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  • C09C1/44—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • C—CHEMISTRY; METALLURGY
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  • C01B32/00—Carbon; Compounds thereof
  • C01B32/15—Nano-sized carbon materials
  • C01B32/152—Fullerenes
  • C01B32/156—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
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  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data

Definitions

• the present invention relates to a fullerene functionalized with at least one oxazoline or dihydro- oxazine group.
• the present invention relates to a fullerene functionalized with at least one oxazoline or dihydro-oxazine group wherein said oxazoline or dihydro-oxazine group can be bound to fullerene through a condensed ring, or through a polyvalent organic group, or directly.
• the present invention also relates to a linear, branched or crosslinked polymer obtained by polymerization and/or crosslinking of said fullerene functionalized with at least one oxazoline or dihydro- oxazine group.
• the present invention also relates to an acceptor compound-donor compound structure, linear or co- crosslinked, obtained by the reaction of at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group, and at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups.
• the present invention also relates to the use of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, as well as of said linear, branched or crosslinked polymer obtained by polymerization of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, as well as of said acceptor compound-donor compound structure, in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, on both rigid and flexible supports .
• photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, on both rigid and flexible supports .
• the present invention also relates to a photovoltaic device comprising at least one fullerene functionalized with at least one oxazoline or dihydro- oxazine group, or at least one linear, branched or crosslinked polymer obtained by polymerization and/or crosslinking of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, or at least one linear or co-crosslinked acceptor compound- donor compound structure obtained by reaction between at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group and at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups, as well as to processes for the preparation thereof.
• Photovoltaic devices are capable of converting the energy of a luminous radiation into electric energy.
• most photovoltaic devices which can be used for practical applications exploit the physico-chemical properties of photoactive materials of the inorganic type, in particular high-purity crystalline silicon.
• high-purity crystalline silicon As a result of the high production costs of silicon, scientific research has long been orienting its efforts towards the development of alternative organic materials having a polymeric structure (so-called polymer photovoltaic cells ⁇ .
• organic polymers are characterized by a relative synthesis facility, a low production cost, a reduced weight of the relative photovoltaic device, in addition to allowing the recycling of said polymer at the end of the life-cycle of the device in which it is used.
• polymer photovoltaic cells The functioning of polymer photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound.
• the most widely-used electron donor compounds in photovoltaic devices are ⁇ -conj ugated polymers belonging to the groups of polyparaphenylene- vinylenes and of polythiophenes.
• the former ones can be used as both acceptor compounds and as donor compounds, on the basis of the electronic properties determined by the substituent groups of the polymeric chain.
• the latter ones are normally used as donor compounds.
• Derivatives of fullerene are most widely-used as acceptor compounds.
• the photo-absorption process with the formation of the exciton and the subsequent yielding of the electron to the acceptor compound involves the excitation of an electron from the HOMO (Highest Occupied Molecular Orbital) to the LUMO ⁇ Lowest Unoccupied Molecular Orbital) of the donor compound and, subsequently, the passage from this to the LUMO of the acceptor compound.
• HOMO Highest Occupied Molecular Orbital
• LUMO ⁇ Lowest Unoccupied Molecular Orbital the passage from this to the LUMO of the acceptor compound.
• the efficiency of a polymer photovoltaic cell depends on the number of free electrons which are generated by dissociation of the excitons, one of the structural characteristics of donor compounds which mostly influences said efficiency is the difference in energy existing between the HOMO and LUMO orbitals of the donor compound (so-called band-gap ⁇ .
• the wavelength of the photons which the donor compound is capable of collecting and of effectively converting into electric energy depends, in particular, on this difference.
• the energy difference between HOMO and LUMO of the donor compound if on one hand must not be excessively high in order to enable the greatest number of photons to be absorbed, on the other must not be excessively low, as it could decrease the voltage to the electrodes of the device.
• Another important characteristic of the materials used for producing photovoltaic devices is the mobility of the electrons in the acceptor compound and of the electronic gaps (or holes) in the donor compound, which determines the facility with which the electric charges, once photo-generated, reach the electrodes.
• the electronic mobility i.e. the mobility of the electrons in the acceptor compound and of the electronic gaps (or holes ⁇ in the donor compound, is not only an intrinsic property of the molecules, but is also greatly influenced by the morphology of the photoactive layer, which, in its turn, depends on the reciprocal miscibility of the compounds used in said photoactive layer and on their solubility.
• the phases of said photoactive layer must neither be excessively dispersed nor excessively segregated .
• the morphology of the photoactive layer is also critical with respect to the dissociation efficacy of the electronic gap (hole ) -electron pairs photo- generated.
• the average lifetime of the exciton is in fact such that this is able to be diffused in the organic material for an average distance not greater than 10 nm - 20 run.
• the donor compound and the acceptor compound phases must therefore be organized in nanodomains having dimensions comparable with this diffusion distance.
• the contact area of the donor compound-acceptor compound must be as large as possible and there must be preferential paths towards the electric contacts. This morphology, moreover, must be reproducible and must not change with time .
• polymer photovoltaic cells are produced by introducing a thin layer (about 100 nanometres) of a mixture of the acceptor compound and of the donor compound (generally known as bulk heteroj unction) , between two electrodes, normally consisting of indium-tin oxide (ITO) (anode) and aluminium (Al) (cathode) .
• ITO indium-tin oxide
• Al aluminium
• a solution of the two components is generally prepared and a photoactive layer is subsequently created on the anode [indium-tin oxide (ITO)] starting from this solution, resorting to suitable deposition techniques such as, for example, spin-coating, spray-coating, ink-jet printing, and the like.
• the counter-electrode i.e. the aluminium cathode (Al)
• Al aluminium cathode
• other additional layers capable of exerting specific functions of an electric, optical or mechanical nature, can be introduced between the anode and the photoactive film.
• the donor compound which is most commonly used in the construction of polymer photovoltaic cells is regioregular poly ( 3-hexylthiophene ) (P3HT).
• P3HT regioregular poly ( 3-hexylthiophene )
• This polymer has optimal electronic and optical characteristics (e.g., good HOMO and LU O orbital values, good adsorption coefficient) , a good solubility in the solvents used in the construction of photovoltaic cells and a reasonable mobility of the electronic gaps (or holes).
• polymers which can be advantageously used as donor compounds are: the polymer MDMO-PPV ⁇ (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1, 4- phenylene] -alt- ( vinylene) ⁇ , the polymer PCDTBT ⁇ poly[N- 9"-heptadecanyl-2, 7-carbazole-alt-5, 5- (4' , 7 ' -di-2-thi- enyl-2' , 1' , 3' -benzothiadiazole ] ⁇ , the polymer PCPDTBT ⁇ poly [2, 6- (4, -bis- (2-ethylhexyl) -4H-cyclopenta [2, 1- b;3, 4-b' ] dithiophene) -alt- 4, 7- (2,1,3- benzothiadiazole) ] ⁇ .
• the most widely-used acceptor compounds are generally derivatives of fullerene (C50 or C 7 o) , in particular methyl phenyl-Cgi-butyrate (PCBM), or methyl phenyl-C 7 i-butyrate (PC70BM) .
• Said derivatives of fullerene are generally capable of obtaining maximum conversion efficiencies of solar radiation of up to 8%.
• a film starting from an aqueous suspension of PEDOT:PSS poly (3, 4- ethylenedioxythiophene ) sulfonated polystyrene] is generally deposited, using suitable deposition techniques such as, for example, spin-coating, spray- coating, ink-jet printing, and the like.
• the morphology of the photoactive layer can be controlled by using, for example, suitable solvents in the deposition of the photoactive layer in which the acceptor compound and the donor compound have solubilities which are such as to form domains in the required dimensions.
• suitable solvents in the deposition of the photoactive layer in which the acceptor compound and the donor compound have solubilities which are such as to form domains in the required dimensions.
• chlorobenzene as deposition solvent of the poly (3-hexylthiophene) (P3HT) - methyl phenyl- C 60 -butyrate (PCBM) pair, allows finer morphologies of the photoactive layer to be obtained with respect to the use of toluene and, consequently, allows to obtain photovoltaic cells having a higher efficiency.
• the use of chlorobenzene can lead to the formation of excessively dispersed morphologies of the photoactive layer and, consequently, to a limited mobility of the electric charges towards the electrodes.
• Said drawback can be at least partially overcome by using mixtures of solvents, or by carrying out thermal treatment (annealing) on the final photovoltaic devices, in order to favour a certain de-mixing degree.
• the control of the experimental conditions for obtaining the desired result remains extremely critical.
• a third compound such as an alkanedithiol (for example, 1,4- butanedithiol , 1, 6-hexanedithiol, 1, 8-octanedithiol, 1 , 9-nonanedithiol ) , as described by Peet J. et al.
• a third compound such as an alkanedithiol (for example, 1,4- butanedithiol , 1, 6-hexanedithiol, 1, 8-octanedithiol, 1 , 9-nonanedithiol ) , as described by Peet J. et al.
• the Applicant consequently considered the problem of finding a new fullerene capable of stabilizing the morphology of the photoactive layer.
• the Applicant has now found a new fullerene functionalized with at least one oxazoline or dihydro- oxazine group, which can be used as acceptor compound in the construction of photovoltaic devices, capable of improving the stability of the photoactive layer.
• Said fullerene moreover, is capable of improving the mobility of the electrons in the acceptor compound and of the electronic gaps ⁇ or holes) in the donor compound, consequently allowing better conversion efficiencies of solar radiation.
• said fullerene is capable of both polymerizing and crosslinking, forming polymers and/or polymer networks, or of binding itself with a functionalized photoactive organic polymer forming linear acceptor compound-donor compound structures [i.e. covalently bound by means of (thio ) e ( s ) terimide bridges] or co-crosslinked .
• An object of the present invention therefore relates to a fullerene functionalized with at least one oxazoline or dihydro-oxazine group, wherein said oxazoline or dihydro-oxazine group can be bound to the fullerene through a condensed ring, or through a polyvalent organic group, or directly.
• said functionalized fullerene can have one of the following general formulae ( I ) , ( I I ) or (III):
• x represents an integer ranging from 50 to 250, preferably ranging from 60 to 90, extremes included, more preferably 60, 70, 84;
• n represents an integer ranging from 1 to 4, extremes included, preferably 1 or 2;
• 1 represents an integer ranging from 1 to 3, extremes included, preferably 1 or 2;
• k represents an integer ranging from 1 to 3, extremes included, preferably 1;
• A represents a ring condensed with the fullerene group selected from cycloalkyl groups having from 3 to 6 carbon atoms; or from heterocyclic groups having from 3 to 6 atoms containing from 1 to 3 heteroatoms selected from nitrogen, oxygen, sulfur;
• Y represents a polyvalent organic group having a valence m+1, selected from linear or branched alkylene groups, cycloalkylene groups, arylene groups, or combinations thereof; said alkylene, cycloalkylene or arylene groups optionally containing in the chain one or more heteroatoms selected from oxygen, nitrogen, sulfur, silicon, phosphorous;
• - Oxa represents an oxazoline or dihydro-oxazine group, preferably a 2-oxazoline group having the formula :
• R 1 , R 2 , R 3 , R 4 , R 5 and R 5 equal to or different from each other, represent a hydrogen atom; or a linear or branched alkyl group, having from 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl; a phenyl group; a benzyl group; a hydroxyalkyl group such as, for example, a hydroxymethyl group.
• the term “fullerene group” means a compound (e.g., a molecule) including a three- dimensional carbon skeleton having a plurality of carbon atoms.
• the carbon skeleton of said fullerene group generally forms a closed shell and can, for example, have a spherical or semi-spherical form. Alternatively, the carbon skeleton can form a not completely closed shell such as, for example, a tubular structure.
• Each carbon atom of said fullerene group is generally bound to three adjacent carbon atoms forming a tetrahedral network.
• the term “fullerene group” refers to either a substituted fullerene, or a non-substituted fullerene.
• said group Y can be selected from alkylene groups containing one or more double bonds and/or one or more triple bonds.
• said group Y can be selected from cycloalkylene groups containing, in the ring, a double and/or a triple bond.
• said group Y can be selected from arylene groups mono- or poly-condensed with cycloaliphatic rings, and/or with aromatic rings, and/or with heteroaromatic rings.
• said group Y can be selected from alkylene, cycloalkylene, or arylene groups, or combinations thereof, said alkylene, cycloalkylene, or arylene groups, being optionally substituted with alkoxyl groups and/or with carbonyl groups.
• said group Y can be selected from polyvalent organic groups having the following formulae :
• n, p, q, r are integers ranging from 1 to 12, preferably from 2 to 8, extremes included.
• said group Y can be selected from polyvalent organic groups having the following formulae :
• said fullerene functionali zed with at least one oxazoline or dihydro-oxazine group having general formula (I) can be selected from fullerenes having the following formulae:
• S 1 r S 2 , S 3 , S 4 , S 5 and S 6 equal to or different from each other, represent:
• said fullerene f nctionalized with at least one oxazoline or dihydro-oxazine group having general formula (II) can be selected from fullerenes having the following formulae:
• Oxa 1 , Oxa 2 , Oxa 3 , and Oxa 4 equal to or different from each other, represent a 2-oxazoline group or a 5 , 6-dihydro-2-oxazine group;
• Y has the same meaning described above ;
• S 1 represents a hydrogen atom; or a group selected from: alkyl groups having from 1 to 44 carbon atoms, linear or branched, saturated or unsaturated, cyclic or acyclic; aromatic groups having from 6 to 18 carbon atoms, mono- or poly- condensed with cycloaliphatic rings, with aromatic rings or with heteroaromatic rings; heteroaromatic groups; alkoxyl groups; carbonyl groups of the ketone or ester type.
• said fullerene functionalized with at least one oxazoline or dihydro-oxazine group having general formula (III) can be selected from fullerenes having the following formulae:
• Oxa 1 and Oxa 2 equal to or different from each other, represent a 2-oxazoline group or a 5, 6-dihydro-2- oxazine group;
• - S 1 represents a hydrogen atom; or a group selected from: alkyl groups having from 1 to 44 carbon atoms, linear or branched, saturated or unsaturated, cyclic or acyclic; aromatic groups having from 6 to 18 carbon atoms, mono- or poly-condensed with cycloaliphatic rings, with aromatic rings or with heteroaromatic rings; heteroaromatic groups; alkoxyl groups; carbonyl groups of the ketone or ester type.
• the fullerenes functionalized with at least one oxazoline or dihydro-oxazine group, object of the present invention can be obtained through various processes known in the art. Examples of these processes are provided hereunder.
• Methanofullerenes having general formula:
• C x represents a fullerene group, x has the same meaning described above;
• S 1 and S 2 equal to or different from each other, represent:
• a process ⁇ Bingel reaction which comprises reacting at least one fullerene having 60, 70, or 84 carbon atoms, with at least one oc-halogen- ketone or one a-halogen-ester having general formula (IV) :
• X represents a bromine atom, or a chlorine atom
• S 1 and S 2 equal to or different from each other, represent:
• At least one of S 1 and S 2 represents a group -CO- [-Y- (Oxa) ra ] , or a group -CO- 0- [-Y- (Oxa) m ] , in the presence of at least one chlorinated or non-chlorinated aromatic solvent such as, for example, chlorobenzene, toluene or mixtures thereof, and of least one base, such as, for example, sodium hydride, 1 , 3-dibutyl-urea (DBU) , lithium diamide, diethylamine, or mixtures thereof, at a temperature ranging from -78 °C to 25°C, for a time ranging from 1 hour to 48 hours
• S 1 and S 2 equal to or different from each other, represent:
• At least one of S 1 and S 2 represents a group - [-Y- (Oxa ) m ] , in the presence of at least one aromatic solvent such as, for example, toluene, at a temperature ranging from 25° C to 50°C [further details can be found in Bestmann H. J. et al., "Tetrahedron Letters” (1994), Vol. 35 (48), pages 9017-9020] ;
• S 1 and S 2 equal to or different from each other, represent:
• At least one of S 1 and S 2 represents a group - [-Y- (Oxa) m ] , in the presence of at least one aromatic solvent such as, for example, toluene, at a temperature ranging from 25° C to 50°C [further details can be found in Wang Y. et al . , "Tetrahedron Letters” (1995), Vol. 36 (38), pages 6843-6846] ;
• S 1 and S 2 equal to or different from each other, represent:
• At least one of S 1 and S 2 represents a group - [-Y- (Oxa) m ] , in the presence of at least one chlorinated aromatic solvent such as, for example, 1 , 2-dichlorobenzene, at room temperature (25° C) , for a time ranging from 24 hours to 72 hours, preferably 24 hours [Hummelen J. C. et al., "Journal of Organic Chemistry” (1995), Vol. 60 (3), pages 532-538].
• chlorinated aromatic solvent such as, for example, 1 , 2-dichlorobenzene
• C x represents a fullerene group
• x has the same meaning described above
• S 1 represents a group -[-Y- (Oxa) m ] wherein Y, Oxa and m have the same meanings described above, can be obtained through the following processes :
• S 1 represents a group - [-Y- (Oxa) m ] wherein Y, Oxa and m have the same meanings described above, in the presence of at least one chlorinated or non-chorinated aromatic solvent such as, for example, chloronaphthalene, chlorobenzene, toluene, or mixtures thereof, at a temperature ranging from 60°C to the reflux temperature of the solvent used, for a time ranging from 1 hour to 24 hours [further details can be found in Grosser T. et al., "Angewante Chemie” (1995), Vol. 34, pages 1343- 1345; Prato M. et al . , “Journal of the American Chemical Society” (1993), Vol. 115 (3), pages 1148- 1150] ;
• chlorinated or non-chorinated aromatic solvent such as, for example, chloronaphthalene, chlorobenzene, toluene, or mixtures thereof
• S 1 represents a group - [ -Y- (Oxa ) m ] , wherein Y, Oxa and m have the same meanings described above, in the presence of at least one chlorinated solvent or non-chorinated aromatic solvent such as, for example, tetrachloroethane, chloro-naphthalene, toluene, or mixtures thereof, at a temperature ranging from 110°C to 160°C, for a time ranging from a few minutes to 1 hour [further details can be found in Smith A.B. et al . , "Tetrahedron” (1996), Vol. 52 (14), pages 5257-5262].
• chlorinated solvent or non-chorinated aromatic solvent such as, for example, tetrachloroethane, chloro-naphthalene, toluene, or mixtures thereof
• C x represents a fullerene group
• x has the same meaning described above
• S 1 , S 2 , S 3 and S 4 equal to or different from each other, represent:
• S 1 , S 2 , S 3 and S 4 equal to or different from each other, have the same meanings described above, with the provision that at least one of S 1 , S 2 , S 3 and S 4 , represents a group - [-Y- (Oxa) m ] , in the presence of at least one aromatic solvent such as, for example, benzene, toluene, or mixtures thereof, at the reflux temperature of the solvent used, for a time ranging from 12 hours to 24 hours [further details can be found in Zhang X. Et al., "Journal of Organic Chemistry” (1996), Vol. 61 (16), pages 5456-5461].
• aromatic solvent such as, for example, benzene, toluene, or mixtures thereof
• C x represents a fullerene group
• x has the same meaning described above
• S 1 and S 2 equal to or different from each other, represent:
• S 1 and S 2 equal to or different from each other, have the same meanings described above, with the provision that at least one of S 1 and S 2 , represents a group - [-Y- (Oxa) m ] , in the presence of an aromatic solvent such as, for example, toluene, at room temperature (25°C), in an inert atmosphere, for irradiation at ⁇ > 530 nm, for a time ranging from 1 minute to 30 minutes [further details can be found in Zhang X. et al., "Journal of the American Chemical Society” (1993), Vol. 115 (23), pages 11024-11025] ;
• S 1 and S 2 equal to or different from each other, have the same meanings described above, with the provision that at least one of S 1 and S 2 , represents a group - [-Y- (Oxa) m ] , in the presence of a chlorinated solvent such as, for example, chlorobenzene, at room temperature (25°C) , for a time ranging from 1 hour to 24 hours [further details can be found in Matsui S. et al., "Tetrahedron Letters" (1999), Vol. 40 (5), pages 899-902] .
• a chlorinated solvent such as, for example, chlorobenzene
• C x represents a fullerene group
• x has the same meaning described above
• S 1 and S 2 equal to or different from each other, represent:
• ⁇ 1 and S 2 represents a group - [-Y- (Oxa) m ]
• trimethylenemethane which comprises reacting at least one fullerene having 60, 70, or 84 carbon atoms, with at least one trimethylenemethane having general formula (XIII):
• S 1 and S 2 represents a group - [-Y- (Oxa) m ] , wherein Y, Oxa and m have the same meanings described above, in the presence of at least one chlorinated solvent such as, for example, 1,2- dichlorobutane (DCB) , at a temperature ranging from 50°C to 100°C, for a time ranging from 12 hours to 24 hours [further details can be found in Prato M. et al . , "Journal of the American Chemical Society” (1993), Vol. 115 (4), pages 1594-1595].
• DCB 1,2- dichlorobutane
• C x represents a fullerene group, x has the same meaning described above;
• S 1 , S 2 , S 3 and S 4 equal to or different from each other, represent:
• S 1 represents a group - [ -Y- (Oxa) m ] , wherein Y, Oxa and m have the same meanings described above, in the presence of at least one chlorinated solvent such as, for example, chlorobenzene, at a temperature ranging from 25°C to 50°C, for a time ranging from 1 hour to 24 hours [further details can be found in Martin N. et al., "Journal of Organic Chemistry” (2000), Vol. 65 (19), pages 5986-5995].
• chlorinated solvent such as, for example, chlorobenzene
• C x represents a fullerene group, x has the same meaning described above;
• S 1 and S 2 equal to or different from each other, represent:
• At least one of S 1 and S 2 represents a group - [-Y- (Oxa) m ]
• S 1 and S 2 represents a group - [-Y- (Oxa) m ]
• S 1 and S 2 equal to or different from each other, have the same meanings described above, with the provision that at least one of S 1 and S 2 represents a group - [-Y- (Oxa) m ] , in the presence of at least one aromatic solvent such as, for example, benzene, at room temperature (25°C) , for a time ranging from 24 hours to several days [further details can be found in Muthu S. et al., "Tetrahedron Letters" (1994), Vol. 35 (11) pages 1763-1766] .
• aromatic solvent such as, for example, benzene
• S 1 represents a group - [-Y- (Oxa) m ] , wherein Y, Oxa and m have the same meanings described above, in the presence of at least one aromatic solvent such as, for example, toluene, at room temperature (25°C) , for a time ranging from 30 minutes to 60 minutes [further details can be found in Nair V. et al., "Tetrahedron Letters” (1999), Vol. 40 (27), pages 5087-5090; Nair V. et al., "Tetrahedron” (2002), Vol. 58 (15), pages 3009- 3013] .
• aromatic solvent such as, for example, toluene
• C x represents a fullerene group, x has the same meaning described above;
• S 1 , S 2 , S 3 , S 4 , S 5 and S 6 equal to or different from each other, represent:
• S 1 , S 2 , S 3 , s ⁇ S 5 and S 6 equal to or different from each other, have the same meanings described above, with the provision that at least one of S 1 , S 2 , S 3 , S 4 , S 5 and S 6 , represents a group - [-Y- (Oxa) m ] , in the presence of at least one aromatic solvent such as, for example, benzene, toluene, or mixtures thereof, at a temperature ranging from 25°C to 90 °C, for a time ranging from 1 hour to 48 hours [further details can be found in Krautler B. et al., "Tetrahedron” (1996) , Vol. 52 (14), pages 5033-5042; Chronakis N. et al., "Journal of Organic Chemistry” (2002), Vol. 67 (10), pages 3284- 3289] .
• aromatic solvent such as, for example, benzene, toluene, or mixtures thereof
• x represents a fullerene group, x has the same meaning described above;
• S 1 and S 2 equal to or different from each other, represent:
• X represents a chlorine atom or a bromine atom
• S 1 represents a group - [-Y- (Oxa) m ] wherein Y, Oxa and m have the same meanings described above, with at least one aliphatic solvent such as, for example, tetrahydrofuran, in the presence of at least one additive such as, for example, dimethylsulfoxide (DMSO) , N, N-dimethylformamide (N,N-DMF), or mixtures thereof, at a temperature ranging from 25°C to 150° C, for a time ranging from a few minutes to 10 hours;
• DMSO dimethylsulfoxide
• N,N-DMF N-dimethylformamide
• X represents a chlorine atom or a bromine atom
• S 2 represents a group - [-Y- (Oxa) m ] , wherein Y, Oxa and m have the same meanings described above, with at least one aromatic solvent (benzonitrile) , at a temperature ranging from 25°C to 150° C, for a time ranging from a few minutes to 8 hours .
• aromatic solvent benzonitrile
• a further object of the present invention relates to a polymer, linear, branched or crosslinked, obtained by the polymerization and/or crosslinking of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group.
• Said polymer, linear, branched or crosslinked can be obtained by means of polymerization and/or crosslinking processes "in situ" known in the art, starting from the fullerene functionalized with at least one oxazoline or dihydro-oxazine group object of the present invention. Examples of said processes can be found in Frump J. A., "Chemical Reviews” (1971), Vol. 71 (5), pages 483-505; Kobayashi S. et al., “Encyclopedia of Polymers Science and Engineering” (1987), Vol. 4, 2nd Ed., Wiley, New York, pages 525TM 537.
• Said polymer, linear, branched or crosslinked can be obtained, for example, by means of a polymerization and/or crosslinking process "in situ" which comprises: preparing a solution including at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group having general formula ( I ) , ( I I ) or (III), at least one initiator, and at least one organic solvent, and maintaining it at a temperature ranging from 15 °C to 35 °C, preferably ranging from 20 °C to 30 °C, for a time ranging from 15 minutes to 48 hours, preferably ranging from 20 minutes to 24 hours, optionally in an inert atmosphere (argon, nitrogen) ;
• evaporating the organic solvent at a temperature ranging from 15°C to 35°C, preferably ranging from 20°C to 30°C, at a pressure ranging from 0.05 mm/Hg to 760 mm/Hg, for a time ranging from 1 hour to 12 hours, preferably ranging from 2 hours to 8 hours, obtaining a film;
• a further object of the present invention relates to an acceptor compound-donor compound structure, linear or co-crosslinked, obtained by the reaction of at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group ⁇ acceptor compound) with at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups (donor compound) .
• Said acceptor compound-donor compound structure, linear or co-crosslinked can be obtained by means of polymerization and/or crosslinking processes "in situ" known in the art, by reaction of the fullerene functionalized with at least one oxazoline or dihydro- oxazine group object of the present invention, with a photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups. Examples of said processes can be found in Kagiya T. et al. "Polymer Letters” (1996), Vol. 4, pages 257-260; Nishikubo T. et al., "Macromolecular Chemie” (1984), Vol.185, pg . 1307- 1316.
• Said acceptor compound-donor compound structure, linear or co-crosslinked, can be obtained, for example, by means of a polymerization and/or crosslinking process "in situ" which comprises:
• photovoltaic devices such as, for example, photovoltaic cells, photo
• a further object of the present invention therefore relates to the use of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, or of said polymer, linear, branched or crosslinked, obtained by the polymerization and/or crosslinking of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, or of said acceptor compound-donor compound structure, linear or co- crosslinked; obtained by the reaction of at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group (acceptor compound) with at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups (donor compound) , in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules.
• a further object of the present invention also relates to a photovoltaic device comprising at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group, or at least one polymer, linear, branched or crosslinked, obtained by the polymerization and/or crosslinking of said fullerene functionalized with at least one oxazoline or dihydro-oxazine group, or at least one acceptor compound-donor compound structure, linear or co- crosslinked, obtained by the reaction of at least one fullerene functionalized with at least one oxazoline or dihydro-oxazine group (acceptor compound) with at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups (donor compound) .
• Said photovoltaic device can be prepared by means of various processes.
• a further object of the present invention therefore relates to a process for the preparation of a photovoltaic device in which the polymerization of the fullerene functionalized with an oxazoline or dihydro- oxazine group is carried out "in situ", which comprises:
• m 1 (acceptor compound), at least one photoactive organic polymer (donor compound) , at least one initiator, and at least one organic solvent, and maintaining it at a temperature ranging from 15°C to 35 °C, preferably ranging from 20°C to 30°C, for a time ranging from 15 minutes to 48 hours, preferably ranging from 30 minutes to 24 hours ;
• anode e.g., an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• PED0T:PSS polystyrene sulfonate
• a cathode e.g., a cathode consisting of aluminium
• a further object of the present invention relates to a process for the preparation of a photovoltaic device in which the polymerization of the fullerene functionalized with an oxazoline or dihydro-oxazine group is carried out "in situ", which comprises:
• m 1 (acceptor compound), at least one photoactive organic polymer (donor compound) , at least one initiator, and at least one organic solvent, and maintaining it at a temperature ranging from 15°C to 35°C, preferably ranging from 20°C to 30°C, for a time ranging from 15 minutes to 48 hours, preferably ranging from 30 minutes to 24 hours ;
• anode e.g., an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• PEDOT:PSS polystyrene sulfonate
• a cathode e.g., a cathode consisting of aluminium
• said photovoltaic device can be prepared by means of processes in which the crosslinking of the fullerene functionalized with at least two oxazoline or dihydro-oxazine groups having general formula (I) wherein k x 1 x m > 1, or having general formula ( I I ) wherein 1 x m > 1, or having general formula (III) wherein m > 1 (acceptor compound) , is carried out "in situ” obtaining a branched and/or crosslinked polymer.
• a further object of the present invention therefore relates to a process for the preparation of a photovoltaic device in which the crosslinking of the fullerene functionalized with at least two oxazoline or dihydro-oxazine groups is carried out "in situ", which comprises :
• anode e.g. an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• at least one layer of poly ( 3 , 4-ethylene- dioxythiophene) polystyrene sulfonate (PEDOT .* PSS) e.g. poly( 3 , 4-ethylene- dioxythiophene) polystyrene sulfonate (PEDOT .* PSS)
• a cathode e.g., a cathode consisting of aluminium
• a further object of the present invention relates to a process for the preparation of a photovoltaic device in which the crosslinking of the fullerene functionalized with at least two oxazoline or dihydro- oxazine groups is carried out "in situ", which comprises :
• anode e.g., an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• PEDOTiPSS polystyrene sulfonate
• a cathode e.g., a cathode consisting of aluminium
• said acceptor compound and said donor compound are bound by means of ( thio ) e ( s ) tereimide bridges.
• a further object of the present invention therefore relates to a process for the preparation of a photovoltaic device in which there is the formation of a linear acceptor compound-donor compound structure, which comprises:
• anode e.g., an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• PEDOTrPSS polystyrene sulfonate
• a cathode e.g., a cathode consisting of aluminium
• a further object of the present invention relates to a process for the preparation of a photovoltaic device in which there is the formation of a linear acceptor compound-donor compound structure, which comprises :
• m 1 (acceptor compound), at least one photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups (donor compound) , and at least one organic solvent, and maintaining it at a temperature ranging from 15°C to 35°C, preferably ranging from 20°C to 30°C, for a time ranging from 15 minutes to 48 hours, preferably ranging from 30 minutes to 24 hours; depositing said solution on the anode [e.g., an anode consisting of indium-tin oxide (ITO) ] , after having optionally previously deposited, on said anode, at least one layer of poly (3, 4-ethylene- dioxythiophene) polystyrene sulfonate ( PEDOT : PSS ) , obtaining the evaporation of the organic solvent and the formation of an anode-photoactive film structure ;
• anode e.g., an anode consisting of indium-tin
• a cathode e.g., a cathode consisting of aluminium
• said photovoltaic device can be prepared by means of processes in which there is the formation of a co-crosslinked acceptor compound-donor compound structure in which the acceptor compound is a fullerene functionalized with at least two oxazoline or dihydro-oxazine groups having general formula (I) wherein k x 1 x m > 1, or having general formula (II) wherein 1 x m > 1, or having general formula (III) wherein m > 1 (acceptor compound) , and the donor compound is a ' photoactive organic polymer functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups.
• a further object of the present invention therefore relates to a process for the preparation of a photovoltaic device in which there is the formation of a co-crosslinked acceptor compound-donor compound structure, which comprises:
• a cathode e.g., a cathode consisting of aluminium
• a further object of the present invention relates to a process for the preparation of a photovoltaic device in which there is the formation of a co- crosslinked acceptor compound-donor compound structure, which comprises:
• anode e.g., an anode consisting of indium-tin oxide (ITO)
• ITO indium-tin oxide
• PEDOT:PSS polystyrene sulfonate
• a cathode e.g., a cathode consisting of aluminium
• said processes can comprise, before depositing the cathode, depositing on said anode- photoactive film structure, at least one layer (cathodic buffer layer) comprising at least one carbonate of an alkaline metal such as, for example, caesium carbonate, or at least one oxide of a transition metal such as, for example, titanium dioxide .
• at least one layer comprising at least one carbonate of an alkaline metal such as, for example, caesium carbonate, or at least one oxide of a transition metal such as, for example, titanium dioxide .
• said processes can comprise, before depositing said solution on the anode, depositing on said anode, in substitution of said layer of poly (3,4- ethylenedioxythiophene ) polystyrene sulfonate ( PE DOT : PSS) , at least one layer (anodic buffer layer) comprising at least one oxide of a transition metal such as, for example, vanadium oxide ( V2O5 ) , molybdenum oxide ( 0O 3 ) , or at least one phthalocyanine of a transition metal such as, for example, copper phthalocyanine .
• a transition metal such as, for example, vanadium oxide ( V2O5 ) , molybdenum oxide ( 0O 3 )
• phthalocyanine of a transition metal such as, for example, copper phthalocyanine .
• said photoactive organic polymer can be selected from:
• polythiophenes such as, for example, poly (3- hexylthiophene ) (P3HT), poly ⁇ 3-octylthiophene ) , poly (3, 4-ethylenedioxythiophene) , or mixtures thereof;
• said photoactive organic polymer can be selected from poly ( 3-hexylthiophene ⁇ (P3HT) , or from polymers having the following general formulae:
• R is a C1-C2 0 , preferably C 6 -Ci 5 , linear or branched alkyl group; and n is an integer ranging from 2 to 500, preferably from 5 to 100.
• Poly (3-hexylthiophene) (P3HT) is preferred.
• said photoactive organic polymer functional! zed with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups can be selected from polythiophenes functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups such as poly (3- hexylthiophene) (P3HT) functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups, poly ( 3-octylthiophene) functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups, poly (3, 4-ethylenedioxythiophene) functionalized with at least one group selected from phenol, thiophenol, carboxyl, thiocarboxyl groups; or mixtures thereof.
• said initiator can be selected from Lewis acids such as, for example, boron trifluoride, iron trichloride, strong protic acids or their esters such as, for example, methyl tosylate (MeOTs) , methyl triflate (MeOTf) ; alkyl or aryl halides such as, for example, methyl iodide, benzyl bromide; or mixtures thereof.
• Lewis acids such as, for example, boron trifluoride, iron trichloride, strong protic acids or their esters
• MeOTs methyl tosylate
• MeOTf methyl triflate
• alkyl or aryl halides such as, for example, methyl iodide, benzyl bromide; or mixtures thereof.
• Methyl tosylate (MeOTs) , methyl triflate (MeOTf) or mixtures thereof, are preferred.
• said polymerization initiator can be used in an amount ranging from 0.1% in moles to 5% in moles, preferably from 0.5% in moles to 3% in moles, with respect to the number of moles of fullerene functionalized with at least one oxazoline or dihydro- oxazine group having general formula (I), (II), or (III) ⁇
• said organic solvent can be selected from aprotic polar solvents such as, for example, N-methyl- 2-pyrrolidone (NMP) , N, -dimethylacetate ( , -DMAc) , N, -dimethylformamide ( ⁇ , ⁇ -DMF), dimethylsulfoxide (DMSO) , acetonitrile ; aromatic solvents such as, for example, toluene, xylene; chlorinated solvents such as, for example, chlorobenzene , 1, 2-dichlorobenzene, chloroform, methylene chloride, trichloroethylene; or mixtures thereof. Chloroform, chlorobenzene, 1,2- dichlorobenzene, or mixtures thereof, are preferred.
• aprotic polar solvents such as, for example, N-methyl- 2-pyrrolidone (NMP) , N, -dimethylacetate ( , -DMAc) , N, -dimethylformamide (
• Said solution can be deposited on the anode by means of techniques known in the art such as, for example, spin-coating, spray-coating, ink-jet printing, and the like.
• the solid reaction product obtained was filtered, washed with methylene chloride (CH 2 C1 2 ) and then introduced, in small pieces, by means of a small spatula, into 1 1 of a 0.3 M aqueous solution of sodium bicarbonate (NaHC0 3 ) .
• the suspension obtained was kept under stirring, for 1 hour, and then filtered.
• the solid reaction product obtained was filtered, washed with methylene chloride (CH 2 C1 2 ) and subsequently introduced, in small pieces, using a small spatula, into 1 litre of an 0.6 M aqueous solution of sodium bicarbonate (NaHC0 3 ) .
• the suspension thus obtained was maintained under stirring, for 1 hour, and then filtered.
• the polymer thus obtained was re-dissolved in 10 ml of chloroform (CHCI 3 ) , at room temperature (25°C) , and subsequently poured into a flask and dried, at room temperature (25°C), by means of a mechanical pump.
• CHCI 3 chloroform
• Compound (10) was obtained by the polymerization of Compound (5 ⁇ (fullerene functionalized according to the present invention) obtained as described in Example 5. Said polymerization was carried out in accordance with Scheme 11 provided hereunder:
• 300 ⁇ of the solution obtained were then placed on a tablet of calcium fluoride (diameter 25 mm, thickness 2 mm) positioned in a spin coater of Chemat Technology, and subjected to a velocity increase profile of 400 revs/min for 30 seconds and 1,500 revs/min for 60 seconds.
• the IR absorption spectrum and the emission spectrum were then carried out respectively on the material thus deposited on the tablet, in order to evaluate the quenching of the fluorescence.
• the tablet was subsequently placed on a heating plate at a temperature of 120°C, for 30 minutes.
• the spectra indicated in Figure 1 were carried out again on the material [the wavenumber in cm "1 is reported in the abscissa, the absorbance in a.u. (arbitrary units) is reported in the ordinate] and in Figure 2 [the wavelength in nm is reported in the abscissa, the light intensity in a.u. (arbitrary units) is reported in the ordinate] .
• the decrease in its intensity to the progress of the heating i.e. a further 30 minutes at 150°C
• shows that the fullerene derivative (Fulloxal, Compound 5 ⁇ polymerizes: as shown in Scheme 11, in fact, the polymerization of Compound 5 involves the opening of the oxazoline ring with the consequent loss of the C N bond.

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