independently of each other
Figure imgf000036_0003
Figure imgf000037_0001
, X, R10, R12, R13. R16. R17. R20, R21 anc| R30 R35 3ΓΘ aS defined above.
Examples of compounds of the formula III are compounds A-1 to A-27. Reference is made to claim 9. Among the compounds A-1 to A-27 compounds A-1 , A-4, A-10, A-11 , A-13, A- 14, A-22 to A-27 are preferred.
A process for the preparation of compounds of formula
Figure imgf000037_0002
wherein R2 is R1*, comprises
(a) reacting (in the presence of a strong base) 2 moles of a compound of formula
Figure imgf000037_0003
(XV) and (XV') (R200 and R200' are independently of each other a Ci-Csalkyl group, or a benzyl group) with 1 mole of a di-nitrile compound of the for-
(b) and then alkylation of the compound of formula
Figure imgf000038_0001
tained in step (a) with a compound R2-X16 (X16 is halogen, especially J, or Br) under basic conditions (preferably K2CO3) in a dry solvent such as e.g. dimethylformamide, wherein A1, A2, A3, R1, R2, Ri* and R2* are as defined above.
The oligomers of formula (II) and (III) are present in pure form. They are not present in form of a mixture with further oligomers and/or polymers.
A process for the preparation of compounds of the formula
Figure imgf000038_0002
(lib) (R1 = R2 = R1* = R2*), comprises
(a) reacting (in the presence of a strong base) 2 mole of a disuccinate with 1 mole of a ni-
trile of the formula
Figure imgf000038_0003
and 2 mole of a nitrile of the formula
A ; N
Figure imgf000038_0004
(b) reacting the compound of formula
(IX") obtained in step a) with a bromide of the formula R1-X16 (X16 is halogen, especially Br, or I) in the presence of a suitable base, like potassium carbonate, in a suitable solvent, like N-methyl-pyrrolidone, R1, R1 ', R2', A1, A3 and A4 are as defined above.
The disuccinates to be used in the process according to the invention include dialkyi, diaryl or monoalkyl-monoaryl succinates. The dialkyi and diaryl succinates may also be asymmetrical. However, it is preferred to use symmetrical disuccinates, most preferably symmetrical dialkyi succinates, most preferably symmetrical dialkyi succinates. If a diaryl or monoaryl-monoalkyl succinate is employed, aryl denotes preferably phenyl which is unsub- stituted or substituted by halogen such as chlorine, Ci-6-alkyl such as ethyl, methyl, isopro- pyl or tert-butyl, or Ci-6-alkoxy such as methoxy or ethoxy. The preferred meaning of aryl is unsubstituted phenyl. If a dialkyl or monoalkyl-monoaryl succinate is employed, then alkyl may be unbranched or branched, preferably branched, and may contain preferably 1 to 18, in particular 1 to 12, more particularly 1 to 8 and more preferably 1 to 5, carbon atoms. Branched alkyl is preferably sec- or tert-alkyl, for example, isopropyl, sec-butyl, tert-butyl, tert-amyl and cyclohexyl.
Examples of disuccinates are dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, dihexyl succinate, diheptyl succinate, dioctyl succinate, diisopropyl succinate, di-sec-butyl succinate, di-tert-butyl succinate, di-tert-amyl suc- cinate, di-[1 ,1-dimethylbutyl] succinate, di-[1 ,1 ,3,3-tetramethylbutyl] succinate, di-[1 ,1- dimethylpentyl] succinate, di-[1-methyl-ethylbutyl] succinate, di-[1 , 1 -diethylpropyl] succinate, diphenyl succinate, di-[4-methylphenyl] succinate, di-[4-chlorophenyl] succinate, mo- noethyl-monophenyl succinate, and dicyclohexyl succinate. Most preferably, the starting disuccinate is diisopropyl succinate.
The disuccinates are known compounds and may be prepared by known methods.
Typically, the nitriles and the disuccinate are used in stoichiometric proportions. It can be advantageous to use the nitriles to be reacted with the disuccinate in more than only stoi- chiometric proportions. An excess of disuccinate over the nitrile can often have a positive influence on the yield, in which case the excess may be up to twice the stoichiometrically required amount of disuccinate.
The reaction of the disuccinate with the nitriles is carried out in an organic solvent. Exam- pies of suitable solvents are primary, secondary or tertiary alcohols containing 1 to 10 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- butanol, tert-butanol, n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3- pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, 2,4,4-trimethyl-2-pentanol, or glycols such as ethylene glycol or diethylene glycol; and also ethers such as tetrahydrofuran or dioxan, or glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; as well as dipolar aprotic solvents such as acetonitrile, benzonitrile, dimethylformamide, N,N- dimethylacetamide, nitrobenzene, N-methylpyrrolidone; aliphatic or aromatic hydrocarbons such as benzene or benzene substituted by alkyl, alkoxy or halogen, for example, toluene, xylene, anisole or chlorobenzene; or aromatic heterocyclic compounds such as pyridine, picoline or quinoline. Mixtures of the above solvents may also be used. It is convenient to use 5 to 20 parts be weight of solvent per 1 part by weight of reactants.
In the process according to the invention, it is preferred to use an alcohol as solvent, in particular a secondary or tertiary alcohol. Preferred tertiary alcohols are tert-butanol and tert-amyl alcohol. Mixtures of these preferred solvents with aromatic hydrocarbons such as toluene or xylene, or halogen-substituted benzene such as chlorobenzene, are also useful.
The process according to the invention is carried out in the presence of a strong base. Suitable strong bases are in particular the alkali metals themselves such as lithium, sodium or potassium, or alkali metal amides such as lithium amide, sodium amide or potassium amide, or alkali metal hydrides such as lithium, sodium or potassium hydride, or alkaline earth metal alcoholates or alkali metal alcoholates which are derived preferably from primary, secondary or tertiary aliphatic alcohols containing from 1 to 10 carbon atoms, for exam- pie, lithium methylate, sodium methylate or potassium methylate, or lithium, sodium or potassium ethylate, lithium, sodium or potassium n-propylate, lithium, sodium or potassium iso-propylate, lithium, sodium or potassium n-butylate, lithium, sodium or potassium sec- butylate, lithium, sodium or potassium tert-butylate, lithium, sodium or potassium 2-methyl- 2-butylate, lithium, sodium or potassium 2-methyl-2-pentylate, lithium, sodium or potassium 3-methyl-3-pentylate, lithium, sodium or potassium 3-ethyl-3-pentylate or lithium, sodium or potassium 3-ethyl-3-pentylate. Additionally, a mixture of these bases may also be employed.
The preferred strong base is an alkali metal alcoholate, the alkali metals being preferably sodium or potassium and the alcoholate being preferably derived from a secondary or tertiary alcohol. Particularly preferred strong bases are therefore, for example, sodium or potassium isopropylate, sodium or potassium sec-butylate, sodium or potassium tert-butylate and sodium or potassium tert-amylate. Moreover, the alkali metal alcoholates may be prepared in situ by reacting the appropriate alcohol with the alkali metal, alkali metal hydride or alkali metal amide.
The strong base is employed in an amount of preferably from about 0.1 to about 10 moles, most preferably from about 1.9 to about 4.0 moles, based on one mole of the disuccinate. Although a stoichiometric amount of base may suffice, an excess of base has been found to have an advantageo
Compounds of formula
Figure imgf000040_0001
can be prepared by reacting
Figure imgf000040_0002
, wherein X14 is halogen, such as, for example, Br, or I, with copper(l)cyanide. The reaction with copper(l)cyanide is carried out in a suitable solvent, like dimethylforamide (DMF) and is carried out at a temperature from about room temperature to about 180°C, preferably from about 100 °C to about 170 °C, e.g. at 130 °C. Reference is made to WO2012/041849 and Frank Wijrthner et al., Chem. Commun., 2011 , 47, 1767- 1769. nds of formula
Figure imgf000041_0001
(lb), wherein R2 is R1*, comprises
(a) reacting (in the presence of a strong base) 2 moles of a compound of formula
Figure imgf000041_0002
(XV) and (XV) (R2oo and R2oo' are independently of each other l group) with 1 mole of a di-nitrile compound of the for-
mula
Figure imgf000041_0003
Figure imgf000041_0004
ined in step (a) with a compound R2-X16
(X16 is halogen, especially J, or Br) under basic conditions (preferably K2CO3) in a dry sol- vent such as e.g. dimethylformamide, A1, A2, A3, R , R2, R ', R2', R * and R2* are as defined above. compounds
Figure imgf000041_0005
under Yamamo- to reaction conditions with the aid of a Nickel complex, wherein compounds of formula III are obtained. X15 is a halogen atom, especially Br, or 1. 1 and z are independently of each other 1 , or 2. k is 0, 1 or 2. r is 0, or 1. R , R2, R1*, R2*, A1 and A2 are as defined above.
Another process for the preparation of compounds of formula (III), wherein R2 is R1*, com- prises (a) reacting (in the presence of a strong base) 2 moles of a compound of formula
Figure imgf000042_0001
(XV') (R200 and R200' are independently of each other a d-Csalkyl group, or a benzyl group) with 1 mole of a di-nitrile compound of the for- mula ^— A3-^ N
(b) and then alkylation of the compound of formula
Figure imgf000042_0002
tained in step (a) with a compound R2-X16 (X16 is halogen, especially J, or Br) under basic conditions (preferably K2CO3) in a dry solvent such as e.g. dimethylformamide.
The compounds of formula XV and XV can be synthesized, for example, in analogy to the methods described in C. Morton et al., Tetrahedron 58 (2002) 5547-5565, or Tetrahedron 62 (2006) 6018-6028.
Alternatively, compounds of the formula (III) (R1 = R1*; R2 = R2*, A3 is a group of formula
-Ar- -Ar- -Ar- -Ar-
, Ar4 is Ar7, k is 1 , or 2, z is 1 , or 2) may be prepared
by reacting a compound of formula Rl ° with a compound of formula
X -Ar- -Ar- -X
, wherein X16' is -B(OH)2, -B(OH)3-, -BF3, -B(OY )2,
Figure imgf000042_0003
and X16 is halogen, such as, for example, Br, or I.
The Suzuki reaction is typically conducted at about 0 °C to 180 °C in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger. A condensation reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.
The compounds of the present invention can also be sythesized by the Stille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 1 1-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). In order to carry out the process, tin compounds
X -Ar- -Ar- -X
, wherein X16' is -SnR207R208R209, anc| the halogen compound
Figure imgf000043_0001
are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200°C, preferably from 30 to 170°C for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours.
Reference is made to WO2009/047104 and WO2012/041849 with respect to the preparation of the starting materials and the compounds of formula I.
In the above Stille and Suzuki coupling reactions the halogen X16 on the halogenated reaction partner can be replaced with the X16' moiety and at the same time the X16' moiety of the other reaction partner is replaced by X16.
Compounds of formula I la can be prepared in analogy to the synthesis of compounds of formula III via Suzuki, or Stille reaction starting from the corresponding building blocks, e.g.
ith one
compound
Figure imgf000043_0002
The compounds, wherein R1, R2, R1', R2', R1 ", R2", R1* and/or R2* are hydrogen, can be obtained by using a protecting group which can be removed after synthesis of the precursor compound (see, for example, EP-A-0648770, EP-A-0648817, EP-A-0742255, EP-A- 0761772, WO98/32802, W098/45757, WO98/58027, WO99/0151 1 , WO00/17275, WOOO/39221 , WOOO/63297 and EP-A-1086984). Conversion of the precursor compound into the desired final compound is carried out by means of fragmentation under known conditions, for example thermally, optionally in the presence of an additional catalyst, for example the catalysts described in WO00/36210.
An example of such a protecting group is group of formula , wherein L is any
O - L
desired group suitable for imparting solubility.
Figure imgf000044_0001
each other Ci-C6alkyl,
Z4 and Z8 are independently of each other Ci-C6alkyl, Ci-C6alkyl interrupted by oxygen, sulfur or N(Z12)2, or unsubstituted or Ci-C6alkyl-, Ci-C6alkoxy-, halo-, cyano- or nitro- substituted phenyl or biphenyl,
Z5, Z6 and Z7 are independently of each other hydrogen or Ci-C6alkyl,
Z9 is hydrogen, Ci-C6alkyl or a group of formula
Figure imgf000044_0002
or
O
15
-O-Z
Z10 and Z11 are each independently of the other hydrogen, Ci-C6alkyl, Ci-C6alkoxy, halogen, cyano, nitro, N(Z12)2, or unsubstituted or halo-, cyano-, nitro-, Ci-C6alkyl- or
Ci-C6alkoxy-substituted phenyl,
Z12 and Z13 are Ci-Cealkyl, Z14 is hydrogen or Ci-Cealkyl, and Z15 is hydrogen, Ci-Cealkyl, or unsubstituted or Ci-C6alkyl-substituted phenyl,
Q is p,q-C2-C6alkylene unsubstituted or mono- or poly-substituted by Ci-C6alkoxy,
Ci-C6alkylthio or C2-Ci2dialkylamino, wherein p and q are different position numbers, X is a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, m' being the number 0 when X is oxygen or sulfur and m being the number 1 when X is nitrogen, and
L1 and L2 are independently of each other unsubstituted or mono- or poly-Ci-Csalkoxy-, -Ci-Cealkylthio-, -C2-C24dialkylamino-, -C6-Ci2aryloxy-, -C6-Ci2arylthio-,
-C7-C24alkylarylamino- or -Ci2-C24diarylamino-substituted Ci-C6alkyl or [-(p',q - C2-C6alkylene)-Z-]n -Ci-C6alkyl , n' being a number from 1 to 1000, p' and q' being different position numbers, each Z independently of any others being a hetero atom oxygen, sulfur or d-Csalkyl-substituted nitrogen, and it being possible for C2-C6alkylene in the repeating [-C2-C6alkylene-Z-] units to be the same or different,
and Li and l_2 may be saturated or unsaturated from one to ten times, may be uninterrupted or interrupted at any location by from 1 to 10 groups selected from the group consisting of -(C=0)- and -C6H4-, and may carry no further substituents or from 1 to 10 further substitu- of halogen, cyano and nitro. Most preferred L is a
Figure imgf000045_0001
Compounds of formula
Figure imgf000045_0002
(X) are intermediates in the production of polymers and form a further subject of the present invention. A1 ' and A2' are independently of each other a group of formula
-Ar -Ar- -Ar R3'
R3' is independently in each occurrence ZnX 2, -SnR 07R 08R209, wherein R207, R208 and R209 are identical or different and are H or Ci-C6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched;
X12 is a halogen atom, very especially I, or Br; -OS(0)2CF3, -OS(0)2-aryl, especially
Figure imgf000045_0003
-OS(0)2CH3, -B(OH)2, -B(OH)3-, -BF3, -B(OY )2, or
.0
-B X
o wherein Y1 is independently in each occurrence a Ci-Csalkyl group and Y2 is independently in each occurrence a C2-Cioalkylene group, such as -CY3Y4-CY5Y6-, or - CY Y8.CY9Y10- CY11Y12-, wherein Y3, Y4, Ys, γβ, Y7, γβ_ γθ γιο. γιι and Yi2 are independently of each other hydrogen, or a Ci-Csalkyl group, especially -C(CH3)2C(CH3)2-, or -C(CH3)2CH2C(CH3)2-, -CH2C(CH3)2 CH2-, and Y13 and Y14 are independently of each other hydrogen, or a Ci-C8alkyl group; a, b, c, p, q, R , R2, R ', R2', R ", R2", R * , R2* , Ar , Ar2, Ar3, A3, A4 and A5 are as defined above.
An example of a compound of formula X is compound A-16 as depicted in claim 9. Compounds of formula X can be obtained in analogy to known procedures, which are, for example, described in US6451459, WO2005/049695, WO2008/000664, WO2009/047104, WO2010/049321 , WO2010/049323, WO2010/108873, WO2010/115767, WO2010/136353, EP2033983 and EP2034537.
The compounds of formula X can be used to prepare polymers. Accordingly, the present invention is also directed to polymers comprising repeating unit(s) of formula R ,1' ' O R" O R' O O
(VI), wherein A1" and 2" are independently of each other a group of formula
Figure imgf000046_0001
, wherein a, b, c, p, q, R , R2, R1 ', R2', R1 ", R2 ', R1* , R2* , Ar1 , Ar2, Ar3, A3, A4 and A5 are as defined above. The polymers of the present invention may be used in the production of semiconductor devices. Accordingly, the present invention is also directed to semiconductor devices comprising a polymer of the present invention.
Halogen is fluorine, chlorine, bromine and iodine.
Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, do- cosyl, tetracosyl or pentacosyl. d-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl. Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl. A haloalkyi group is an alkyl group, wherein one, or more than one hydrogen atoms are repled by halogen atoms. A haloalkyi group is an alkyl group, wherein one, or more than one hydrogen atoms are repled by halogen atoms.
C2-C25alkenyl (C2-Cisalkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4- dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl. C2-25alkynyl (C2-isalkynyl) is straight-chain or branched and preferably C2-salkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn- 4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6- yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.
Ci-C25alkoxy groups (Ci-Cisalkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2- dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1 ,1 ,3,3-tetramethylbutoxy and 2- ethylhexoxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, iso- propoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term "alkylthio group" means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.
Ci-Ci8perfluoroalkyl, especially Ci-C4perfluoroalkyl, is a branched or unbranched radical such as for example -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
The term "carbamoyl group" is typically a Ci-i8carbamoyl radical, preferably d-scarbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcar- bamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.
The term "alkanoyl" represents an alkyl group attached to the parent molecular group through a carbonyl group and is exemplified by formyl, acetyl, propionyl, and butanoyl. The term "silyl group" means a group of formula -SiR62R63R64, wherein R62, R63 and R64 are independently of each other a d-Csalkyl group, in particular a C1-C4 alkyl group, a C6- C24aryl group, or a C7-Ci2aralkylgroup, such as a trimethylsilyl group. The term "siloxanyl group" means a group of formula -0-SiR62R63R64, wherein R62, R63 and R64 are as defined above, such as a trimethylsiloxanyl group.
Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are d-Csalkoxy or d-Csalkylthio groups as exemplified further below. The term "aliphatic group" comprises also alkyl groups wherein certain non-adjacent carbon atoms are re- placed by oxygen, like -CH2-0-CH2-CH2-0-CH3. The latter group can be regarded as methyl substituted by -0-CH2-CH2-0-CH3.
An aliphatic hydrocarbon group having up to 25 carbon atoms is a linear or branched alkyl, alkenyl or alkynyl (also spelled alkinyl) group having up to 25 carbon atoms as exemplified above.
Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) free valencies, e.g. tri- methylene or tetramethylene. Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one) free valencies, e.g. -CH2-CH=CH-CH2-.
Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are d-Csalkoxy or d-Csalkylthio groups as exemplified further below. The term "aliphatic group" comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like -CH2-O-CH2-CH2-O-CH3. The latter group can be regarded as methyl substituted by -O-CH2-CH2-O-CH3. A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl group which may be substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups.
A cycloaliphatic-aliphatic group is an aliphatic group substituted by a cycloaliphatic group, wherein the terms "cycloaliphatic" and "aliphatic" have the meanings given herein and wherein the free valency extends from the aliphatic moiety. Hence, a cycloaliphatic- aliphatic group is for example a cycloalkyl-alkyl group.
A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkyl group, e.g. cyclohex- yl-methyl.
A "cycloalkenyl group" means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups and/or condensed with phenyl groups.
A bivalent group of the formula
Figure imgf000048_0001
(X1 is , S, Se, or NR10) wherein R20 and R21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, is e.g. a group of the formula
Figure imgf000048_0002
wherein A represents linear or branched alkylene having up to 25 carbon atoms, preferably ethylene or propylene which may be substituted by one or more alkyl groups, and Y represents oxygen or sulphur. For example, the bivalent group of the formula -Y-A-O- represents -O-CH2-CH2-O- or -O-CH2-CH2-CH2-O- .
A cycloalkyl group is typically C3-Ci2cycloalkyl (especially C5-Ci2cycloalkyl), such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloun- decyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The cycloalkyl group, or cycloalkenyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with Ci-C4-alkyl, halogen and cyano. Examples of such condensed
Figure imgf000049_0001
R155 and R156 are independently of each other d-Cs-alkyl, d-Cs-alkoxy, halogen and cy- ano, in particular hydrogen.
C6-C24aryl (C6-Cisaryl) is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, as- indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted. Examples of C6-Ci2aryl are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted. C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ro,co-dimethyl-co-phenyl-butyl, o-phenyl-dodecyl, co-phenyl-octadecyl, co-phenyl-eicosyl or co-phenyl-docosyl, preferably Cz-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, co-phenyl-dodecyl or co-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, or ω,ω-dimethyl-co-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2- phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl. Heteroaryl is typically C2-C2oheteroaryl, i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrol- yl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, in- dolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, ben- zotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazi- nyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsub- stituted or substituted.
Possible substituents of the above-mentioned groups are d-Csalkyl, a hydroxyl group, a mercapto group, d-Csalkoxy, d-Csalkylthio, halogen, halo-d-Csalkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially d-Csalkyl, d-Csalkoxy, d- Cealkylthio, halogen, halo-d-Csalkyl, or a cyano group.
Ci-dsalkyl (Ci-Cisalkyl) interrupted by one or more O is, for example, (CH2CH20)i-9-Rx, where R* is H or d-doalkyl, CH2-CH(ORy')-CH2-0-Ry, where Ry is Ci-dsalkyl (Ci- Ci8alkyl), and Ry' embraces the same definitions as Ry or is H.
If a substituent, such as, for example R3, occurs more than one time in a group, it can be different in each occurrence.
Advantageously, the compositions, or compounds of the present invention, or an organic semiconductor material, layer or component, comprising the compositions, or compounds of the present invention can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
The compounds of the present invention can show p-type transistor behavior and can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to a semiconductor device comprising as a semiconducting effective means a compound of the present invention.
The invention relates especially to a semiconductor device comprising as as a semiconducting effective means a composition, or a compound of the present invention. With respect to the composition, or compound of the present invention the above-mentioned preferences apply. The compounds are especially selected from compounds A-1 to A-27 and B-1 , respectively, which are depicted in claim 9.
Preferably said semiconductor device is a diode, a photodiode, a sensor, an organic field effect transistor (OFET), a transistor for flexible displays, or a solar cell, or a device containing a diode and/or an organic field effect transistor, and/or a solar cell. There are numerous types of semiconductor devices. Common to all is the presence of one or more semiconductor materials. Semiconductor devices have been described, for example, by S. M. Sze in Physics of Semiconductor Devices, 2nd edition, John Wiley and Sons, New York (1981 ). Such devices include rectifiers, transistors (of which there are many types, including p-n-p, n-p-n, and thin-film transistors), light emitting semiconductor devices (for example, organic light emitting diodes in display applications or backlight in e.g. liquid crystal displays), pho- toconductors, current limiters, solar cells, thermistors, p-n junctions, field-effect diodes, Schottky diodes, and so forth. In each semiconductor device, the semiconductor material is combined with one or more metals and/or insulators to form the device. Semiconductor devices can be prepared or manufactured by known methods such as, for example, those described by Peter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill, New York (2000). In particular, organic electronic components can be manufactured as described by D.R. Gamota et al. in Printed Organic and Molecular Electronics, Kluver Academic Publ., Boston, 2004. A particularly useful type of transistor device, the thin-film transistor (TFT), generally includes a gate electrode, a gate dielectric on the gate electrode, a source electrode and a drain electrode adjacent to the gate dielectric, and a semiconductor layer adjacent to the gate dielectric and adjacent to the source and drain electrodes (see, for example, S. M. Sze, Physics of Semiconductor Devices, 2nd edition, John Wiley and Sons, page 492, New York (1981)). These components can be assembled in a variety of configurations. More specifically, an organic thin-film transistor (OTFT) has an organic semiconductor layer.
Typically, a substrate supports the OTFT during manufacturing, testing, and/or use. Optionally, the substrate can provide an electrical function for the OTFT. Useful substrate ma- terials include organic and inorganic materials. For example, the substrate can comprise silicon materials inclusive of various appropriate forms of silicon, inorganic glasses, ceramic foils, polymeric materials (for example, acrylics, polyester, epoxies, polyamides, polycarbonates, polyimides, polyketones, poly(oxy-1 ,4-phenyleneoxy-1 ,4-phenylenecarbonyl-1 ,4- phenylene) (sometimes referred to as poly(ether ether ketone) or PEEK), polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalenedicarboxylate) (PEN), poly(ethylene ter- ephthalate) (PET), poly(phenylene sulfide) (PPS)), filled polymeric materials (for example, fiber-reinforced plastics (FRP)), and coated metallic foils. The substrate can have any suitable thickness, preferably in the range of 10μιη to 10mm, even more preferably from 10μιη to 1 mm.
The gate electrode can be any useful conductive material. For example, the gate electrode can comprise doped silicon, or a metal, such as aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, and titanium. Conductive oxides, such as indium tin oxide (ITO), or conducting inks/pastes comprised of carbon black/graphite or colloidal silver dis- persions, optionally containing polymer binders can also be used. Conductive polymers also can be used, for example polyaniline or poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS). In addition, alloys, combinations, and multilayers of these materials can be useful. In some OTFTs, the same material can provide the gate electrode function and also provide the support function of the substrate. For example, doped silicon can function as the gate electrode and support the OTFT.
The gate dielectric is generally provided on the gate electrode. This gate dielectric electrically insulates the gate electrode from the balance of the OTFT device. Useful materials for the gate dielectric can comprise, for example, an inorganic electrically insulating material.
The gate dielectric (insulator) can be a material, such as, an oxide, nitride, or it can be a material selected from the family of ferroelectric insulators (e.g. organic materials such as poly(vinylidene fluoride/trifluoroethylene or poly(m-xylylene adipamide)), or it can be an organic polymeric insulator (e.g. poly(methacrylate)s, poly(acrylate)s, polyimides, benzocy- clobutenes (BCBs), parylenes, polyvinylalcohol, polyvinylphenol (PVP), polystyrenes, poly- ester, polycarbonates) as for example described in J. Veres et al. Chem. Mat. 2004, 16, 4543 or A. Facchetti et al. Adv. Mat. 2005, 17, 1705. Specific examples of materials useful for the gate dielectric include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, and zinc sulphide, including but not limited to PbZrxTii-x03 (PZT), Bi4Ti30i2, BaMgF4, Ba(Zri-xTix)03 (BZT). In addition, alloys, hybride materials (e.g. polysiloxanes or nanoparticle-filled polymers) combinations, and multilayers of these materials can be used for the gate dielectric. The thickness of the dielectric layer is, for example, from about 10 to 1000 nm, with a more specific thickness being about 100 to 500 nm, providing a capacitance in the range of 0.1 - 100 nanofarads (nF).
The source electrode and drain electrode are separated from the gate electrode by the gate dielectric, while the organic semiconductor layer can be over or under the source electrode and drain electrode. The source and drain electrodes can be any useful conductive material favourably providing a low resistance ohmic contact to the semiconductor layer. Useful materials include most of those materials described above for the gate electrode, for example, aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof, combinations thereof, and multilayers thereof. Some of these materials are appropriate for use with n- type semiconductor materials and others are appropriate for use with p-type semiconductor materials, as is known in the art.
The thin film electrodes (that is, the gate electrode, the source electrode, and the drain electrode) can be provided by any useful means such as physical vapor deposition (for example, thermal evaporation or sputtering) or (ink jet) printing methods. The patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.
The present invention further provides a thin film transistor device comprising
a plurality of electrically conducting gate electrodes disposed on a substrate;
a gate insulator layer disposed on said electrically conducting gate electrodes;
a plurality of sets of electrically conductive source and drain electrodes disposed on said insulator layer such that each of said sets is in alignment with each of said gate electrodes; an organic semiconductor layer disposed in the channel between source and drain electrodes on said insulator layer substantially overlapping said gate electrodes; wherein said organic semiconductor layer comprise a composition, or a compound of the present invention.
The present invention further provides a process for preparing a thin film transistor device comprising the steps of:
depositing a plurality of electrically conducting gate electrodes on a substrate;
depositing a gate insulator layer on said electrically conducting gate electrodes; depositing a plurality of sets of electrically conductive source and drain electrodes on said layer such that each of said sets is in alignment with each of said gate electrodes;
depositing a layer comprising a composition, or a compound of the present invention on said insulator layer such that said layer comprising the composition, or the compound of the present invention substantially overlaps said gate electrodes, thereby producing the thin film transistor device.
The ratio of the compound of formula I to the polymeric material can vary from 5 to 95 percent based on the amount of the compound of formula I and the polymeric material.
The polymeric material may be a semi-conducting polymer, or a polymeric binder. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). With this technique, a degradation of the electrical performance can be avoided (cf. WO
2008/001123 A1).
The above-mentioned layer comprising a compound of the present invention may additionally comprise at least another material. The other material can be, but is not restricted to another compound of the present invention, a semi-conducting polymer, a polymeric bind- er, organic small molecules different from a compound of the present invention, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.). Any suitable substrate can be used to prepare the thin films of the compositions, or compounds of the present invention. Preferably, the substrate used to prepare the above thin films is a metal, silicon, plastic, paper, coated paper, fabric, glass or coated glass.
Alternatively, a TFT is fabricated, for example, by solution deposition, or vacuum deposition of a composition, or compound of the present invention on a highly doped silicon substrate covered with a thermally grown oxide layer followed by vacuum deposition and patterning of source and drain electrodes.
In yet another approach, a TFT is fabricated by deposition of source and drain electrodes on a highly doped silicon substrate covered with a thermally grown oxide and then solution deposition of a composition, or compound of the present invention to form a thin film.
The gate electrode could also be a patterned metal gate electrode on a substrate or a conducting material such as a conducting polymer, which is then coated with an insulator ap- plied either by solution coating or by vacuum deposition on the patterned gate electrodes.
Any suitable solvent can be used to dissolve, and/or disperse a compound of the formula I, provided it is inert and can be removed partly, or completely from the substrate by conventional drying means (e.g. application of heat, reduced pressure, airflow etc.). Suitable or- ganic solvents for processing the semiconductors of the invention include, but are not lim- ited to, aromatic or aliphatic hydrocarbons, halogenated such as chlorinated or fluorinated hydrocarbons, esters, ethers amides, such as chloroform, tetrachloroethane, tetrahydrofu- ran, toluene, tetraline, anisole, xylene, ethyl acetate, methyl ethyl ketone, dimethyl forma- mide, dichlorobenzene, trichlorobenzene, propylene glycol monomethyl ether acetate (PGMEA) and mixtures thereof. The solution, and/or dispersion is then applied by a method, such as, spin-coating, dip-coating, screen printing, microcontact printing, doctor blading or other solution application techniques known in the art on the substrate to obtain thin films of the semiconducting material. The term "dispersion" covers any composition comprising a composition, or compound of the present invention, which is not fully dissolved in a solvent. The dispersion can be done selecting a composition including at least a compound of formula I, or a mixture containing a compound of formula I, and a solvent, wherein the oligomer and/or polymer exhibits lower solubility in the solvent at room temperature but exhibits greater solubility in the solvent at an elevated temperature, wherein the composition gels when the elevated temperature is lowered to a first lower temperature without agitation;
- dissolving at the elevated temperature at least a portion of the compound of the formula I in the solvent; lowering the temperature of the composition from the elevated temperature to the first lower temperature; agitating the composition to disrupt any gelling, wherein the agitating commences at any time prior to, simultaneous with, or subsequent to the lowering the elevated temperature of the composition to the first lower temperature; depositing a layer of the composition wherein the composition is at a second lower temperature lower than the elevated temperature; and drying at least partially the layer. The dispersion can also be constituted of (a) a continuous phase comprising a solvent, a binder resin, and optionally a dispersing agent, and (b) a disperse phase comprising a compound of formula I, or a mixture containing a compound of formula I of the present invention. The degree of solubility of the compound of formula I in the solvent may vary for example from 0.5 % to about 20 % solubility, particularly from 1 % to about 5 % solubility.
Preferably, the thickness of the organic semiconductor layer is in the range of from about 5 to about 1000 nm, especially the thickness is in the range of from about 10 to about 100 nm. The compositions, or compounds of the present invention can be used alone as the organic semiconductor layer of the semiconductor device. The layer can be provided by any useful means, such as, for example, vapor deposition and printing techniques. The compositions, or compounds of the present invention, which are sufficiently soluble in organic solvents, can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).
The compositions, or compounds of the present invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles. Such articles in- elude, for example, radio-frequency identification (RFID) tags, backplanes for flexible dis- plays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like. Due to its ambi-polarity the material can also be used in Organic Light Emitting Transistors (OLET).
In addition, the invention provides organic photovoltaic (PV) devices (solar cells) comprising a composition, or a compound of the present invention. The structure of organic photovoltaic devices (solar cells) is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
The PV device comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(c) a photoactive layer,
(d) optionally a smoothing layer,
(e) an anode (electrode),
(f) a substrate.
The photoactive layer comprises the compositions, or compounds of the present invention. Preferably, the photoactive layer is made of a composition, or a compound of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor.
The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene {Ceo) and the related "spherical" fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C20-C1000. Preferably, the fullerene is selected from the range of Ceo to C96. Most preferably the fullerene is Ceo or C70, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of another compound of formula I or any semi-conducting polymer provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.).
For heteroju notion solar cells (bulk heteroju notion solar cells) the active layer comprises preferably a mixture of a compound of the present invention and a fullerene, such as
[60]PCBM (= 6,6-phenyl-C6i-butyric acid methyl ester), or [70]PCBM, in a weight ratio of 1 :1 to 1 :3. Methanofullerene Phenyl-Cei-Butyric-Acid-Methyl-Ester ([60]PCBM), i.e. 1-[3- (methoxycarbonyl)propyl]-1-phenyl-[6.6]C6i-3'H-cyclopropa[1 ,9][5,6]fullerene-C6o-lh-3'- butanoic acid 3'-phenyl methyl ester, is an effective solution processable n-type organic semiconductor. It is blended with conjugated polymers with nano-particles such as C60. The electrodes are preferably composed of metals or "metal substitutes". Herein the term "metal" is used to embrace both materials composed of an elementally pure metal, e.g., Mg, and also metal alloys which are materials composed of two or more elementally pure metals, e.g., Mg and Ag together, denoted Mg:Ag. Here, the term "metal substitute" refers to a material that is not a metal within the normal definition, but which has the metal-like properties that are desired in certain appropriate applications. Commonly used metal substitutes for electrodes and charge transfer layers would include doped wide-bandgap semiconductors, for example, transparent conducting oxides such as indium tin oxide (ITO), gallium indium tin oxide (GITO), and zinc indium tin oxide (ZITO). Another suitable metal substitute is the transparent conductive polymer polyanaline (PANI) and its chemical relatives, or PEDOT:PSS. Metal substitutes may be further selected from a wide range of non- metallic materials, wherein the term "non-metallic" is meant to embrace a wide range of materials provided that the material is free of metal in its chemically uncombined form. Highly transparent, non-metallic, low resistance cathodes or highly efficient, low resistance metallic/non-metallic compound cathodes are, for example, disclosed in US-B-6,420,031 and US-B-5,703,436.
The substrate can be, for example, a plastic (flexible substrate), or glass substrate. In another preferred embodiment of the invention, a smoothing layer is situated between the anode and the photoactive layer. A preferred material for this smoothing layer comprises a film of 3,4-polyethylenedioxythiophene (PEDOT), or 3,4-polyethylenedioxy- thiophene:polystyrene-sulfonate (PEDOT:PSS). In a preferred embodiment of the present invention, the photovoltaic cell comprises, as described for example, in US-B-6,933,436 a transparent glass carrier, onto which an electrode layer made of indium/tin oxide (ITO) is applied. This electrode layer generally has a comparatively rough surface structure, so that it is covered with a smoothing layer made of a polymer, typically PEDOT, which is made electrically conductive through doping. The photoactive layer is made of two components, has a layer thickness of, for example, 100 nm to a few μιτι depending on the application method, and is applied onto this smoothing layer. The photoactive layer is made of a compound of the formula I, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-
Blodgett ("LB") method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.
In the case of forming the layer by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, Ν,Ν-dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
Before a counter electrode is applied, a thin transition layer, which must be electrically insulating, having a layer thickness of, for example, 0.6 nm, is applied to the photoactive layer. In this exemplary embodiment, this transition layer is made of an alkali halogenide, namely a lithium fluoride, which is vapor deposited in a vacuum of 2 · 10-6 torr at a rate of 0.2 nm/minute.
If ITO is used as a hole-collecting electrode, aluminum, which is vapor deposited onto the electrically insulating transition layer, is used as an electron-collecting electrode. The electric insulation properties of the transition layer obviously prevent influences which hinder the crossing of the charge carrier from being effective, particularly in the transition region from the photoactive layer to the transition layer.
In a further embodiment of the invention, one or more of the layers may be treated with plasma prior to depositing the next layer. It is particularly advantageous that prior to the deposition of the PEDOT SS layer the anode material is subjected to a mild plasma treatment.
As an alternative to PEDOT SS a crosslinkable hole-transport material based on triaryla- mines as referenced in Macromol. Rapid Commun. 20, 224-228 (1999) can be used.
In addition to the triarylamine material the layer can also include an electron acceptor to improve electron transport. Such compounds are disclosed in US 2004/0004433. Preferably, the electron acceptor material is soluble in one or more organic solvents. Typically, the electron acceptor material is present in the range fo 0.5 to 20 % by weight of the triarylamine material.
The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
A so called 'tandem solar cell' comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (c) a photoactive layer,
(d) optionally a smoothing layer,
(e) a middle electrode (such as Au, Al, ZnO, T1O2 etc.)
(f) optionally an extra electrode to match the energy level,
(g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (h) a photoactive layer, (i) optionally a smoothing layer,
G) an anode (electrode),
(k) a substrate. The PV device can also be processed on a fiber as described, for example, in
US20070079867 and US 20060013549.
Due to their excellent self-organising properties the materials or films comprising the compounds of the formula I, especially I la, lib and III can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.
Various features and aspects of the present invention are illustrated further in the examples that follow. While these examples are presented to show one skilled in the art how to operate within the scope of this invention, they are not to serve as a limitation on the scope of the invention where such scope is only defined in the claims. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degrees centigrade and pressures are at or near atmospheric.
Examples
Figure imgf000058_0001
1 2
a) 4.28 g of sodium hydride and 8.41 g of diethyl carbonate are suspended in dry toluene. The mixture is heated to 80-90°C and 5.00 g of 2-acetyl-5-methylthiophene (1 ) dissolved in dry toluene is added dropwise. The mixture is stirred for 3 hours at 90°C. After cooling to room temperature, glacial acetic acid and ice-cold water are added. The mixture is extracted with toluene. The organic phase is washed with water, dried over MgSCu and evaporated. Compound 2 is obtained after Kugelrohr distillation. H NMR (300 MHz, CDC ) <5
Figure imgf000058_0002
b) 1.54 g of sodium ethanolate (, 22.6 mmol), 4.00 g ethyl 3-(5-methylthiophen-2-yl)-3- oxopropanoate (2) and 6.67 g of ethyl bromoacetate are suspended under argon in absolute ethanol at 0°C. The mixture is stirred overnight. Water is added, ethanol is evaporated and the aqueous solution is extracted with diethyl ether. The organic phase is washed with water containing few drops of concentrated HCI, dried and evaporated to provide diethyl 2- (5-methylthiophene-2-carbonyl)succinate (3) which is used without further purification. A mixture of compound 3 and 1 1.64 g of ammonium acetate in glacial acetic acid is stirred at 120°C under argon for 4 hours. After cooling to room temperature, the mixture is poured into water. The precipitate formed is isolated by filtration, washed with water and diethyl ether to provide compound 4 . H NMR (300 MHz, CDC ) <5 9.57 1 H s, 7.61 1 H d, 6.81 1 H m, 4.24 2H
Figure imgf000059_0001
5
c) 2.00 g of sodium ferf-amyl alcoholate (1 M in ferf-amyl alcohol) is added to dry ferf-amyl alcohol under argon. 0.73 g of 2-cyanothiophene and 1.2 g of ethyl 2-(methylthiophen-2-yl)- 5-0X0-4, 5-dihydro-1 /-/-pyrrole-3-carboxylate (4) are added. The mixture is refluxed for 2 hours. After cooling to room temperature, the mixture is poured into methanol acidified with concentrated HCI. The formed precipitate is isolated by filtration, washed successively with water, methanol and diethyl ether and dried to give DPP compound 5. 1H NMR (300 MHz, DMSO-d6) <5 11.20 1 H s, 1 1.15 1 H s, 8.17 1 H dd, 8.02 1 H d, 7.93 1 H dd, 7.28 1 H dd, 7.02 1 H m, 2.56 3H large s.
Figure imgf000059_0002
d) 2.62 g of DPP derivative 5 and 4.60 g of K2CO3 are suspended under argon in anhydrous A/-methyl-2-pyrrolidone and refluxed for 30 minutes. 5.98 g of 1-lodooctane is added and the reaction is further refluxed for 1 hour. After cooling to room temperature, the mixture is poured into water and a precipitate is isolated by filtration and dried. Compound 6 is obtained after column chromatography on silica gel. 1 H NMR (300 MHz, CD2CI2) <5 8.84 1 H dd, 8.78 1 H d, 7.65 1 H dd, 7.28 1 H dd, 6.98 1 H m, 4.03 4H m, 2.61 3H large s, 1.71 4H m, 1.47 - 1.1
Figure imgf000059_0003
e) To a solution of 3.50 g of DPP derivative 6 in chloroform, under light exclusion, is added 1.28 g of /V-bromosuccinimide. The mixture is stirred overnight and washed with water. The organic phase is dried, and evaporated to provide compound 7. 1H NMR (300 MHz, CDCb) <5 8.79 1 H d, 8.61 1 H d, 7.22 1 H d, 6.96 1 H m, 4.00 4H m, 2.61 3H large s, 1.72 4H m, 1.47
Figure imgf000060_0001
8 f) 300 mg of compound 7, 37 mg of Pd(OAc)2 and 63 mg of diisopropylethylamine are suspended in anhydrous toluene under argon. The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered and washed with hot toluene, methanol and diethyl ether. DPP dimer 8 (Cpd. A-15) is obtained after Soxhlet extraction with chloroform. 1 H NMR (300 MHz, CDCb, 40°C) <58.88 2H d, 8.79 2H d, 7.43 2H d, 6.96 2H d, 4.16 - 3.98 8H m, 2.61 6H s, 1.77 8H m, 1.51 - 1.20 40H m, 0.88 12H m.
Figure imgf000060_0002
10 11
a) Compound 11 was synthesized according to a literature procedure, [(a) Morton, C. J. H.; Gilmour, R.; Smith, D. M.; Lightfoot, P.; Slawin, A. M. Z.; MacLean, E. J. Tetrahedron, 2002, 58, 5547. (b) Pfenninger, J.; Iqbal, A.; Rochat, A. C; Wallquist, O. US Patent 4778899, 1986. (c) Pfenninger, J.; Iqbal, A.; Rochat, A. C. US Patent 4749795, 1986.]
Figure imgf000060_0003
11 12
b) 1.5 g of compound 11 and 0.71 g of 2-cyanothiophene are added to a boiling solution of 11.0 imL of sodium ferf-amyl alcoholate (1 M in ferf-amyl alcohol) in dry ferf-amyl alcohol under argon. The mixture is refluxed for 3 hours. After cooling to room temperature, the mixture is poured into methanol acidified with concentrated HCI. The formed precipitate is isolated by filtration, washed successively with water and methanol and dried to give DPP compound 12. H NMR (300 MHz, DMSO-d6) <5 11.30 1 H s, 1 1.26 1 H s, 8.45 - 8.42 2H m, 8.28 1 H
Figure imgf000061_0001
12 13
c) 294.3 mg of DPP 12 and 552.8 mg of K2CO3 are suspended in anhydrous DMF and heated for 40min at 120°C before 3 equivalents of the alkyliodide are added. The mixture is further stirred at 120°C for 3h. After cooling to room temperature, the mixture is poured into water, extracted with CHC and evaporated. The mixture is brought into MeOH and the formed precipitate is isolated by filtration, washed with methanol and dried to give DPP compound 13.
Compound 13a, R = n-octyl:
1 H NMR (300 MHz, CDCI3): 5 8.95 1 H dd, 7.81 - 7.78 2H m, 7.66 1 H dd, 7.54 - 7.51 3H m, 7.30 1 H dd, 4.00 2H t, 3.82 2H t, 1.76 - 1.66 2H m, 1.65 - 1.59 2H m, 1.41 - 1.20 20H m, 0.90 - 0.83 6H m.
Compound 13b, R = 3,7-dimethyl-octyl:
H NMR (300 MHz, CDCI3): 5 8.93 1 H dd, 7.82 - 7.79 2H m, 7.65 1 H dd, 7.54 - 7.49 3H m, 7.29 1 H dd, 4.1 1 - 3.96 2H m, 3.90 - 3.79 2H m, 1.77 - 1.05 20H m, 0.97 6H d, 0.86 - 0.82 12H m.
Figure imgf000061_0002
d) 88 mg of /V-bromosuccinimide is added under light exclusion to a solution of DPP deriva- tive 13 (0.45 mmol) in chloroform under argon. The mixture is stirred overnight and then washed with water. The water phase is extracted with CHCI3. The combined organic phases are dried, filtered and the solvent is removed under reduced pressure. MeOH is added to the crude mixture and compound 14 is obtained as the precipitate which is filtered off, washed with MeOH and dried.
Compound 14a, R = n-octyl:
1 H NMR (300 MHz, CDCI3): <5 8.70 1 H d, 7.80 - 7.77 2H m, 7.53 - 7.51 3H m, 7.25 1 H d, 3.92 2H t, 3.81 2H t, 1.74 - 1.58 2H m, 1.38 - 1.17 20H m, 0.91 - 0.80 6H m.
Compound 14b, R = 3,7-dimethyl-octyl:
1 H NMR (300 MHz, CDCI3): δ 8.67 1 H d, 7.81 - 7.77 2H m, 7.52 - 7.50 3H m, 7.25 1 H d, 4.04 - 3.80 4H m, 1.70 - 1.05 20H m, 0.98 6H d, 0.84 12H t.
Figure imgf000062_0001
e) 0.3 mmol of compound 14, 20 mg of Pd(OAc)2 and 39 mg of diisopropylethylamine are suspended in anhydrous toluene under argon. The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered over celite, toluene is evaporated and the crude mixture is brought in MeOH. Compound 15 is obtained as the precipitate which is filtered off, washed with MeOH and dried.
Compound 15a, R = n-octyl (Cpd. A-6):
1 H NMR (300 MHz, CDCb) δ 8.88 2H d, 7.75 - 7.71 4H m, 7.48 - 7.43 6H m, 7.40 2H d, 3.96 4H t, 3.76 4H t, 1.73 - 1.62 4H m, 1.60 - 1.49 4H m, 1.36 - 1.08 40H m, 0.85 - 0.78 12H m.
Compound 15b, R = 3,7-dimethyl-octyl (Cpd. A-7):
1 H NMR (300 MHz, CDCb) δ 8.96 2H d, 7.83 - 7.79 4H m, 7.55 - 7.51 6H m, 7.46 2H d, 4.11 - 4.00 4H m, 3.90 - 3.82 4H m, 1.67 - 1.42 4H m, 1.79 - 1.06 4H m, 1.02 12H d, 0.84 24H d.
Example 3
Figure imgf000062_0002
16 [1044598-80-2] a) 0.47 g of /V-bromosuccinimide is added under light exclusion to a solution of 2 g DPP derivative 16 [1044598-80-2] in chloroform under argon. The mixture is stirred overnight and then washed with water. The water phase is extracted with CHC . The combined organic phases are dried, filtered and the solvent is removed under reduced pressure. Compound 17 is obtained after chromatography over silica gel. 1H NMR (300 MHz, CDCb): δ 8.88 1 H dd, 8.61 1 H d, 7.64 1 H dxd, 7.27 1 H d, 7.22 1 H d, 4.01 2H d, 3.93 2H d, 1.94 - 1.84 2H m, 1.35 - 1.15 48H m, 0.88 - 0.82 12H m.
Figure imgf000063_0001
b) 259 mg of DPP compound 17, 21 mg of Pd(OAc)2 and 40 mg of diisopropylethylamine are suspended in anhydrous toluene under argon. The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered over celite, toluene is evaporated and the crude mixture is brought in MeOH. The precipitate is filtered off, washed with MeOH and dried. Compound 18 (Cpd. A-5) is obtained after chromatography over silica gel. 1H NMR (300 MHz, CDCb) <58.93 - 8.90 4H m, 7.64 2H dd, 7.43 2H d, 7.28 2H dd, 4.04 8H d, 1.99-1.89 4H m, 1.30 - 1.22 48H m, 0.88 - 0.82 12H m. Exampl
Figure imgf000063_0002
19 [1000623-98-2]
454 mg of DPP compound 19 [1000623-98-2], 34 mg of Pd(OAc)2 and 65 mg of diisopropylethylamine are suspended in anhydrous toluene under argon. The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered over celite, toluene is evaporated and the crude mixture is brought in MeOH. The precipitate is filtered off, washed with MeOH and dried. Compound 20 (Cpd. A-16) is obtained after chromatography over silica gel. H NMR (300 MHz, CDCb) <5 8.91 2H d, 8.63 2H d, 7.41 2H d, 7.21 2H d, 4.02 4H d, 3.95 4H d, 1.98-1.85 4H m, 1.35 - 1.18 48H m, 0.90 - 0.79 12H m. Exam
Figure imgf000063_0003
a) 500 mg of brominated DPP compound 17, 0.5 equiv / 52mg of the boron-compound 21a
[26076-46-0] and 70 mg of Pd(PP i3)4 are suspended in 15 mL anhydrous toluene under argon. Subsequently, a few drops aliquat 336 are added and 0.23 mL of K2CO3 aqueous (2M). The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered over celite, toluene is evaporated and the crude mixture is brought in MeOH. The precipitate is filtered off, washed with MeOH and water, and dried. Compound 22a (Cpd. A-4) is obtained after chromatography over silica gel.
H NMR (300 MHz, CDCb) <5 8.93 - 8.88 4H m, 7.62 2H dd, 7.34 2H d, 7.28 - 7.25 4H m, 4.03
Figure imgf000064_0001
b) 500 mg of brominated DPP compound 17, 0.5 equiv / 126mg of the boron-compound 21b [239075-02-6] and 70 mg of Pd(PPh3)4 are suspended in 15 mL anhydrous toluene under argon. Subsequently, a few drops aliquat 336 are added and 0.23 mL of K2CO3 aqueous (2M). The mixture is refluxed overnight. After cooling to room temperature, the mixture is filtered over celite, toluene is evaporated and the crude mixture is brought in MeOH. The precipitate is filtered off, washed with MeOH and water, and dried. Compound 22b (Cpd. A- 8) is obtained after chromatography over silica gel.
H NMR (300 MHz, CDCb) <5 8.93 2H d, 8.89 2H d, 7.62 2H dd, 7.31 2H d, 7.28 - 7.23 4H m, 7.16 2H d, 4.03 8H d, 2.04 - 1.87 4H m, 1.31 - 1.21 48H m, 0.86 - 0.82 12H m.
Figure imgf000064_0002
[1000623-98-2]
a) 12.47g of [1000623-98-2], 4.02g of [479719-88-5], 0.25g of Pd2(dba)3, and 0.19g Tri-tert- butyl-phosphonium-tetrafluoroborate are suspended under argon in oxygen free tetrahydro- furan. The mixture is refluxed for 30 minutes and then a degassed solution of 7.30g K3PO4 in 6ml of water are added. The reaction mixture is then refluxed over night. The reaction mixture is poured on water and extracted with methylene chloride. The organic phase is dried and evaporated. The compound of formula 23 is obtained after chromatography over silica gel. i H-NMR data (ppm, CDCb): 8.92 1 H d, 8.59 1 H d, 7.29-7.26 2H m, 7.22-7.19 3H m, 7.12 1 H d, 7.04 1 H dxd, 4.00 2H d, 3.93 2H d, 1.94 1 H broad s, 1.89 1 H broad s, 1.41- 1.15 48H m, 0.91-0.79 12H m.
Figure imgf000065_0001
Figure imgf000065_0002
b) 500mg of compound 23, 85mg of [175361-81-6], 12mg of Pd2(dba)3, and 7mg Tri-tert- butyl-phosphonium-tetrafluoroborate are suspended under Argon in oxygen free tetrahydro- furan. The mixture is refluxed for 30 minutes and then a degassed solution of 0.32g K3PO4 in 1 ml of water are added. The reaction mixture is then refluxed over night. The reaction mixture is poured on water and extracted with chloroform. The organic phase is dried and evaporated. The compound of formula 24 (Cpd. A-1 ) is obtained after chromatography over silica gel. 1H-NMR data (ppm, CDC ): 9.05-8.83 4H broad s, 7.82-7.12 12H m, 7.11 2H d, 7.04 2H dxd, 4.04 8H d, 1.97 4H broad s, 1.45-1.15 96H m, 0.86 24H t. The structure of the compound is additionally confirmed by HPLC-MS.
Figure imgf000065_0003
[1000623-98-2]
a) 4.846g of [1000623-98-2], 1.031g of [849062-17-5], 50mg of Pd2(dba)3, and 40mg Tri- tert-butyl-phosphonium-tetrafluoroborate are suspended under Argon in oxygen free tetra- hydrofuran. The mixture is refluxed for 30 minutes and then a degassed solution of 2.8g K3PO4 in 5ml of water are added. The reaction mixture is then refluxed over night. The reaction mixture is poured on water and extracted with chloroform. The organic phase is dried and evaporated. The compound of formula 25 is obtained after chromatography over silica gel. 1 H-NMR data (ppm, CDC ): 8.94 1 H d, 8.61 1 H d, 7.32-7.16 6H m, 7.12-7.08 2H m, 7.03 1 H dxd, 4.01 2H d, 3.94 2H d, 1.95 1 H broad s, 1.91 1 H broad s, 1.45-1.15 48H m,
Figure imgf000066_0001
b) 17.4mg of 2,2'-bipyridine and 30.7mg of Ni(COD)2 are added to a reaction flask under Argon and then 3ml of degassed toluene are added. The reaction mixture is stirred at room temperature for 30 minutes and then 100mg of compound 25 are added. The reaction mixture is then stirred at 80°C for two hours. The reaction mixture is poured on water containing 1 10mg of EDTA and stirred for 1 hour at 60°C. The product is then extracted with chlo- roform. The organic phase is dried and evaporated. The compound of formula 26 (Cpd. A- 2) is obtained after chromatography over silica gel. 1H-NMR data (ppm, CDCb): 9.05-8.85 4H broad s, 7.26-7.05 8H m, 7.05-6.95 10H m, 4.00 8H broad s, 1.94 4H broad s, 1.45-1.15 96H m, 0.84 24H broad s.
Figure imgf000066_0002
[1143585-17-4] a) 4g of compound [1143585-17-4] are dissolved in 100ml chloroform and the mixture is cooled to -5°C. Then 20mg perchloric acid (70%) are added, followed by the addition of 630mg of N-bromo-succinic acid (NBS). The mixture is stirred for 1 hour at -5°C, and then washed with water. The organic phase is dried and evaporated. The compound of formula 27 is obtained after chromatography over silica gel. 1 H-NMR data (ppm, CDCb): 8.91 1 H d,, 8.84 1 H d, 7.34-7.29 3H m, 7.21 1 H d, 7.08-7.01 3H m, 4.02 2H broad d, 4.00 2H broad d, 1.60 1 H broad s, 1.56 1 H broad s, 1.48-1.15 80H m, 0.90-0.80 12H m.
Figure imgf000067_0001
Figure imgf000067_0002
28 b) 500mg of compound 27, 207 mg of [175361-81-6], 15mg of Pd2(dba)3, and 11 mg tri-tert- butyl-phosphonium-tetrafluoroborate are suspended under Argon in oxygen free tetrahydro- furan. The mixture is refluxed for 30 minutes and then a degassed solution of 430mg K3PO4 in 1.5ml of water are added. The reaction mixture is then refluxed for 3 hours. The reaction mixture is poured on water and extracted with methylene chloride. The organic phase is dried and evaporated. The compound of formula 28 (Cpd. A-3) is obtained after chromatography over silica gel. 1H-NMR data (ppm, CDC ): 8.90 4H broad d, 7.30-7.15 8H m, 7.16 2H d, 7.09-7.00 6H m, 4.01 8H broad d, 1.95 4H broad s, 1.45-1.15 160H m, 0.86 24H broad t.
Application Examples 1 to 7
Bottom Gate Bottom Contact (BGBC) Field-Effect Transistors (FETs):
Standard procedure for transistors on silicon substrates: Heavily doped silicon wafers (Si n- - (425 + 40 μιη) with a 230 nm thick thermally grown silicon dioxide layer having on top of the silicon dioxide layer indium tin oxide (15 nm)/gold (30 nm) contacts are used as substrates.
The substrates are prepared by standard cleaning in acetone and i-propanol followed by oxygen plasma treatment for 30 minutes and are then transferred in a glove box and treated with octyltrichlorosilane (OTS) to achieve a hydrophobic monolayer.
Deposition of oligomer film: The semiconductor is dissolved in a proper solvent (see Table 1) in a concentration of 0.75 % by weight at elevated temperature and is spin-coated at 1500 rounds per minute (rpm) for 60 seconds onto the silicon dioxide/silicon substrate. Deposition of oligomer/polymer film: The oligomer and polymer are separately dissolved in dry toluene (0.75 % by weight) at 80°C for 4h, then mixed to achieve the desired ratio and spin-coated at 1500 rpm for 60 seconds onto the silicon dioxide/silicon substrate. All electrical measurements are performed under a nitrogen atmosphere in a glove box with a gate voltage (Vg) varying from 10 to -30 V and at a drain voltage (Vd) equal to 3 and 30V for the transfer characterisation. For the output characterization Vd is varied from 0 to -30V at Vg = 0, 10, 20, 30 V. The reported mobilities represent the saturation mobilities at Vd =30V.
Results of BGBC FET measurements are shown in Table 1 below.
Figure imgf000068_0002
Figure imgf000068_0001
(WO2010/049321 ; Example 1 of Mw = 39'500, Polydis- persity = 2.2 (measured by HT-GPC).
Application Examples 8 to 12
Top Gate Bottom Contact (TGBC) FETs
Standard procedure for transistors on PET substrates:
PET substrates with lithographically patterned gold contacts (50 nm) covered with a photoresist are used as substrates. The substrates are prepared by cleaning in acetone and eth- anol and dried at 60°C for 30 min. The oligomer and polymer are separately dissolved in dry toluene (0.75 wt%) at 80°C for 4 h and then mixed to achieve the desired ratio, filtered through a 0.45μ filter, spin-coated to achieve a 50 nm semiconductor layer and dried at 80°C for 30 seconds. Immediately thereafter a 500 nm thick layer of a dielectric (Allresist GmbH, 950K, 4 % by weight polymethylmethacrylate (PMMA) in butylacetate: ethyllactate solvent mixture) is spin-coated and dried at 80°C for 2 minutes. A 120 nm thick gold electrode is evaporated through a shadow mask for gate contact. The results of the TGBC FET measurements are reported in the Table 2 below:
Figure imgf000069_0001
Example 15: Organic Bulk Heterojunction Solar Cell
The solar cell has the following structure: Al electrode/LiF layer/organic layer, comprising a compound of the present invention and [60]PCBM /[poly(3,4-ethylenedioxy-thiophene)
(PEDOT) in admixture with poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate. The solar cells are made by spin coating a layer of the PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1 :1 mixture of the compound of the present invention (1 % by weight) : [60]PCBM (a substituted Ceo fullerene) is spin coated from ortho-dichlorobenzene (DCB). (organic layer). LiF and Al are sublimed under high vacuum through a shadow- mask.
Solar cell performance:
The solar cell is measured under Aescusoft solar light simulator with halogen light source. The current is estimated under AM 1.5 conditions using the External Quantum Efficiency (EQE) graph.
The results of the measurements are reported in Table 3 below.
Figure imgf000069_0002
Adding small amounts of oligomer A-4 (up to 10%) to polymer P-1 preserves a good field effect mobility of polymer P-1 , while at the same time the homogeneity of the films is improved and the statistical stread of the mobility from device to device is reduced, i.e. device reproducibility is enhanced.

Claims

Claims
A composition, comprising
(a) a compound of the formula
Figure imgf000070_0001
(b) a polymeric material, wherein
p is 0, or 1 , q is 0, or 1 ,
A1 and A2 are independently other a group of formula
-Ar1 -Ar- -Ar R3
Figure imgf000070_0002
, or have the meaning of R5,
A3, A4 and A5 are independently of each other a group of formula
-Ar- -Ar- -Ar- -Ar- a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
k is 0, 1 , or 2; I is 1 , 2, or 3; r is 0, or 1 ; z is 0, 1 or 2;
R1, R2, Ri', R2', Ri", R2", RI* and R2* may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, al- lyl, d-d4aryl, C2-C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -O-, -S-, -N R39-, -COO-, -CO- or -OCO-,
a C2-Ciooalkenyl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, d- C24aryl, C2-C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -O-, -S-, -N R39-, -COO-, -CO- or -OCO-,
a C3-Ciooalkinyl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, C6-C24aryl, C2-C2oheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -0-, -S-, -N R39-, -COO-, -CO- or -OCO-,
a C3-Ci2cycloalkyl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, C5-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, d- d4aryl, d-doheteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by -O-, -S-, -N R39-, -COO-, -CO- or -OCO-,
a C6-d4aryl group which can optionally be substituted one or more times with Ci- dalkyl, Ci-dalkoxy, halogen, d-Ci2cycloalkyl, nitro, cyano, vinyl, silyl, d-d4aryl, d-doheteroaryl, a silyl group or a siloxanyl group,
a d-doheteroaryl group which can optionally be substituted one or more times with Ci-dalkyl, Ci-dalkoxy, halogen, d-Ci2cycloalkyl, nitro, cyano, vinyl, silyl , d- d4sryl, d-doheterosryl, s silyl group or s siloxsnyl group,
-CO-Ci-Ci8Slkyl, -CO-C5-Ci2cycloalkyl, -COO-Ci-Ci8slkyl; R3 is hydrogen, halogen, cyano, Ci-C25alkyl, Ci-C2salkyl which is substituted one or
more times by E and/or interrupted one or more times by D,
Figure imgf000071_0001
, COO-C-i-
Ciealkyl, C3-Ci2cycloalkyl, C3-Ci2cycloalkyl, which is substituted by G, C2-Cisalkenyl, C2-Ci8alkynyl, d-dsthioalkoxy, Ci-Cisalkoxy, Ci-Cisalkoxy which is substituted by E and/or interrupted by D, C7-C2saralkyl, or C7-C2saralkyl, which is substituted by G, or
Figure imgf000071_0002
Ar1 , Ar2, Ar3, Ar4, Ar5, Ar6 and Ar7 are independently of each other a bivalent group of formula
Figure imgf000072_0001
Figure imgf000073_0001
X is is -0-, -S-, -NR10-, -Si(R 8)(R19)-, -Ge(R 8)(R19)-, -C(R 2)(R13)-, -C(=0)-,
Figure imgf000073_0002
R10 and R11 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl, C7-C25arylalkyl, Ci-Cisalkanoyl,
R12 and R13 are independently of each other hydrogen, Ci-Cisalkyl, Ci-Cishaloalkyl,
C2-C2oheteroaryl, or R12 and R13 together represent oxo,
Figure imgf000073_0003
six membered ring, which is unsubstituted or substituted by Ci-Cisalkyl and/or d-dsalkoxy;
R14 and R15 are independently of each other hydrogen, Ci-Cisalkyl, C6-C24aryl, C2- C2oheteroaryl, -CN or COOR50;
R16 and R17 are independently of each other hydrogen, halogen, Ci-C2salkyl, Ci-
— R x
C25alkoxy, C7-C2sarylalkyl, or ^ , Rx is a Ci-CsalkyI group, or a tri(Ci-
Cealkyl)silyl group,
R18 and R19 are independently of each other hydrogen, Ci-Cisalkyl, C7-C2sarylalkyl, or a phenyl group, which optionally can be substituted one to three times with Ci-CsalkyI and/or Ci-Csalkoxy,
R20 and R21 are independently of each other hydrogen, Ci-C2salkyl, C2-C2salkenyl, C2-C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci- Ciealkoxy, C6-C24aryl, C7-C2sarylalkyl, halogen or C2-C2oheteroaryl, or R20 and R21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which may both have up to 4 carbon atoms,
R3o to R38 are independently of each other hydrogen, Ci-C25alkyl, d-dsalkenyl, C2- C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci- Ciealkoxy, C6-C24aryl, d-dsarylalkyl, halogen or C2-C2oheteroaryl,
R40 and R41 are independently of each other hydrogen, d-dsalkyl, d-dsalkenyl, C2-C25alkyl which is interrupted by one or more -O- or -S-, COOR50, cyano, Ci- Ciealkoxy, C6-C24aryl, d-dsarylalkyl, halogen or C2-C2oheteroaryl,
R50 is Ci-C25alkyl, d-dshaloalkyl, d-dsarylalkyl, C6-C24aryl or C2-C2oheteroaryl; R60 to R68 represent independently of each other H, halogen, cyano, d-dsalkyl, Ci- C25alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C3-Ci2cycloalkyl, C3-Ci2cycloalkyl, which is substituted by G, C2-Cisalkenyl, C2- Ciealkynyl, Ci-Cisalkoxy, d-dsalkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or d-dsaralkyl, which is substituted by G,
D is -CO-, -COO-, -S-, -0-, -NR39-, or -C(=0)NR39-,
E is d-Csthioalkoxy, COO-Ci-Ci8alkyl, Ci-C8alkoxy, CN, -NR39R39', -CONR39R39', or halogen,
G is E, or Ci-Ci8alkyl, and
R39 and R39' are independently of each other hydrogen, C-i-C-isalkyl, d-dshaloalkyl, C7-C25arylalkyl, or Ci-Cisalkanoyl, with the proviso that, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, the quotient of the weight average molecular weight of the DPP polymer and the molecular weight of the repeating unit of the polymer is at least 5.
The aim 1 , wherein the polymeric material b) is selected
Figure imgf000074_0001
from (n' is usually in the range of 10 to 1000) and polymers containing diketopyrrolopyrrole (DPP) repeating units.
The composition accordi l is a polymer
represented by formula:
Figure imgf000074_0002
(VII), wherein each R101 and R102 have the meaning of R1; each A6 and A7 is independently selected from optionally substituted aryl and heteroaryl groups; each M is an optional, conjugated moiety; s represents a number from 1 to 4; t represents a number from 1 to 4; u represents a number that is at least 1 ; v represents a number from 0 to 20; and n represents a number that is at least 5.
4. The composition according to any of claims 1 to 3, wherein the compound of the formula I is a compound of the formula
Figure imgf000075_0001
ein Ai , A2, A3, A4, As, Ri , R2, Ri', R2', R1", R2", Ri* and R2* are as defined in claim 1.
A compound of the formula
Figure imgf000075_0002
(II), wherein q is 0, or 1 , A1, A2, A3, A4, A5, R1, R2, R1', R2', R1", R2', R * and R2* are as defined in claim 1 , with the proviso that compounds of formula
Figure imgf000075_0003
wherein R103 = 2-hexyldecyl and y is 3, or 4, are excluded.
6. The compound according to claim 6, which is a compound of the formula r
Figure imgf000076_0001
(lib), wherein Ai, A2, A3, A* As, Ri, R2,
R1', R2', Ri", R2", Ri*and R2* are as defined in claim 5.
A compound of the formula
Figure imgf000076_0002
(III), wherein
A1 and A2 are independently of each other a group of formula
-Ar1 -Ar- -Ar R3
, or R5,
-Ar- -Ar- -Ar- -Ar-
A3 is a group of formula
a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
k is 0, 1 , or 2; I is 1 , 2, or 3; r is 0, or 1 ; z is 0, 1 or 2;
R1, R2, Ri', R2', R3and R5are as defined in claiml;
Ar1, Ar2 and Ar3 are independently of each other a bivalent group of formula
Figure imgf000077_0001
Figure imgf000078_0001
Ar4, Ar5, Ar6 and Ar7 are independently of each other a bivalent group of formula
Figure imgf000078_0002
Figure imgf000079_0001
, wherein X, R , R12, R13, M R-IS, RIB. RI7. R20,
R21, R3o to R37, R40 and R41 are as defined in claim 1,
with the proviso that Ar1, Ar4, Ar5, or Ar7 does not represent a six membered ring, which is attached di
Figure imgf000080_0001
are excluded.
8. a
laim 7, g is an is
Figure imgf000080_0002
Figure imgf000081_0001
(lllc), wherein Ar5, A1 and A2 are as defined above, R1 , R2, R1* and R2* are a Ci-C38alkyl group and Ar4 and Ar6 are independently
Figure imgf000081_0002
Figure imgf000082_0001
The compound according to any of claims 5 to 8:
Figure imgf000082_0002
Figure imgf000083_0001
5
Figure imgf000084_0001
(A-13),
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
10. A semiconductor device comprising a composition as claimed in anyone of claims 1 to 4, or a compound as claimed in any one of claims 5 to 9.
11. A semiconductor device according to claim 10 in the form of a diode, a photodiode, a sensor, an organic field effect transistor, a transistor for flexible displays, or a hetero- junction solar cell.
Use of a compound as claimed in any one of claims 5 to 9 as a p-type transistor.
13. of compounds of formula
Figure imgf000087_0002
III), wherein R2 is R1*, comprising
(a) reacting (in the presence of a strong base) 2 moles of a compound of formula
Figure imgf000087_0003
(XV) and/or (XV') (R200 and R200' are independently of each other a d-Csalkyl group, or a benzyl group) with 1 mole of a di-nitrile compound of the formula N A N ; (b) and then alkylation of the compound of formula
Figure imgf000088_0001
obtained in step (a) with a compound R2-X16 (X16 is halogen) under basic conditions i R1, R2, R1* and R2* are as defined in claim 1 ; or
Figure imgf000088_0002
(lib) (R1 = R2 = R1* = R2*), comprises
(a) reacting (in the presence of a strong base) 2 mole of a disuccinate with 1 mole of
a nitrile of the formula
Figure imgf000088_0003
and 2 mole of a nitrile of the formula A
(b) reacting the compound of formula
Figure imgf000088_0004
(IX") obtained in step a) with a bromide of the formula R1-X16 (X16 is halogen) in the presence of a suitable base in a suitable solvent, wherein R1, R1 ', R2', A1, A3 and A4 are as defined above; or mpound of the formula
Figure imgf000089_0001
(lib) (R2 = R *), comprising
(a) reacting (in the presence of a stronngg bba; se) 2 moles of a compound of formula
Figure imgf000089_0002
(XV) and / or (XV') (R2oo and R2oo' are independently of each other a d-Csalkyl group, or a benzyl group) with 1 mole of a di-
nitrile compound of the
(b) reacting the compou
Figure imgf000089_0003
nd of formula
(IX") obtained in step a) with a halogenide of the formula R2-X16 (X16 is halogen) in the presence of a suitable base in a suitable solvent, wherein R1, R2, R1', R2', R1*, R2* A1, A2, A3 and A4 are as in claim 1.
14. A compound of formula
Figure imgf000089_0004
(X), wherein
A1' and A2' are independently of each other a group of formula
-Ar- -Ar- -Ar R3'
Jb R3' is independently in each occurrence ZnX 2, -SnR 07R 08R209, wherein R207, R2os and R209 are identical or different and are H or Ci-C6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or un- branched;
-OS(0)2CH3, -B(OH)2, -B(OH)3-,
Figure imgf000090_0001
, wherein Y1 is independently in each occurrence a Ci-CsalkyI group and Y2 is independently in each occurrence a C2-Cioalkylene group, and Y13 and Y14 are independently of each other hydrogen, or a Ci-C8alkyl group; a, b, c, p, q, R1, R2, Ri ', R2', Ri", R2", Ri* , R2* , A , Ar2, Ar3, A3, A4 and A5 are as defined in claim 1.
15. Use of a compound of formula (X) according to claim 14 for the preparation of a pol
Figure imgf000090_0002
(VI), wherein
A1" and A2" are independently of each other a group of formula
-Ar- -Ar- -Ar
Jb
, wherein a, b, c, p, q, R , R2, R ', R2', R ", R2", R1* , R2* , Ar1, Ar2, Ar3, A3, A4 and A5 are as defined in claim 1.
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Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749795A (en) 1984-11-07 1988-06-07 Ciba-Geigy Corporation Phenyl substituted pyrrolinones
US4778899A (en) 1984-11-07 1988-10-18 Ciba-Geigy Corporation Process for the preparation of pyrrolo (3,4-c) pyrroles
EP0648817A1 (en) 1993-10-13 1995-04-19 Ciba-Geigy Ag Novel fluorescent dyes
EP0648770A2 (en) 1993-10-13 1995-04-19 Ciba-Geigy Ag Pyrrolo(3,4-c)pyrroles
EP0742255A1 (en) 1995-05-12 1996-11-13 Ciba-Geigy Ag Colouration of high molecular weight organic materials in the mass with soluble phthalocyanine precursors
EP0761772A1 (en) 1995-07-28 1997-03-12 Ciba SC Holding AG Soluble chromophors containing solubility-enhancing groups which separate easily therefrom
US5703436A (en) 1994-12-13 1997-12-30 The Trustees Of Princeton University Transparent contacts for organic devices
WO1998032802A1 (en) 1997-01-27 1998-07-30 Ciba Specialty Chemicals Holding Inc. Soluble chromophores having improved solubilising groups
WO1998045757A1 (en) 1997-04-09 1998-10-15 Ciba Specialty Chemicals Holding Inc. Black-pigmented structured high molecular weight material
WO1998058027A1 (en) 1997-06-17 1998-12-23 Ciba Specialty Chemicals Holding Inc. Pigmented porous material
WO1999001511A1 (en) 1997-06-30 1999-01-14 Ciba Specialty Chemicals Holding Inc. Method for producing fine pigment dispersions
WO2000017275A1 (en) 1998-09-21 2000-03-30 Ciba Specialty Chemicals Holding Inc. Substituted phthalocyanine
WO2000036210A1 (en) 1998-12-16 2000-06-22 Ciba Specialty Chemicals Holding Inc. Pigmented porous material
WO2000039221A1 (en) 1998-12-29 2000-07-06 Ciba Specialty Chemicals Holding Inc. Improved method for producing thermally cleavable, soluble pigment derivatives
WO2000063297A1 (en) 1999-04-16 2000-10-26 Ciba Specialty Chemicals Holding Inc. Azophthalocyanine and pigment precursors and their use
EP1086984A2 (en) 1999-09-24 2001-03-28 Ciba SC Holding AG Compounds for mass colouration of polymers
EP1119231A2 (en) 2000-01-18 2001-07-25 Rohde & Schwarz GmbH & Co. KG High frequency power amplifier
US6420031B1 (en) 1997-11-03 2002-07-16 The Trustees Of Princeton University Highly transparent non-metallic cathodes
US6451459B1 (en) 1999-08-26 2002-09-17 Ciba Specialty Chemicals Corporation DPP-containing conjugated polymers and electroluminescent devices
US20030021913A1 (en) 2001-07-03 2003-01-30 O'neill Mary Liquid crystal alignment layer
WO2003048268A1 (en) 2001-12-03 2003-06-12 Toyo Ink Mfg. Co., Ltd. Composition for organic electroluminescence element and organic electroluminescence element using the same
US20040004433A1 (en) 2002-06-26 2004-01-08 3M Innovative Properties Company Buffer layers for organic electroluminescent devices and methods of manufacture and use
WO2004112161A2 (en) 2003-06-12 2004-12-23 Konarka Technologies, Inc. Tandem solar cell with a shared organic electrode
WO2005049695A1 (en) 2003-10-28 2005-06-02 Ciba Specialty Chemicals Holding Inc. Novel diketopyrrolopyrrole polymers
US6933436B2 (en) 2000-04-27 2005-08-23 Konarka Austria Forschungs Und Entwicklungs Gmbh Photovoltaic cell
US20060013549A1 (en) 2004-07-16 2006-01-19 Max Shtein Organic devices having a fiber structure
WO2006061343A1 (en) 2004-12-09 2006-06-15 Ciba Specialty Chemicals Holding Inc. Fluorescent diketopyrrolopyrroles
JP2006310538A (en) 2005-04-28 2006-11-09 Toray Ind Inc Light-emitting element
WO2007003520A1 (en) 2005-07-05 2007-01-11 Ciba Specialty Chemicals Holding Inc. Fluorescent diketopyrrolopyrroles and derivatives
US20070079867A1 (en) 2005-10-12 2007-04-12 Kethinni Chittibabu Photovoltaic fibers
WO2008000664A1 (en) 2006-06-30 2008-01-03 Ciba Holding Inc. Diketopyrrolopyrrole polymers as organic semiconductors
WO2008001123A1 (en) 2006-06-29 2008-01-03 Cambridge Enterprise Limited Blended polymer fets
EP2034537A2 (en) 2007-09-06 2009-03-11 Xerox Corporation Diketopyrrolopyrrole-based derivatives for thin film transistors
EP2033983A2 (en) 2007-09-06 2009-03-11 Xerox Corporation Diketopyrrolopyrrole-Based Polymers
WO2009047104A2 (en) 2007-10-09 2009-04-16 Basf Se Pyrrolopyrrole derivatives, their manufacture and use
EP2075274A1 (en) 2007-12-27 2009-07-01 Industrial Technology Research Institute Soluble polythiophene derivatives
WO2010049323A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010049321A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic field effect transistors
WO2010108873A1 (en) 2009-03-23 2010-09-30 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010115767A1 (en) 2009-04-08 2010-10-14 Basf Se Pyrrolopyrrole derivatives, their manufacture and use as semiconductors
WO2010136352A1 (en) 2009-05-27 2010-12-02 Basf Se A process for polymerising (hetero)aromatic compounds
WO2010136353A1 (en) 2009-05-27 2010-12-02 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
US20100326525A1 (en) 2009-03-26 2010-12-30 Thuc-Quyen Nguyen Molecular semiconductors containing diketopyrrolopyrrole and dithioketopyrrolopyrrole chromophores for small molecule or vapor processed solar cells
WO2011144566A2 (en) 2010-05-19 2011-11-24 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2012041849A1 (en) 2010-09-29 2012-04-05 Basf Se Semiconductors based on diketopyrrolopyrroles

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101072842A (en) * 2004-12-09 2007-11-14 西巴特殊化学品控股有限公司 Fluorescent diketopyrrolopyrroles
US8946376B2 (en) 2010-09-29 2015-02-03 Basf Se Semiconductors based on diketopyrrolopyrroles
WO2012175530A1 (en) * 2011-06-22 2012-12-27 Basf Se Diketopyrrolopyrrole oligomers for use in organic semiconductor devices
JP2013055322A (en) * 2011-08-11 2013-03-21 Mitsubishi Chemicals Corp Photoelectric conversion element, solar cell, and solar cell module

Patent Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749795A (en) 1984-11-07 1988-06-07 Ciba-Geigy Corporation Phenyl substituted pyrrolinones
US4778899A (en) 1984-11-07 1988-10-18 Ciba-Geigy Corporation Process for the preparation of pyrrolo (3,4-c) pyrroles
EP0648817A1 (en) 1993-10-13 1995-04-19 Ciba-Geigy Ag Novel fluorescent dyes
EP0648770A2 (en) 1993-10-13 1995-04-19 Ciba-Geigy Ag Pyrrolo(3,4-c)pyrroles
US5703436A (en) 1994-12-13 1997-12-30 The Trustees Of Princeton University Transparent contacts for organic devices
EP0742255A1 (en) 1995-05-12 1996-11-13 Ciba-Geigy Ag Colouration of high molecular weight organic materials in the mass with soluble phthalocyanine precursors
EP0761772A1 (en) 1995-07-28 1997-03-12 Ciba SC Holding AG Soluble chromophors containing solubility-enhancing groups which separate easily therefrom
WO1998032802A1 (en) 1997-01-27 1998-07-30 Ciba Specialty Chemicals Holding Inc. Soluble chromophores having improved solubilising groups
WO1998045757A1 (en) 1997-04-09 1998-10-15 Ciba Specialty Chemicals Holding Inc. Black-pigmented structured high molecular weight material
WO1998058027A1 (en) 1997-06-17 1998-12-23 Ciba Specialty Chemicals Holding Inc. Pigmented porous material
WO1999001511A1 (en) 1997-06-30 1999-01-14 Ciba Specialty Chemicals Holding Inc. Method for producing fine pigment dispersions
US6420031B1 (en) 1997-11-03 2002-07-16 The Trustees Of Princeton University Highly transparent non-metallic cathodes
WO2000017275A1 (en) 1998-09-21 2000-03-30 Ciba Specialty Chemicals Holding Inc. Substituted phthalocyanine
WO2000036210A1 (en) 1998-12-16 2000-06-22 Ciba Specialty Chemicals Holding Inc. Pigmented porous material
WO2000039221A1 (en) 1998-12-29 2000-07-06 Ciba Specialty Chemicals Holding Inc. Improved method for producing thermally cleavable, soluble pigment derivatives
WO2000063297A1 (en) 1999-04-16 2000-10-26 Ciba Specialty Chemicals Holding Inc. Azophthalocyanine and pigment precursors and their use
US6451459B1 (en) 1999-08-26 2002-09-17 Ciba Specialty Chemicals Corporation DPP-containing conjugated polymers and electroluminescent devices
EP1086984A2 (en) 1999-09-24 2001-03-28 Ciba SC Holding AG Compounds for mass colouration of polymers
EP1119231A2 (en) 2000-01-18 2001-07-25 Rohde & Schwarz GmbH & Co. KG High frequency power amplifier
US6933436B2 (en) 2000-04-27 2005-08-23 Konarka Austria Forschungs Und Entwicklungs Gmbh Photovoltaic cell
US20030021913A1 (en) 2001-07-03 2003-01-30 O'neill Mary Liquid crystal alignment layer
WO2003048268A1 (en) 2001-12-03 2003-06-12 Toyo Ink Mfg. Co., Ltd. Composition for organic electroluminescence element and organic electroluminescence element using the same
US20040004433A1 (en) 2002-06-26 2004-01-08 3M Innovative Properties Company Buffer layers for organic electroluminescent devices and methods of manufacture and use
WO2004112161A2 (en) 2003-06-12 2004-12-23 Konarka Technologies, Inc. Tandem solar cell with a shared organic electrode
WO2005049695A1 (en) 2003-10-28 2005-06-02 Ciba Specialty Chemicals Holding Inc. Novel diketopyrrolopyrrole polymers
US20060013549A1 (en) 2004-07-16 2006-01-19 Max Shtein Organic devices having a fiber structure
WO2006061343A1 (en) 2004-12-09 2006-06-15 Ciba Specialty Chemicals Holding Inc. Fluorescent diketopyrrolopyrroles
JP2006310538A (en) 2005-04-28 2006-11-09 Toray Ind Inc Light-emitting element
WO2007003520A1 (en) 2005-07-05 2007-01-11 Ciba Specialty Chemicals Holding Inc. Fluorescent diketopyrrolopyrroles and derivatives
US20070079867A1 (en) 2005-10-12 2007-04-12 Kethinni Chittibabu Photovoltaic fibers
WO2008001123A1 (en) 2006-06-29 2008-01-03 Cambridge Enterprise Limited Blended polymer fets
WO2008000664A1 (en) 2006-06-30 2008-01-03 Ciba Holding Inc. Diketopyrrolopyrrole polymers as organic semiconductors
EP2034537A2 (en) 2007-09-06 2009-03-11 Xerox Corporation Diketopyrrolopyrrole-based derivatives for thin film transistors
EP2033983A2 (en) 2007-09-06 2009-03-11 Xerox Corporation Diketopyrrolopyrrole-Based Polymers
WO2009047104A2 (en) 2007-10-09 2009-04-16 Basf Se Pyrrolopyrrole derivatives, their manufacture and use
EP2075274A1 (en) 2007-12-27 2009-07-01 Industrial Technology Research Institute Soluble polythiophene derivatives
WO2010049323A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010049321A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic field effect transistors
WO2010108873A1 (en) 2009-03-23 2010-09-30 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
US20100326525A1 (en) 2009-03-26 2010-12-30 Thuc-Quyen Nguyen Molecular semiconductors containing diketopyrrolopyrrole and dithioketopyrrolopyrrole chromophores for small molecule or vapor processed solar cells
WO2010115767A1 (en) 2009-04-08 2010-10-14 Basf Se Pyrrolopyrrole derivatives, their manufacture and use as semiconductors
WO2010136352A1 (en) 2009-05-27 2010-12-02 Basf Se A process for polymerising (hetero)aromatic compounds
WO2010136353A1 (en) 2009-05-27 2010-12-02 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2011144566A2 (en) 2010-05-19 2011-11-24 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2012041849A1 (en) 2010-09-29 2012-04-05 Basf Se Semiconductors based on diketopyrrolopyrroles

Non-Patent Citations (27)

* Cited by examiner, † Cited by third party
Title
A. FACCHETTI ET AL., ADV. MAT., vol. 17, 2005, pages 1705
ADV. FUNCT. MATER., vol. 16, 2006, pages 1897 - 1903
APP. PHYS. LET., vol. 90, 2007, pages 143512
ARNOLD B. TAMAYO ET AL: "A Low Band Gap, Solution Processable Oligothiophene with a Diketopyrrolopyrrole Core for Use in Organic Solar Cells", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 112, no. 30, 31 July 2008 (2008-07-31), pages 11545 - 11551, XP055017336, ISSN: 1932-7447, DOI: 10.1021/jp8031572 *
B. M. NOVAK, J. ORG. CHEM., vol. 59, 1994, pages 5034 - 5037
BABUDRI ET AL., J. MATER. CHEM., vol. 14, 2004, pages 11 - 34
C. DEIBEL ET AL., REP. PROG. PHYS., vol. 73, 2010, pages 096401
C. MORTON ET AL., TETRAHEDRON, vol. 58, 2002, pages 5547 - 5565
CHRISTOPH BRABEC, ENERGY ENVIRON. SCI, vol. 2, 2009, pages 347 - 303
FRANK WURTHNER ET AL., CHEM. COMMUN., vol. 47, 2011, pages 1767 - 1769
J. K. STILLE, ANGEW. CHEMIE INT. ED. ENGL., vol. 25, 1986, pages 508
J. VERES ET AL., CHEM. MAT., vol. 16, 2004, pages 4543
M. REMMERS; M. SCHULZE; G. WEGNER, MACROMOL. RAPID COMMUN., vol. 17, 1996, pages 239 - 252
M. SMET ET AL., TETRAHEDRON LETTERS, vol. 42, 2001, pages 6257 - 6530
MACROMOL. RAPID COMMUN., vol. 20, 1999, pages 224 - 228
MATTHIAS HORN ET AL., EUR. POLYMER J., vol. 38, 2002, pages 2197 - 2205
MORTON, C. J. H.; GILMOUR, R.; SMITH, D. M.; LIGHTFOOT, P.; SLAWIN, A. M. Z.; MACLEAN, E. J., TETRAHEDRON, vol. 58, 2002, pages 5547
PETER VAN ZANT: "Microchip Fabrication", 2000, MCGRAW-HILL
R. A. J. JANSSEN ET AL., MACROMOL. CHEM. PHYS., vol. 212, 2011, pages 515 - 520
R. A. J. JANSSEN ET AL.: "Ma molecule DPP derivatives cromol", RAPID COMMUN, vol. 3, no. 1, 2010, pages 1554 - 1559
S. M. SZE: "Physics of Semiconductor Devices", 1981, JOHN WILEY AND SONS
S. M. SZE: "Physics of Semiconductor Devices", 1981, JOHN WILEY AND SONS, pages: 492
STEPHEN LOSER ET AL., J. AM. CHEM. SOC., vol. 133, 5 May 2011 (2011-05-05), pages 8142 - 8145
T.-Q. NGUYEN ET AL., APPLIED PHYSICS LETTERS, vol. 93, 2008, pages 163306
TETRAHEDRON, vol. 62, 2006, pages 6018 - 6028
WALKER B ET AL: "Nanoscale Phase Separation and High Photovoltaic Efficiency in Solution-Processed, Small-Molecule Bulk Heterojunction Solar Cells", ADVANCED FUNCTIONAL MATERIALS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 19, no. 19, 9 October 2009 (2009-10-09), pages 3063 - 3069, XP001548629, ISSN: 1616-301X, DOI: 10.1002/ADFM.200900832 *
Y. XU ET AL., SYNTHETIC METALS, vol. 160, 2010, pages 2135 - 2142

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