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WO2011069554A1 - Polymères comportant des fractions thiophènes 3-substituées comme couches actives pour photopiles - Google Patents

Polymères comportant des fractions thiophènes 3-substituées comme couches actives pour photopiles Download PDF

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Publication number
WO2011069554A1
WO2011069554A1 PCT/EP2009/066896 EP2009066896W WO2011069554A1 WO 2011069554 A1 WO2011069554 A1 WO 2011069554A1 EP 2009066896 W EP2009066896 W EP 2009066896W WO 2011069554 A1 WO2011069554 A1 WO 2011069554A1
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carbon atoms
group
polymer
linear
blend
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Laurence Lutsen
Dirk Vanderzande
Bert Campo
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Hasselt Universiteit
Interuniversitair Microelektronica Centrum vzw IMEC
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Hasselt Universiteit
Interuniversitair Microelektronica Centrum vzw IMEC
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Priority to EP09806085.8A priority Critical patent/EP2509972B1/fr
Priority to PCT/EP2009/066896 priority patent/WO2011069554A1/fr
Priority to JP2012542368A priority patent/JP2013513554A/ja
Publication of WO2011069554A1 publication Critical patent/WO2011069554A1/fr
Priority to US13/491,934 priority patent/US8765882B2/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to new thiophene monomers, as well as conjugated polymers comprising the same.
  • the present invention also relates 5 to blends of conjugated polymers comprising new thiophene units with electro- accepting compounds, and opto-electronic devices, such as photovoltaic cells, made with such blends.
  • the present invention also relates to methods for producing and polymerising such new thiophene monomers.
  • Conjugated polymers and in particular polythiophene polymers have been widely used in opto-electronic devices such as field-effect transistors and photovoltaic cells.
  • polythiophene polymers are usually used as the electron donor and an electron acceptor is brought in contact with it in the device. Electron acceptors that have been used for this
  • a promising photovoltaic structure comprises a bulk- heterojunction (BHJ) of an electron donor and an electron acceptor.
  • BHJ bulk- heterojunction
  • the donor-acceptor interface is highly folded such that
  • photogenerated excitons have a high probability of finding a donor-acceptor interface within a distance L D of their generation site.
  • Bulk-heterojunctions are typically fabricated by spin-coating a mixture of soluble versions of the electron donor and electron acceptor materials. During spin coating and solvent evaporation, the donor and acceptor materials phase separate,
  • phase separation leads to a decrease in the surface of the donor/acceptor
  • One method of enhancing bulk heteroj unction stability is to cross-link the network.
  • crosslinkable materials In the field of organic semi-conducting materials, the interest in crosslinkable materials is increasing, notably for electroluminescent devices and the application of the active layer in a direct structured manner, thereby avoiding the use of shadow masks.
  • Zhu et al Journal of macromolecular science, part A, pure and applied chemistry, vol. 41 , N°12, pp. 1467-1487, 2004 discloses an epoxy- functionalized fullerene Ceo derivative as well as cross-linkable polythiophene derivatives for the purpose of stabilizing film morphology in a bulk- heterojunction involving a mixture polythiophene - fullerene.
  • the stabilizing effect was sought via the polymerization or cross-linking of these entities once the bulk-heterojunction is formed.
  • the epoxy-functionalized fullerene Ceo derivative, once polymerized, was found to stabilize the phase-separated morphology.
  • Cross-linkable polythiophene derivatives were also prepared but were much less effective in stabilizing film morphology. These techniques make use of photoinitiators and require UV light for the polymerization/cross- linking process. Such UV induced reactions involve the formation of radicals that are detrimental to the polymer structure.
  • an admixed electronically active compound such as a photoinitiator
  • its inclusion introduces a reactive impurity, which can adversely affect the film composition, the film morphology and then affecting the functioning of the organic device.
  • organic devices such as organic bulk hetero-junction solar cells in which the nano-morphology of the active layer is very sensitive to any parameter change (during the fabrication process but also over time after fabrication).
  • a cross- linking step was up to now believed to be required for stabilizing bulk heterojunction.
  • thiophene-based polymers can be produced that permit the stabilisation in time of the nano-morphology of an active layer comprising said thiophene- based polymer.
  • an active layer in organic bulk heterojunction solar cells comprising a thiophene-based polymer according to an embodiment of the present invention can have a stable nano-morphology without cross-linking of said material.
  • the physical stabilisation of the morphology is accompanied by a stabilisation of the performance characteristics of the device, such as for instance the power efficiency and/or the short circuit current of a bulk heterojunction solar cell.
  • the stabilisation of the morphology is accompanied by an increase in the lifetime to predetermined performance levels of the devices, in particular solar cells.
  • the stability in time of the power efficiency of the solar cells may be linked to the stability in time of the active layer.
  • This active layer may be processed as a thin film from an organic solvent in which both a polymer according to embodiments of the present invention (p-type, electron donor) and an n-type (electron acceptor) components are soluble, and may be made from a blend of a p-type polymer according to embodiments of the present invention and a n-type material (for example a Ceo fullerene derivative or a n-type semiconducting polymer) which would tend to de-mix with time if the p-type material was not a polymer according to an embodiment of the present invention.
  • a polymer according to embodiments of the present invention p-type, electron donor
  • n-type (electron acceptor) components are soluble
  • a n-type material for example a Ceo fullerene derivative or a n-type semiconducting polymer
  • This blend may be made of a p-type polymer comprising thiophene units having specific side chains and a n-type material mixed together in various ratios and processed e.g. as a thin film from solution.
  • the n-type material included in such blends can be any molecule, oligomer or polymer able to accept an electron from the polymer according to an embodiment of the present invention.
  • n-type materials known to operate an electron transfer when brought into contact with poly(3-hexyl- thiophene) (P3HT) can usually be used. This is true because the polymers according to embodiments of the present invention are electronically similar to P3HT.
  • the present invention relates to a compound represented by the structural formula (I)
  • L is a linear or branched alkylene group having from 1 to 10 carbon atoms
  • J is a hydrogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms;
  • X and Y are independently selected from the group consisting of hydrogen, chloro, bromo, iodo, pseudo-halogens, boronic acid, boronic esters and organotin.
  • This compound is a monomer suitable for being incorporated as a repeat unit or an end group in a polymer or a copolymer. At least one of functions X and Y is such to permit such incorporation.
  • the compound of the first aspect of the present invention may be polymerized or copolymerized via a reductive coupling reaction such as, but not limited to, Rieke coupling (e.g. following a procedure analog to the one disclosed in T.-A.Chen, R. D. Rieke, J. Am. Chem. Soc. (1992) 114, 10087), McCullough coupling (e.g. following a procedure analog to the one disclosed in R. D. McCullough et al., J. Chem. Soc, Chem. Commun., 1992. 70 or U.S. Pat. No. 6,166,172), Stille coupling (e.g.
  • Suzuki coupling e.g. following a procedure analog to the one disclosed in N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun., 1981, 11, 513
  • Yamamoto coupling e.g. following a procedure analog to the one disclosed in T. Yamamoto, A. Morita, Y. Miyazaki, T. Maruyama, H. Wakayama, Z. H. Zhou, Y. Nakamura, T. Kanbara, S. Sasaki and K. Kubota, Macromolecules, 1992, 25, 1214).
  • Reductive coupling is advantageous because it permits the synthesis of regioregular polymers, i.e. polymers with a regioregularity of 80% or more, preferably 85% or more and more preferably 89% or more.
  • Y or different reactive halogens (e.g. I, Br or CI) or pseudo-halogen.
  • This has the effect of permitting its polymerisation or co-polymerisation in a Rieke or Yamamoto coupling polymerisation, or its co-polymerisation in a Suzuki coupling with a co-monomer comprising two identical or different reactive groups selected from the group consisting of boronic acid and boronic esters, or its co-polymerisation in a Stille coupling with a co-monomer comprising two identical or different organotin reactive groups.
  • the monomer may comprise one reactive halogen (e.g. I, Br or CI) or pseudo-halogen and another reactive group (i.e. X and Y are different) selected from the group consisting of boronic acid or boronic esters.
  • one reactive halogen e.g. I, Br or CI
  • another reactive group i.e. X and Y are different
  • X and Y are different
  • both co- monomers are preferably present in equimolar proportions.
  • the monomer may comprise one reactive halogen (e.g. I, Br or CI) or pseudo-halogen and one reactive organotin group (i.e. X and Y are different). This has the effect of permitting its polymerisation or co-polymerisation via a Stille coupling
  • both co-monomers are preferably present in equimolar proportions.
  • a first method involves the addition of ending molecules together with the monomer or co-monomers into the reaction mixture right from the start of the polymerisation.
  • a second method involves a first step of producing the (co)polymer as described in the previous paragraphs, and a second step of reacting this (co)polymer with the ending molecules.
  • the ending molecules are aromatic molecules and preferably comprise only one reactive halogen (e.g. I, Br or CI), boronic acid, boronic ester, organotin or other group known by the person skilled in the art be useful in reductive coupling and are otherwise analog to the co-monomers described above.
  • L is preferably a linear alkylene group.
  • L preferably has from 2 to 8 carbon atoms, more preferably from 4 to 6 carbon atoms and most preferably has 5 carbon atoms.
  • L is a linear alkylene group having 5 carbon atoms, i.e. a pentamethylene group.
  • J is preferably a linear alkyl group having from 1 to 3 carbon atoms, most preferably 2 carbon atoms.
  • the monomer of the first aspect of the present invention has the following structure:
  • the monomer of the first aspect of the present invention has the following structure:
  • the present invention relates to a polymer having at least one monomer unit according to formula (IV):
  • L and J are as defined in any embodiment of the first aspect of the present invention.
  • This polymer can be a homopolymer or a copolymer.
  • the weight average molecular weight Mw (measured against a polystyrene standard) of the polymer (homo- or copolymer) of this invention may be for instance in the range from about 10,000 to about 300,000 Dalton, e.g. from about 12,500 to 200,000 Dalton or from 15,000 to 100,000 Dalton;
  • the polymers according to the second aspect of this invention include homopolymers comprising monomer units represented by the structural formula (IV), and copolymers comprising two or more different monomer units, including at least one co- monomer Ar in addition to the monomer unit (IV), in a random, alternating or block arrangement.
  • a random arrangement can be obtained for instance if a first and a second co-monomer can react with each other and with themselves (e.g. Yamamoto reaction).
  • An alternating arrangement can be obtained for instance if a first and a second co-monomer can only react with each other but not with themselves (e.g. Suzuki reaction when the first monomer comprises two bromine functions and the second monomer comprises two boronic ester functions).
  • a block arrangement can be obtained if a first co-monomer able to react with itself is allowed to polymerize for some time before a second monomer able to react with itself and with the first monomer is introduced in the reaction medium.
  • Another way to obtain a block arrangement can be to first synthesise a polymer comprising only monomers of a first type, followed by the reaction of this polymer with another polymer comprising only monomers of a second type.
  • Suitable monomers that can be co-polymerised with the monomers according to any embodiments of the first aspect of the present invention, especially as represented by the structural formula (I), include monomers of the following general formula:
  • X'-Ar-Y' (V), wherein X' and Y' are independently selected from the group consisting of hydrogen, chloro, bromo, iodo, pseudo-halogens, boronic acid, boronic esters and organotin.
  • This compound (V) is a co-monomer suitable for being incorporated in a copolymer. At least one of functions X' and Y' is such as to permitting such incorporation either via copolymerisation or as end groups.
  • the compound of the first aspect of the present invention may be copolymerized via a reductive coupling reaction such as mentioned above with a co-monomer of formula (V).
  • the comonomer may comprise two reactive groups selected from the group consisting of halogen (e.g. I, Br or CI), pseudo halogens, boronic acid, boronic esters, organotin, and other groups known by the person skilled in the art be useful in reductive coupling reactions.
  • Co- monomers suitable for the formation of co-polymers according to the second aspect of the present invention includes monomers such as among others fluorene derivatives (such as but not limited to 2,7-dibromo-9,9-dialkylfluorene or 2,7-dibromo-9,9-diarylfluorenes (see e.g. C. Ego et al, Adv. Mater. 14 (2002) 809-811)) , indenofluorene derivatives (see e.g. S. Setayesh, Macromolecules (2000)33:2016), phenylene or ladder-type phenylene derivatives (see e.g. J. Grimme et al., Adv. Mat.
  • aniline derivatives such as 2,5-dibromothiophenes and 2,5- dibromo-3-Ci-2o alkylthiophenes
  • fluorenone derivatives such as but not limited to 2,7-dibromoflurenone
  • naphthalene derivatives such as but not limited to 2,6-dibromonaphthalene and 1 ,4-dibromonaphthalene
  • anthracene derivatives such as but not limited to 1 ,4-dibromoanthracene, 2,6- dibromoanthracene and 9,10-dibromoanthracene
  • furane derivatives such as, but not limited to, 2,5-dibromofurane
  • pyrrole derivatives such as, but not limited to, 2,5-dibromopyrrole
  • the co-monomer may comprise one reactive halogen (e.g. I, Br or CI) or pseudo-halogen and another reactive group (i.e. X' and Y' are different) selected from the group consisting of boronic acid or boronic esters.
  • one reactive halogen e.g. I, Br or CI
  • pseudo-halogen e.g. X' and Y' are different
  • a monomer according to formula (I) comprising one reactive halogen (e.g. I, Br or CI) or pseudo-halogen and another reactive group (i.e. X and Y are different) selected from the group consisting of boronic acid or boronic esters.
  • the co-monomer may comprise one reactive halogen (e.g. I, Br or CI) or pseudo-halogen and one reactive organotin group (i.e. X' and Y' are different).
  • one reactive halogen e.g. I, Br or CI
  • pseudo-halogen e.g. I, Br or CI
  • one reactive organotin group i.e. X' and Y' are different.
  • the polymer may be a random, alternating or block co-polymer comprising monomer units according to formula (IV) and at least a comonomer.
  • said at least one comonomer is a homocyclic or heterocyclic aromatic group.
  • This aromatic group can be substituted. For instance it can be substituted with one or more substituents independently selected from the group consisting of Ci-20-alkyl, d -2 o-alkoxy, Ci-20-alkylsulfate, phenyl and benzyl.
  • the polymer may be a copolymer (e.g. a random copolymer) having a constituent unit comprising:
  • Ar is a homocydic or heterocyclic aromatic group. This group can be substituted. For instance it can be substituted with one or more substituents independently selected from the group consisting of Ci -2 o- alkyl, Ci-20-alkoxy, Ci-20-alkylsulfate, phenyl and benzyl, m and n are the number of repeat unit, and L and J are as defined in the first aspect of the present invention.
  • Ar is substituted with one or more linear or branched alkyl groups having 6 to 10 carbon atoms.
  • the comonomer may be according to the following formula:
  • R is a linear or branched alkyl group having from 6 to 10 carbon atoms
  • Another embodiment of the second aspect of the present invention relates to a copolymer according to the following formula:
  • R is a linear or branched alkyl group having from 6 to 10 carbon atoms
  • the copolymer may have monomer units according to formula IV and comonomers in a ratio of from 3:2 to 1 :49, preferably from 3:2 to 1 :19, more preferably from 1 :4 to 1 :19.
  • m/(m+n) may be 0.40 or more, 0.60 or more or 0.80 or more.
  • the m/(m+n) ratio can be 0.98 or less or 0.95 or less. Any of these higher limit for the m/(m+n) ratio can be combined with any of the lower limit mentioned above.
  • the m/(m+n) ratio can be from 0.40 to 0.98 (this correspond to a m/n ratio of from 0.67 to 49), preferably m/(m+n) is from 0.40 to 0.95, more preferably from 0.80 to 0.98 or from 0.80 to 0.95.
  • the present invention relates to a method for producing a polymer according to the second aspect of the present invention, comprising polymerising by reductive coupling a compound according to the first aspect and optionally a co-monomer of formula (V).
  • the present invention relates to a blend for photovoltaic device, comprising:
  • L is a linear or branched alkylene group having from 1 to 10 carbon atoms
  • J is a hydrogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms
  • J' is a group having from 1 to 10 carbon atoms, being saturated or unsaturated, linear or branched, comprising a phenyl unit or not comprising a phenyl unit
  • R' is a hydrogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms
  • Fullerene derivatives includes for instance C 2 8, C 3 6, C 5 o, C 6 o, C 7 o, C 72 ,
  • fullerene derivatives C 6 and Cs 4 derivatives.
  • the most commonly used fullerene derivatives are C6o and C 7 o derivatives.
  • An example is [6, 6]-phenyl-C6i -butyric acid methyl ester (PCBM) which is a Ceo derivative.
  • PCBM [6, 6]-phenyl-C6i -butyric acid methyl ester
  • Polymers incorporating fullerene units are also to be understood as being fullerene derivatives.
  • the blend is preferably a bulk heterojunction.
  • L is preferably a linear alkylene group. L preferably has from 2 to 8 carbon atoms.
  • L' has the formula L-C(O)O-J or L-C(O)NR'-J
  • L has more preferably from 4 to 6 carbon atoms and most preferably has 5 carbon atoms.
  • L has the formula L-C(O)O-J or L- C(O)NR'-J
  • L is a linear alkylene group having 5 carbon atoms, i.e. a pentamethylene group.
  • J is preferably a linear alkyl group having from 1 to 3 carbon atoms, most preferably 2 carbon atoms.
  • L' has the following structure:
  • L has preferably from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms and most preferably 2 carbon atoms (i.e. is an ethylene group).
  • J' has preferably from 1 to 8 carbon atoms.
  • J' can be a methyl group or a cinnamoyl group.
  • L is of the formula L-O-J, L-S-J or L-Se-J
  • L has preferably from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms and most preferably 2 carbon atoms (i.e. is an ethylene group).
  • J is preferably a hydrogen or a methyl and most preferably a hydrogen.
  • the present invention relates to a blend wherein the polymer may be a random, alternating or block co-polymer comprising monomer units according to formula (IV) and at least a comonomer.
  • the at least one comonomer may be a homocyclic or heterocyclic aromatic group.
  • This comonomer can be substituted. For instance it can be substituted with one or more substituents independently selected from the group consisting of Ci -2 o-alkyl, Ci -2 o-alkoxy, Ci-20-alkylsulfate, phenyl and benzyl.
  • the polymer may be a copolymer according to the following formula:
  • Ar is a homocyclic or heterocyclic aromatic group. This group can be substituted. For instance it can be substituted with one or more substituents independently selected from the group consisting of Ci -2 o- alkyl, Ci-20-alkoxy, Ci-20-alkylsulfate, phenyl and benzyl, and
  • n and n are the number of repeat units.
  • the present invention relates to a blend wherein said comonomer is according to the following formula:
  • R is a linear or branched alkyl group having from 6 to 10 carbon atoms
  • the polymer may be a copolymer according to the following formula:
  • R is a linear or branched alkyl group having from 6 to 10 carbon atoms.
  • the copolymer may have monomer units according to formula IV and comonomers in a ratio of from 3:2 to 1 :19, preferably from 1 :4 to 1 :19.
  • m/(m+n) may be from 0.40 to 0.98, preferably form 0.80 to 0.98, more preferably from 0.80 to 0.95.
  • the polymer may be a random copolymer, an alternating copolymer or a block copolymer.
  • the polymer entering said blend is according to any embodiment of the second aspect of the present invention.
  • the present invention relates to an opto-electronic device comprising a blend according to any embodiment of the fourth aspect of the present invention.
  • the polymers and blends according to the invention are generally applied in the form of a thin film to a substrate by known methods familiar to the person skilled in the art, such as dipping, spin coating, inkjet printing, screen printing, etc.
  • spin coating is used.
  • the invention likewise relates to organic solar cells having one or more active layers, where at least one of these active layers comprises one or more polymers or blends according to the invention.
  • the opto-electronic device is a photovoltaic device comprising an anode, a cathode and a blend according to the fourth aspect of the present invention wherein at least one of said anode or cathode is transparent to at least a portion of the solar spectrum.
  • the blend is sandwiched between said anode and said cathode.
  • Organic solar cells with active layers containing a polymer or a blend according the invention are fabricated using state-of-the-art procedures as described in literature (especially relating to parameters such as substrates, electrodes, p-type/n-type ratios, solvents, concentration, etc).
  • a typical organic photovoltaic device generally comprises:
  • a substrate preferably a transparent substrate such as glass
  • a first conductive layer preferably a transparent conductive layer such as ITO
  • a hole transport layer • optionally, one or more hole transport layers
  • a second conducting layer such as a metal electrode.
  • the substrate can be formed of one material or of more than one material.
  • the substrate can be organic or inorganic, planar or non-planar.
  • suitable inorganic substrates are glass and quartz.
  • suitable organic substrates are transparent polymers such as but not limited to poly(methylmethacrylate) (PMMA) and polycarbonate.
  • PMMA poly(methylmethacrylate)
  • the substrate can be rigid or flexible.
  • the first conductive layer plays the role of an anode.
  • a typical example is indium-tin oxide (ITO).
  • Other examples are tin oxides doped with e.g. Sn or F.
  • hole transport layers are well known to the person skilled in the art and include for instance polyaniline (“PANI”), poly(3,4- ethylenedioxythiophene) (“PEDOT”), PEDOTPSS, polypyrrole, organic charge transfer compounds (such as e.g. tetrathiafulvalene tetracyanoquinodimethane (“TTF-TCNQ”)), as well as high work function metal oxides such as molybdenum oxide, vanadium oxide, and tungsten oxide, amongst others.
  • PANI polyaniline
  • PEDOT poly(3,4- ethylenedioxythiophene)
  • PEDOTPSS polypyrrole
  • organic charge transfer compounds such as e.g. tetrathiafulvalene tetracyanoquinodimethane (“TTF-TCNQ”)
  • TTF-TCNQ tetrathiafulvalene tetracyanoquinodimethane
  • TTF-TCNQ tetrathiafulval
  • Usable materials for electron transport layer are well known to the person skilled in the art and include for instance a metal-chelated oxinoid compound (e.g., Alq3 or aluminum(lll)bis(2-methyl-8-quinolinato)4- phenylphenolate (“BAIq”)); a phenanthroline-based compound (e.g., 2,9- dimethyl-4,7-diphenyl-1 ,10-phenanthroline ("DDPA”) or 9,10- diphenylanthracence (“DPA”)); an azole compound (e.g., 2-tert-butylphenyl-5- biphenyl-1 ,3,4-oxadiazole (“PBD”) or 3-(4-biphenyl)-4-phenyl-5-(4-t- butylphenyl)-1 ,2,4-triazole (“TAZ”); a diphenylanthracene derivative; a dinaphthylanthracene derivative; 4,4-bis(2,2-diphenyl-
  • the active layer is preferably subject to an annealing step at a temperature dependent upon the copolymer ratio used in the copolymer, before the top electrode is applied.
  • the choice of top electrode (cathode), e.g. 20nm Ca and 80 nm Al or 100 nm Ytterbium, has little effect upon the ageing characteristics of the solar cell, but affects the absolute value of the initial power efficiency.
  • the invention likewise relates to organic solar cells having one or more active layers, where at least one of these active layers is made from a blend according to the fourth aspect of the present invention having one type of electronic conductivity and a second semi-conducting material (e.g. small molecule such as for example Ceo derivatives or polymers such as n-type (electron accepting) semi-conducting).
  • a second semi-conducting material e.g. small molecule such as for example Ceo derivatives or polymers such as n-type (electron accepting) semi-conducting.
  • Polymers and blends according to the invention are furthermore suitable for organic based devices, for example but not limited to photovoltaic cells (bi-layers, bulk heterojunction, tandem cells, dye-sensitized, organic/organic, organic/polymer, organic/inorganic, reversed device structure, etc).
  • photovoltaic cells bi-layers, bulk heterojunction, tandem cells, dye-sensitized, organic/organic, organic/polymer, organic/inorganic, reversed device structure, etc).
  • a time-stable organic solar cell comprising one or more "stable" active layer. No curing and especially no UV curing of the active layer is required to assure said stability.
  • the present invention relates to the use of a polymer having a monomer unit of formula (IX) wherein L' is as defined in any embodiment of the fourth aspect of the present invention for stabilizing the morphology of a bulk-heterojunction photovoltaic cell.
  • Fig. 1 shows optical micrographs of a P3HT : PCBM 1 :1 blend (top,
  • Fig. 2 shows optical micrographs of a P1 9/1 : PCBM 1 :1 blend (left,
  • a P1 7/3 : PCBM 1 :1 blend (middle, embodiment) and a P1 1/1 : PCBM blend (right, embodiment) annealed at 125°C for a) 15 min, b) 2h, and c) 24h.
  • Fig. 3 shows optical micrographs of a P3 9/1 : PCBM 1 :1 blend (left, embodiment), a P3 7/3 : PCBM 1 :1 blend (middle, embodiment), and a P3 1/1 : PCBM blend (right, embodiment) annealed at 125°C for a) 15 min, b) 2h, and c) 24h.
  • Fig. 4 shows a DSC curve of P3HT(comparative), its 1 :1 blend with PCBM
  • Fig. 5 shows a DSC curve of P1 9/1 (embodiment), its 1 :1 blend with PCBM
  • Fig. 6 shows a DSC curve of P2 9/1 (embodiment), its 1 :1 blend with PCBM
  • Fig. 7 shows a DSC curve of P3 9/1 (embodiment), its 1 :1 blend with PCBM
  • Fig. 8 shows XRD diffraction patterns of P3HT:PCBM 1 :1 (comparative)
  • Fig. 10 shows XRD diffraction patterns of P3HT:PCBM 1 :1 (comparative), P1
  • Fig.1 1 shows the relative efficiency as a function of time for
  • Fig. 12 shows the relative efficiency as a function of time for ITO/PEDOT/P3
  • Fig. 13 shows the relative efficiency as a function of time for
  • Fig. 14 shows the relative current density as a function of time for
  • Fig. 15 shows the relative open circuit voltage as a function of time for
  • Fig. 16 shows the relative fill factor as a function of time for
  • Fig. 17 shows the relative current density as a function of time for
  • Fig. 18 shows the relative open circuit voltage as a function of time for ITO/PEDOT/P3 9/1 :PCBM 1 :1/Ca/AI solar cells at 80 (squares), 100 (triangles) and 125°C (stars) (embodiment).
  • Fig. 19 shows the relative fill factor as a function of time for ITO/PEDOT/P3
  • Fig. 20 shows the short circuit current density as a function of time for
  • Fig. 21 shows the maximum power point as a function of time for
  • Fig. 22 shows the open circuit voltage as a function of time for
  • Fig. 23 shows the fill factor as a function of time for
  • Fig. 24 shows the short circuit current density as a function of time for
  • Fig. 25 shows the maximum power point as a function of time for
  • Fig. 26 shows the open circuit voltage as a function of time for
  • Fig. 27 shows the fill factor as a function of time for
  • the term “electron donor” refers to a compound capable of donating one or more electrons to an electron acceptor.
  • electron acceptor refers to a compound capable of accepting one or more electrons from an electron donor.
  • Well- known electron acceptor materials are fullerenes and/or fullerene derivatives. However, other materials like, for example, cyano-substituted conjugated polymers (e.g.
  • CN-MEH-PPV poly-[2-methoxy-5-(2'-ethylhexyloxy)-1 ,4-(1 - cyanovinylene)-phenylene]
  • benzothiadiazole-comprising conjugated polymers e.g. F8TB (poly(9,9'-dioctlyfluoreneco-benzothiadiazole)
  • perylene based small molecules e.g. perylene dicarboxyimide derivatives
  • the electron acceptor may be a fullerene derivative, such as [6,6]-phenyl-C6i-butyric acid methyl ester.
  • boronic ester refers to a boronic acid derivative wherein hydrogen is replaced by any organic residue, preferably a hydrocarbyl group, and which can be obtained by condensation with alcohols or diols, including but not limited to dioxaborolanes and dioxaborinanes.
  • organotin refers to a group represented by the structural formula SnR 9 Ri 0 Rn wherein each of Rg, Rio and Rn is independently selected from the group consisting of halogen, d -2 o alkyl, C 3- io cycloalkyl, aryl, benzyl and C 2- 7 alkenyl, provided that R 9 , Rio and Rn are not simultaneously halogen; such organotin groups may be derived from tin compounds including, but not limited to, di-n-butyltin dibromide, di-n-butyltin dichloride, di-terf-butyltin dichloride, dimethyltin dibromide, dimethyltin dichloride, dimethyltin difluoride, dimethyltin diiodide, diphenyltin dichloride, diphenyltin dibromide, diphenyltin difluoride, diphenyltin difluoride, diphenyltin dibro
  • pseudo- halogen refers to a chemical group that behave like a halogen in reductive coupling reactions. For instance it can be selected from the group consisting of trifluoromethylmethanesulfonyl, para-toluenesulfonyl and methanesulfonyl.
  • the term “stable” indicates that the nano-morphology of the blend does not change substantially in time upon annealing under inert atmosphere for 15 min at 125°C or even for 2 hours or 24 hours at this temperature.
  • homocyclic aromatic designates any mono- or polycyclic aromatic monovalent hydrocarbon group having from 6 to 15 carbon atoms such as, but not limited to, phenyl, naphthyl, anthracenyl, phenanthracyl, fluoranthenyl, chrysenyl, carbazolyl, pyrenyl, biphenylyl, terphenyl, picenyl, indenyl, biphenyl, indacenyl, tetrahydropyrenyl, benzocyclobutenyl, benzocyclooctenyl and the like, including fused benzo-C 4- s cycloalkyl groups such as, for instance, indanyl, tetrahydronaphthyl, fluorenyl and the like.
  • substituents can be independently selected from the group consisting of halogen, Ci-12 alkyl, nitro, trifluoromethoxy, trifluoromethyl and Ci-12 alkoxy (all of such substituents being such as herein defined, including individual species and sub-groups thereof), such as, but not limited to, 4-fluorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl, 2- fluorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, trifluoromethylphenyl, 3,4- dimethoxyphenyl, iodophenyl, and bromophenyl.
  • C 1-n alkyl refers to a straight (non-branched) or branched chain saturated acyclic hydrocarbon monovalent group having from 1 to n carbon atoms such as, if n is 4, methyl, ethyl, propyl, n-butyl, 1 -methylethyl (isopropyl), 2-methylpropyl (isobutyl), and 1 ,1 -dimethylethyl (terf-butyl).
  • d -2 o alkyl refers to straight (non-branched) or branched chain groups having from 1 to 20 carbon atoms such as, for example, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like.
  • heterocyclic aromatic means a mono- or polycyclic, polyunsaturated, aromatic hydrocarbon group having from 4 to 12 carbon atoms and including one or more heteroatoms in one or more heterocyclic rings, each of said rings having 5 or 6 atoms (and optionally further including one or more heteroatoms attached to one or more carbon atoms of said ring, for instance in the form of a carbonyl, and/or to one or more heteroatoms of said ring, for instance in the form of a N-oxide), each of said heteroatoms being independently nitrogen, oxygen or sulphur, also including groups wherein a heterocyclic ring is fused to one or more aromatic homocyclic rings for instance in the form of benzo- fused, dibenzo-fused and naphtho-fused heterocyclic groups; within this definition are included hetero aromatic groups such as, but not limited to, thienyl(-ene), pyrrolyl(-ene), pyrid
  • halogen means any atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • Ci -n alkoxy refers to substituents wherein a carbon atom of a Ci -n alkyl group (such as defined herein above, including sub-groups thereof), is attached to an oxygen atom through a single bond, including methoxy, ethoxy, propoxy, n-butoxy, isopropoxy, sec-butoxy, and tert-butoxy.
  • Ci -n alkylsulfate refers to substituents wherein a carbon atom of a Ci -n alkyl group (such as defined herein above, including sub-groups thereof), is attached to an oxygen atom of a sulfate group through a single bond such as, but not limited to methylsulfate (methoxysulfonyloxy), ethylsulfate (ethoxysulfonyloxy), n- butylsulfate (n-butoxysulfonyloxy), terf-butylsulfate (terf-butoxysulfonyloxy), undecylsulfate (undecyloxysulfonyloxy), and the like.
  • active layer designates an organic layer which includes an organic semiconductor material exhibiting one type of electronic conductivity and possibly a second semiconductor material having the same or opposite type conductivity.
  • UV-Vis spectra were recorded using films dropcast from a CHCI3 solution on a quartz substrate on a Varian CARY 500 UV-Vis- NIR spectrophotometer from 200 to 800 nm at 600 nm/ min.
  • Fourier transform infrared (FT-IR) was performed on a Perkin Elmer Spectrum One FT-IR spectrometer with a nominal resolution of 4 cm "1 .
  • Samples for the FTIR were pellets in KBr or films dropcast from a CHCI3 solution.
  • Gas chromatography/mass spectrometry (GC-MS) was carried out on TSQ-70 and Voyager mass spectrometers.
  • Size exclusion chromatography was performed on a 1wt% polymer solution, which was filtered with a 0.45 ⁇ pore PTFE syringe filter.
  • a Spectra series P100 (Spectra Physics) pump equipped with two mixed-B columns (10 ⁇ , 2x30cm, Polymer Labs) and a refractive index detector (Shodex) at 40°C in THF at a flow rate of 1 .0 ml/min were used. Molecular weight distributions were measured relative to polystyrene standards. Toluene was used as a flow rate marker.
  • M1 2,5-dibromo-3-hexylthiophene
  • the organic phase was washed using 100ml of 2.5M NaOH solution, H 2 O and NaCl sa t and dried with MgSO 4 to obtain a yellow liquid that was purified using short path distillation to yield 81 % (15.50 g, 0.048mol) of a colourless liquid.
  • M2 was obtained after stirring 2 (1 eq, 36.2g, 0.143 mol) under reflux with 1 .3 eq. (18.93 g, 0.185 mol) of acetic anhydride and 140 ml of pyridine for 5 hours.
  • the mixture was neutralised by adding HCI, extracted with 3x100ml diethyl ether and washed with 3x100ml H 2 O.
  • the extract was dried over MgSO , filtered and evaporated.
  • M3 6-(2,5-dibromo-thiophen-3-yl)-hexanoic acid ethyl ester
  • 6-Bromo-hexanoic acid ethyl ester (20 g, 89 mmol) was added to active zinc and stirred for 2 h at room temperature under argon atmosphere. The zinc particles were allowed to settle overnight. The supernatant organozinc compound was added dropwise to a solution of 16.81 g 3-Bromothiophene (103 mmol) and 0.05 eq Ni(dppp)CI 2 in THF. The reaction was stirred for 48h at room temperature and quenched with a saturated NH CI solution. After extraction with Et 2 O (3 x 200 ml_), the organic phase was dried over MgSO and filtrated.
  • P3HT for use in a solar cell as a reference system was synthesized using the Rieke method for the production of highly regioregular poly(3- alkylthiophene)s.
  • a solution of M1 (1 eq, 10.04 g, 0.031 mol) in 80ml THF was added to active Zinc at -78°C.
  • the organozinc solution formed was added to a solution of 0.002 eq (0.035 g, 6.4 10 "5 mol) Ni(dppp)CI 2 in 40ml THF and stirred under inert atmosphere at 60°C for 18h.
  • the crude polymer was precipitated in a MeOH/ 2M HCI (2/1 , v/v) mixture and purified by solid phase extraction with methanol and hexane.
  • the purified polymer was extracted with chloroform and precipitated in MeOH before filtration and drying, yielding 3.63g (67%) of conjugated polymer.
  • the crude co-polymer was purified using a soxhlet extraction with methanol and pentane.
  • the purified poly-3- hexylthiophene-co-3-(2-acetoxyethyl)thiophene (P1 9/1 ) was extracted with chloroform and precipitated again in MeOH, before filtration and drying to obtain 3.18 g of a 9/1 copolymer in 61 % yield, which was characterised as follows:
  • P1 7/3 was obtained with a Mw of 45,000, a polydispersity index D of 2.1 and a regioregularity of 93%.
  • P1 1/1 was obtained with a Mw of 26800, a polydispersity index D of 1 .5 and a regioregularity of 93%.
  • 0.61 g P3 9/1 was obtained in 95% yield by reacting 0.60 g poly-3- hexylthiophene-co-3-(2-hydroxyethyl)thiophene (P2 9/1 ) with 0.62 g (0.004 mol) cinnamoyl chloride in THF in the presence of 0.37 g (0.004 mol) triethylamine, and was purified using soxhiet extraction with methanol and acetone before characterisation as follows:
  • UV-Vis ( ⁇ max .film) 521 ;
  • the synthesis proceeds according to the following scheme and provides a copolymer comprising recurrent units from a monomer represented by the structural formula (IX) wherein L' is L-NR'CO-J', L is ethylene, R' is H, and J' is cinnamoyl.
  • the synthesis proceeds according to the following scheme and provides a copolymer comprising recurrent units from a monomer represented by the structural formula (IX) wherein L' is L-SCO-J', L is ethylene and J' is cinnamoyl.
  • Copolymer P4 was synthesized following the Rieke method using active zinc (Zn*) and a nickel catalyst.
  • the monomer solution comprising M1 and M3 monomers in THF was added to Zn* at -78°C to obtain an organozinc compound.
  • This compound was added to a solution of 0.002 mol % nickel-catalyst in THF and stirred at 60°C for 18 h under inert atmosphere.
  • the polymers were precipitated in a 2/1 (v/v) mixture of methanol and 2M HCI and purified using a Soxhlet extraction with methanol, pentane and acetone.
  • the polymer was isolated by extraction with chloroform, precipitated in MeOH, filtered and dried. To obtain copolymers with different ratios of hexyl (m) and functionalized (n) side chains, monomer mixtures of various molar compositions were used. The various m/n ratios in the monomer feed before reaction with Zn* allowed to obtain copolymers with different m/n ratios of functional groups.
  • m/n ratios were chosen to be 9/1 , 7/3 and 1/1 to obtain P4 9/1 , P4 7/3, and P4 1/1 respectively.
  • the dibrominated monomers M1 and M3 were mixed in several molar ratios. Respectively 26.8, 28 and 20.1 mmol M1 (8.73, 9.13 and 6.55 g) were mixed with 3, 12 and 20.1 mmol of M3 (1 .14, 4.61 and 7.74 g) in a THF solution before applying the polymerization procedure.
  • the products of the bulk copolymerization were random copolymers, based on observations in 1 HNMR.
  • the M1/M3 ratio in the monomer solution corresponded to the m/n ratio in the copolymers.
  • the solubility of functionalized copolymers P4 was comparable to the solubility of P3HT in organic solvents like chlorobenzene (CB), chloroform (CHC ) or tetrahydrofurane (THF).
  • PCBM All blends of polymer: PCBM were made in a 1/1 ratio (w/w). PCBM has the following chemical formulae:
  • Optical micrographs were taken from blends spin-coated on silicon substrates.
  • Solar cells were made on glass ITO patterned substrates. All substrates were cleaned with sonicating in soapy water, Mili-Q water, acetone and heated in isopropanol followed by a UV/O3 treatment.
  • a PEDOTPSS (Baytron P) layer was spincoated from aqueous solution on the ITO electrode.
  • the polymer: PCBM (1 :1 ) blend was spincoated from a 10 mg ml_ "1 polymer solution in chlorobenzene and annealed for 15 minutes at 100 °C on a hotplate.
  • Differential scanning calorimetry (DSC) was done to measure the melting temperature (7m) and melting enthalpy (Hm) on a TA Instruments Q2000 (TzeroTM) with Refrigerator Cooling System (RCS) and nitrogen 50 ml_ min-i , aluminum TzeroTM crucible at a scan rate of 10.0 K min 1 .
  • the first cooling and second heating run were used for discussion.
  • the relative efficiency of P3HT:PCBM solar cells are displayed in Fig. 1 1 as a function of time for several temperatures.
  • the device efficiency is fairly constant for at least 100 h.
  • the efficiency of the P3HT:PCBM device decreases increasingly fast.
  • the degradation of Jsc is largely responsible for the decreasing efficiency.
  • the decrease in FF (see Fig. 16) and Voc (see Fig. 15) may also be related to reorganization effects in the blend, but other ageing mechanisms cannot be excluded at these temperatures and in this time interval.
  • Fig. 20-23 show the absolute short circuit current density, the absolute maximum power point, the absolute open circuit voltage and the absolute fill factor for P3HT, P1 9/1 , P2 9/1 and P3 9/1 solar cells in function of time upon continuous annealing at 100°C. There also, the solar cell performance is clearly much more stable in the case of the blends according to the present invention that in the P3HT:PCBM blend.
  • Fig. 24-27 show the absolute short circuit current density, the absolute maximum power point, the absolute open circuit voltage and the absolute fill factor for P3HT, P2 9/1 and P3 9/1 solar cells in function of time upon continuous annealing at 100°C. There also, the solar cell performance is clearly much more stable in the case of the blends according to the present invention that in the P3HT:PCBM blend.
  • the Jsc and efficiency of the P3HT solar cells decreases much more rapidly compared to the copolymer solar cells.
  • the morphology in a copolymer: PCBM blend according to embodiments of the present invention is much less sensitive to reorganization compared to P3HT, resulting in the increased thermal stability of copolymer:PCBM solar cells.
  • Introducing 10% of functionalized side chains does not affect the power conversion efficiency (PCE) significantly when compared to P3HT:PCBM devices processed according to the same procedure, but increases the morphological stability.
  • PCBM blends PCBM crystallization visible with optical microscopy, crystalline P3HT stacking in XRD
  • the presence of the functionalized side chains slows down the crystallization rate (not visible with DSC at 10 K min "1 ) which stabilizes the blend morphology.
  • the stable blend morphology in the device leads to a more stable photocurrent in solar cells at 125 °C.
  • the increased thermal morphological stability for the 9/1 copolymers presents a compromise between high efficiency and increased thermal stability in polythiophene:fullerene bulk heterojunction solar cells.

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Abstract

L'invention concerne de nouveaux monomères et polymères ainsi que des mélanges de tels polymères avec un accepteur d'électrons. L'invention concerne également un mélange qui est destiné à être utilisé dans un dispositif photovoltaïque et qui comporte : (a) un polymère comportant des motifs monomères selon la formule (I), dans laquelle L' est choisi dans le groupe constitué par L-C(O)O-J, L-C(O)NR'-J, L-OCO-J', L-NR'CO-J', L-SCO-J', L-O-J, L-S-J, L-Se-J, L-NR'-J et L-CN, où L représente un groupe alkylène linéaire ou ramifié ayant de 1 à 10 atomes de carbone, J représente un atome d'hydrogène ou un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, J' représente un groupe ayant de 1 à 10 atomes de carbone, qui est saturé ou insaturé, linéaire ou ramifié, comportant un motif phényle ou non, R' représente un atome d'hydrogène ou un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, et (b) un accepteur d'électrons tel qu'un dérivé de fullerène.
PCT/EP2009/066896 2009-12-11 2009-12-11 Polymères comportant des fractions thiophènes 3-substituées comme couches actives pour photopiles Ceased WO2011069554A1 (fr)

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JPWO2013094456A1 (ja) * 2011-12-22 2015-04-27 コニカミノルタ株式会社 有機光電変換素子
JP2013170187A (ja) * 2012-02-17 2013-09-02 Fujifilm Corp 有機光電変換素子組成物、これを含む薄膜、光電池、これに用いられる有機半導体ポリマー、化合物およびポリマーの製造方法
US9680103B2 (en) 2012-02-17 2017-06-13 Fujifilm Corporation Organic photoelectric conversion element composition, thin film and photovoltaic cell each containing the same, organic semiconductor polymer and compound each for use in these, and method of producing the polymer
EP2975391A1 (fr) 2014-07-17 2016-01-20 Peptisyntha Sa Capteur chimique, son procédé de fabrication et procédé pour la détection sélective d'analytes

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