Classifications

• • 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
• • H—ELECTRICITY
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
  • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
  • H10K2102/10—Transparent electrodes, e.g. using graphene
  • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
  • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
• • H—ELECTRICITY
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/50—Photovoltaic [PV] devices
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  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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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
• • 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
  • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
• • 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
  • H10K85/221—Carbon nanotubes
  • H10K85/225—Carbon nanotubes comprising substituents
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to the field of photovoltaic devices, said third generation, which implement semiconductors of organic nature.
• Such devices which, to ensure a photovoltaic effect, implement organic semiconductors (often referred to as OSC, for the English "Organic Semi-Conductors”), are of recent design.
• OSC organic semiconductors
• These systems which began to be developed in the 1990s, are intended to replace, in the long term, the first and second generation devices, which use inorganic semiconductors.
• CSO Organic Semi-Conductors
• a first organic compound having a P-type semiconductor character which is generally a compound, preferably a polymer, which has electrons engaged in pi bonds, advantageously delocalized, and which is most often a conjugated polymer, typically poly (3-hexylthiophene), called P3HT; and
• this second compound being most often a derivative of fullerene, such as, for example, PCBM ([6,6] -phenyl-C 6 -methyl butyrate).
• the photovoltaic effect is obtained by placing the two organic semiconductors between two electrodes, in the form of a layer comprising these two mixed semiconductors (this layer being in direct contact with the two electrodes, or possibly connected at least to one of the electrodes via an additional layer, for example a charge collection layer); and irradiating the photovoltaic cell thus produced with adequate electromagnetic radiation, typically by the light of the solar spectrum.
• one of the electrodes is generally transparent to the electromagnetic radiation employed: in a manner known per se, a transparent anode of ITO (indium oxide doped with tin) may in particular be used.
• Obtaining the layer based on the mixture of two organic semiconductor compounds between the electrodes is typically made by depositing a solution of the two compounds in a suitable solvent (ortho-xylene, for example, in the case of a P3HT / PCBM mixture) and then evaporating this solvent.
• a suitable solvent ortho-xylene, for example, in the case of a P3HT / PCBM mixture
• ⁇ - ⁇ * transition from the highest occupied orbital (HOMO) to the orbital vacant molecular molecule (LUMO)
• HOMO highest occupied orbital
• LUMO orbital vacant molecular molecule
• the exciton thus created can be dissociated at the P / N interface and the excited electron created during irradiation can thus be conveyed by the N type semiconductor to the anode, the hole being led to the cathode via the P-type semiconductor.
• Photovoltaic devices employing organic semiconductors are potentially promising. Indeed, taking into account the use of organic compounds of the polymer type to replace inorganic semiconductors, they offer the advantage of being more mechanically flexible, and therefore less fragile, than the first and second generation systems. . In addition, they are lighter and they are also easier to manufacture and they are less expensive.
• additives proposed in this context are toxic or harmful to the environment, especially when these additives have a volatile nature inducing their release in the environment close to the photovoltaic cell.
• the presence of these additives, reagents may have a more or less short-term negative influence on the mechanical and electrical properties of the layer ensuring the photovoltaic effect.
• it can induce the presence of non-conductive impurities, or even affect the stability of the mixture of semiconducting organic compounds (this is in particular the case of additives capable of generating free radicals (such as thiols for example) which induces in particular an accelerated degradation of P-type semiconductor compounds such as P3HT.
• An object of the present invention is to provide a more systematic method for improving the photocatalytic efficiency of a mixture of P and N semiconductor organic compounds as used in third-generation photovoltaic devices, without having to this to introduce reactive additives of the aforementioned type within the mixture of compounds used to obtain the photovoltaic effect.
• the present invention provides a new technique for producing layers based on a mixture of P-type and N-type semiconductor organic compounds, which makes it possible to optimize the mixing of the two compounds within the layer produced. and which proves to ensure increased photovoltaic efficiency irrespective of the semiconductor pair considered.
• the subject of the present invention is a method allowing the application on all or part of the surface of a support of an organic coating of a photovoltaic nature based on a mixture of organic semiconductors, which comprises at least a first organic P -type semiconductor compound P, and at least one second N -type organic compound C N, immiscible in the Cp compound in the coating produced.
• This method of applying the coating comprises the following steps:
• a second fraction, miscible with the first fraction consisting of a solvent or mixture of solvents S2 which has a boiling point greater than that of the solvent or mixture of solvents S1 and lower than that of the compounds C P and C N and which is capable of selectively solvating one of the compounds C P or C N but not the other (ie incapable of solvating respectively C N or C P ); and
• the mixture of organic semiconducting compounds C P and C N is deposited in solvated form, as in the deposits of such mixtures made in currently known processes, but with a fundamental difference, namely that employs a very specific solvent, consisting of the mixture of fractions S1 and S2 as defined above.
• fraction S1 more volatile than fraction S2
• evaporates first which leads to an enrichment in phase S2 in the solvent medium of the deposit produced, which makes the solvent medium less and less capable of solvating the compound that fraction S2 is not capable of solvating. It follows a desolvation of at least a part of one of the compounds C P or C N proper to lead to a demixing phenomenon of this compound, the other compound (respectively C N or C P ) remaining instead, at first, in a solvated form, given the presence of a sufficient amount of S1 fraction in the medium, not yet evaporated.
• step (B) It is only in a second phase of step (B) that all the solvents are evaporated, to leave as a coating a mixture of compounds C N and C P substantially free of solvent.
• the solid coating obtained on the support has a specific morphology, having a high contact interface between the C N compounds. and C P.
• the method of the present invention has, inter alia, the advantage of leading to obtaining such properties without having to introduce into the coating any additive remaining in the final coating.
• the solvent S responsible for obtaining the structure is indeed removed during step (B) of the process.
• the steps (A) and (B) are carried out without using in the solution of the compounds C N and C P any additive capable of reacting chemically with the compounds C N and C. P.
• the solution comprising the C P and C N compounds which is carried out in step (A) is excluded compounds likely to remain in the coating at the end of the step (B), in particular of compounds having a boiling point greater than or equal to that of the compounds C N and C P.
• the solution comprising the compounds C P and C N of the step (A) consists of the compounds C P and C N and the solvent S (resulting from the mixture of the fractions S1 and S2), to the exclusion of any other compound.
• the method of the invention may comprise an additional step (C) of heat treatment of the solid coating obtained at the end of the annealing step (B), which generally allows, among other things, to consolidate or even further optimize the morphology of the coating resulting from step (B).
• Such a step is however not required to obtain an improvement in properties as observed in the context of the present invention. Therefore, according to a particular embodiment, the method of the invention may not include such an additional step (C) heat post-treatment of the coating obtained at the end of step (B).
• step (C) is preferably carried out by bringing the coating to a temperature of 70 ° to 200 ° ⁇ (for example between 100 and ⁇ ⁇ ' ⁇ , in particular between 130 and ⁇ ⁇ ' ⁇ ) generally for 1 to 30 minutes typically for 5 to 15 minutes. If necessary, this step is advantageously carried out under a controlled atmosphere (nitrogen, argon in particular), for example in the case where one and / or the other of the compounds C N or C P proves to be sensitive to oxidation, atmospheric humidity or any other compound likely to be present in the air (sulfur pollutant for example).
• a controlled atmosphere nitrogen, argon in particular
• step (C) The work carried out by the inventors in the context of the present invention has made it possible to demonstrate that the morphology obtained by implementing steps (A) and (B) makes it possible to improve the photovoltaic properties of the coating produced, compared to the known methods of the type where the two compounds are deposited in solution in a solvent medium capable of solvating the two compounds, namely without the presence of the specific fraction S2 implemented in the process of the invention, and this so quite pronounced when step (C) is implemented.
• the method of the invention leads to a clear improvement in the photovoltaic efficiency of the coating, which is reflected in particular by an increase in power conversion efficiency (PCE, for English “ Power conversion efficiency ”) as well as the filling factor (FF, namely" FUI Factor "in English) of photovoltaic devices implementing a photovoltaic coating as obtained according to the invention
• PCE power conversion efficiency
• FF filling factor
• the values of PCE and FF are characteristic quantities of photovoltaic devices which are commonly used and which are defined in particular in the article "Conjugated Polymer-Based Organic Solar Cells", published in Chemical Reviews, 107, (4), pp. 1324-1338 (2007).
• the value of the ECP corresponds to the ratio of the maximum power delivered by the material related to the power of the luminous flux illuminating it.
• the fill factor (between 0 and 1) reflects the more or less distant nature of the material from that of an ideal diode (a form factor of 1 corresponding to the case of an ideal diode).
• the method of the invention makes it possible to obtain multiple entangled domains of C compounds N and C P , these domains having dimensions of the order of at most a few tens of nanometers, which are suitable for inducing both a large number of C N / C P interfaces made (essential in organic photovoltaic materials to ensure a chemical potential gradient strong enough to separate the electron-hole pairs created by photovoltaic effect, which are coupled much more strongly than in the case of inorganic semiconductors) with very short distances to cover for holes and electrons within the material (allowing the electron and the hole can reach respectively the anode and the cathode without being trapped by the material).
• the method of the present invention has the advantage of being able to be conducted with any pair of organic compounds C N and C P, respectively N type and P type and immiscible with each other under the conditions of formation and use of the photovoltaic coating.
• organic semiconductor compound C N any electron acceptor material known to have such properties, which may for example be chosen from the following compounds:
• PCBM [6,6] -phenyl-C61-methylbutyrate
• PCNEPV poly [oxa-1,4-phenylene- (1-cyano-1,2-vinylene) - (2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylene) -1,2 - (2-cyanovinylene) -1,4-phenylene
• PCBM [6,6] -phenyl-C61-methylbutyrate
• PCNEPV poly [oxa-1,4-phenylene- (1-cyano-1,2-vinylene) - (2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylene) -1,2 - (2-cyanovinylene) -1,4-phenylene
• PSS poly (styrene sulfonate)
• fullerene derivatives in particular the PCBM ([6,6] -phenyl-C61-methyl butyrate), are particularly particularly suitable as the semiconductor organic compound C N according to the present invention.
• organic semiconductor compound C P any material known to have a P-type semiconductor character can be used in the context of the present invention.
• the organic semiconductor compound C P is a chosen organic conjugated polymer. preferably from the following compounds:
• polythiophene derivatives such as P3HT (poly (3-hexylthiophene)
• MDMO-PPV poly [2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylenevinylene]
• MEH-PPV poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene]
• P3HT poly (3-hexylthiophene) are particularly suitable as the organic semiconductor compound C P in the process of the present invention.
• organic semiconductor compounds (C N and C P) which are used in the context of the present invention may also be chosen from conjugated aromatic molecules containing at least three aromatic nuclei, optionally fused.
• Organic semiconductor compounds of this type may for example comprise 5, 6 or 7 conjugated aromatic rings, preferably 5 or 6. These compounds may be monomers as well as oligomers or polymers.
• T1 and T2 are, for example, independently H, Cl, F, or C1-C6 alkyl (i.e. having 1 to 6 carbon atoms), preferably C4 and Rc is H, an optionally substituted alkyl or an optionally substituted aryl.
• aromatic rings may also be optionally substituted with one or more groups selected from alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl or substituted aryl, halogen (in particular -F or Cl, preferably F), cyano, nitro, and optionally substituted secondary or tertiary amines (preferably amines of formula -NRaRb where each of Ra and Rb is, independently, H, or an optionally substituted (and optionally fluorinated or even perfluorinated) alkyl group, optionally substituted aryl (for example fluoro), alkoxy or polyalkoxy, More generally, organic semiconductor compounds (C N and C P ) which can be used according to the present invention include compounds and polymers chosen from polymers and conjugated hydrocarbon oligomers such as polyacenes, polyphenylenes, poly (phenylene vinylene), polyfluorene, condensed aromatic hydrocarbons such as t etracene, chrysen
• Suitable solvents as fractions S1 and S2 for a couple of compounds C N and C P considered can typically be selected by considering the Hansen parameters of the two compounds C N and C P and with reference to the Hansen space.
• Hansen's parameters also known as Hansen solubility parameters
• the Hansen parameters of a given chemical species generally designated by ⁇ 0 , ⁇ ⁇ , and ⁇ ⁇ , which respectively reflect the dispersal energy, the polar energy and the hydrogen bonding energy between these chemical species.
• Hansen's space These three parameters define the coordinates of a point in Hansen's three-dimensional space.
• the indexing of chemical species in the Hansen space allows a prediction of the affinity of two species, species being generally all the more compatible between them that they are close to each other in space from Hansen.
• Hansen's space and their uses for predicting affinities between molecules we can refer in particular to "Solubility parameters"; Charles M. Hansen, Alan Beerbower, Othmer Kirk, supplement volume, pp. 889 to 8902 th edition 1971.
• solubility volume located around the coordinate point ⁇ 0 , ⁇ ⁇ and ⁇ ⁇ , which typically has the shape of a more or less deformed ellipsoid , characterized in the three dimensions of the Hansen space by rays r D , r P and r H, respectively.
• This solubility range makes it possible to define the solvents capable of solubilizing or solvating the chemical species in question, these solvents being those whose solubility volume at least partially covers the solubility volume of the chemical species.
• ⁇ (e, s) [(5 D (e> - ⁇ 0 (s)) / r D ] 2 + [( ⁇ ⁇ ( ⁇ ) - ⁇ ⁇ (s) ) / r P ] 2 + [( ⁇ ⁇ (e ) - ⁇ ⁇ (s) ) / r H f - 1
• ⁇ 0 (e), ⁇ ⁇ ( e) and ⁇ ⁇ ⁇ e ) are the three Hansen solubility parameters of species e
• r D , r P and r H are the rays of the Hansen solubility space of species e in each of the three directions of Hansen space; and
• ⁇ ⁇ (s) and ⁇ ⁇ (s) are the Hansen solubility parameters of the solvent s.
• This parameter ⁇ (e, s) reflects the location of the coordinate point ⁇ D (s) , ⁇ ⁇ (s) and ⁇ ⁇ ⁇ S) representative of the solvent s in the Hansen space, with respect to the solubility volume of species e, namely
• the fraction S 1 of the solvent S used in the solution of step (A) may advantageously be chosen from solvents whose solubility volume partially cuts both the volume of solubility of the compound C N and the solubility volume of the compound C P , as well as mixtures of such solvents.
• fraction S 2 of the solvent S this may advantageously consist of:
• At least one solvent for which (C P , s)> 0 and (C N , s) ⁇ 0 solvent capable of selectively solvating C N but not C P ) or a mixture of such solvents.
• the ratio of solvent fractions S1 and S2 to implement can vary to a large extent.
• the fraction S2 is a minority in the solvent S, the volume ratio S2 / (S1 + S2) of the volumes of the two fractions S1 and S2, measured before mixing (to overcome possible contraction effects), being generally less than 50%, in general less than 25%, or even 10%.
• the observation of the effect of improving the properties of the photovoltaic material according to the invention does not also require very high concentrations of fraction S2, sensitive results being observed with values of the volume ratio S2 / (S1 + S2). as low as 0.001%.
• this volume ratio S 2 / (S 1 + S 2) is greater than or equal to 0.01%, more preferably greater than or equal to 0.05%, and even more preferentially from less 0.1%.
• the volume ratio S 2 / (S 1 + S 2) is between 0.05% and 10%, for example between 0.1% and 5%.
• the concentration of each of these compounds in the solvent S is advantageously between 0.1% and 5% by weight relative to the mass of the solution, preferably between 0.5% and 2%, before the implementation of step (B), the thickness of the coating obtained at the end of step (B) being as much as this concentration is important but also depending on the mode of application of the solution on the surface in step (A).
• the ratio of the amount of the compounds C P and C N is preferably such that the ratio of the total number of proton acceptor sites of the compounds C P relative to the total number of proton acceptor sites of the compounds C P and C order of 1, for example between 0.8 and 1, 2.
• the method of the present invention adapted to the use of a very large number of N and P type organic semiconductor compounds, finds, inter alia, an interesting application in the specific case where the organic semiconductor compound C N is a fullerene derivative, in particular PCBM, where the organic semiconductor compound C P is a polythiophene derivative, such as P3HT (poly (3-hexylthiophene)
• the two compounds are preferably used in step (A) with a weight ratio of between 0.2 and 5, and typically of the order of 1: 1 in the solvent S.
• the total concentration of PCBM / P3HT in the solution is preferably between 0.5 and 10%, for example of the order of 2% by weight relative to the total mass composition S before use of step (B).
• the solvent S used in steps (A) and (B) of the process is advantageously a mixture of two fractions S1 and S2 chosen as follows:
• ⁇ the S1 fraction implementation in the case of torque PCBM / P3HT may be chosen from solvents generally recommended to carry out the deposition of the mixture of polymers of this type, well known per se.
• the fraction S1 may comprise one or more solvents chosen from chlorobenzene, dichlorobenzene (o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene), trichlorobenzene, benzene, toluene, chloroform and dichloromethane. , dichloroethane, xylenes (in particular ortho-xylene), ⁇ , ⁇ , ⁇ trichlorotoluene, methylnaphthalene (1-methylnaphthalene and / or 2-methylnaphthalene), chloronaphthalene (1-chloronaphthalene and / or 2-chloronaphthalene) .
• chlorobenzene o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene
• trichlorobenzene benzene
• benzene toluene
• the fraction S1 comprises at least one xylene, preferably at least one of ortho-xylene.
• the fraction S1 is entirely composed of one or more xylene (s), for example by ortho-xylene.
• the S2 fraction implementation in the case of torque PCBM / P3HT comprises advantageously at least one solvent selected from one of the compounds corresponding to one of general formulas (I), (II), (III) and (IV) below:
• each of the groups E 1 , E 2 , E 3 and E 4 is a linear or optionally branched, saturated or unsaturated, optionally aromatic, hydrocarbon group, respectively mono-, di-, tri- and tetravalent, and typically comprising from 1 to at 20 carbon atoms, these spacer groups being typically alkyl, aryl, arylalkyl, or alkylaryl (respectively alkylene, arylene, arylalkylene, or alkylarylene for the polyvalent groups) groups; and
• each of the groups Y 1 , Y 2 , Y 3 and Y 4 which are identical or different, is a group carrying at least one polar function, possibly capable of producing intermolecular associations of the hydrogen bond or dipole-dipole type.
• each of the groups A, B, D and E carries (or consists of) at least one amide, ester, ketone, carboxylic acid, aldehyde, amine, phosphonium, sulfonium, or allylphosphonate group.
• the fraction S2 used in the case of the pair PCBM / P3HT is more preferably constituted by one or more solvents corresponding to one of the general formulas (I), (II), (III) and (IV).
• the fraction S 2 used in the case of the pair PCBM / P3HT comprises (and preferably consists of) one or more of the following solvents:
• each of the groups R and R 2 which may be identical or different, is a linear or branched, cyclic or non-cyclic C 1 -C 20 alkyl, aryl, alkylaryl or arylalkyl group (i.e. having from 1 to 20 carbon atoms; ); and
• the group A represents a linear or branched divalent alkylene group.
• the groups R 1 and R 2 which may be identical or different, may especially be chosen from methyl, ethyl, n-propyl, isopropyl, benzyl, phenyl, n-butyl and isobutyl groups. cyclohexyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl.
• R 1 and R 2 are two methyl, ethyl or isobutyl groups, preferably identical.
• Group A compounds of formula (11-1) is, for its part, preferably a divalent alkylene group in CC 6 , preferably in C 2 -C 4.
• the compounds of formula (11-1) can be described as the result of an esterification of a dicarboxylic acid of formula HOOC-A-COOH with alcohols of formulas R -OH and R 2 -OH, which are identical or different.
• the compounds of formula (I) may be in the form of a mixture of molecules which may be described as resulting from an esterification of a carboxylic acid diol of formula HOOC-A-COOH with a mixture of alcohols, for example a mixture of natural alcohols.
• the alcohols present in the triglycerides of natural oils for example fusel oil.
• group A is an ethylene group (-CH 2 -CH 2 -), propylene (-CH 2 -CH 2 -CH 2 -) or butylene (-CH 2 -CH 2 -CH 2 -CH 2 -),
• the Compounds of formula (11-1) is a succinate diester diester, glutarate diesters, and adipate diesters, respectively.
• the fraction S2 is used a mixture of several dicarboxylic acid diesters of formula (11-1) distinct. Alternatively, one can only use one.
• the group A of the compounds of formula (11-1) is a linear divalent group, in particular ethylene (-CH 2 -CH 2 -), propylene (-CH 2 -CH 2 -CH 2 -) or butylene (-CH 2 -CH 2 -CH 2 -CH 2 -).
• compounds of formula (II-1) which are well adapted to the formation of fraction S2 are dimethyl adipate, dimethyl glutarate and dimethyl succinate, preferably employed in a mixture, preferably employed in the form of a mixture of these three compounds, advantageously with the following proportions for the 3 compounds (proportions given by mass), which can be determined in particular by gas chromatography)
• the group A is a branched group, in general a branched C3-C10 divalent alkylene.
• Group A compounds of formula (11-1) may in particular be a group C 3, C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , or a mixture.
• Compounds of formula (11-1) in which the group A is a C 4 group (ie comprising 4 carbon atoms) are particularly well suited for the formation of a fraction S 2 adapted to the case of the pair PCBM / P3HT.
• compounds of formula (II-1) may in particular be a group C 3, C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , or a mixture.
• a particularly suitable compound is dimethyl ester of 2-methylglutaric acid, corresponding to the following formula:
• the fraction S2 implemented in the case of the pair PCBM / P3HT comprises a mixture comprising the following diester of dicarboxylic acids:
• R and R 2 are preferably methyl, ethyl or isobutyl groups.
• This mixture preferably comprises:
• R-OOC-A MG -COO-R 2 diester from 70 to 95% by weight of the R-OOC-A MG -COO-R 2 diester, wherein R 1 and R 2 are preferably two methyl groups;
• R-OOC-A ES -COO-R 2 diester from 5 to 30% by weight of the R-OOC-A ES -COO-R 2 diester, where R 1 and R 2 are preferably two methyl groups;
• R-OOC- (CH 2) 4 -COO-R 2 diester optionally up to 10% by weight of the R-OOC- (CH 2) 4 -COO-R 2 diester, preferably the methyl diester.
• R 3 is a group chosen from hydrocarbon groups comprising a number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic,
• R 4 and R 5 which are identical or different, are groups chosen from hydrocarbon groups comprising a number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, optionally substituted, R 2 and R 3 may optionally together form a ring, optionally substituted and / or optionally comprising a heteroatom, and A is a linear or branched cleavage alkyl group, preferably comprising an average number of carbon atoms ranging from 2 to 12, preferably from 2 to 4.
• the groups R 3 , R 4 and R 5 which may be identical or different, may in particular be groups chosen from alkyl, aryl, alkaryl, arylC 1 -C 12 alkyl or phenyl groups.
• the groups R 2 and R 3 may optionally be substituted, in particular with hydroxyl groups.
• the group R 3 can especially be chosen from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, isoamyl, n-hexyl, cyclohexyl, 2-ethylbutyl, n-octyl, isooctyl, 2 -ethylhexyl, tridecyl.
• the groups R 4 and R 5 which may be identical or different, may especially be chosen from methyl, ethyl, propyl (n-propyl), isopropyl, n-butyl, isobutyl, n-pentyl, amyl, isoamyl, hexyl and cyclohexyl groups. hydroxyethyl.
• the group A present in the compounds of formula (II-2) can be a group A as defined in the context of the compounds (11-1).
• the group A of the compounds of formula (II-2) is a divalent linear alkyl group; typically -CH 2 -CH 2 - (ethylene); -CH 2 -CH 2 -CH 2 - (n-propylene); or -CH 2 -CH 2 -CH 2 - (n-butylene).
• compound examples of formula (II-2) well adapted to the formation of the S2 fraction are the following compounds:
• the group A of the compounds of formula (II-2) is a divalent branched alkylene group, preferably corresponding to one of the following formulas:
• x is an integer greater than 0,
• y is an average integer greater than or equal to 0,
• z is an average integer greater than or equal to 0,
• each of R 6 which may be identical or different, is a CC 6 alkyl group, preferably CC 4 , and
• each of R 7 which is identical or different, is a hydrogen atom or a CC 6 alkyl group, preferably CC 4 .
• M G represents a group -CH (CH 3 ) -CH 2 -CH 2 -, or a group -CH 2 -CH 2 -CH (CH 3 ) - or a mixture of such groups
• ES represents a group -CH (C 2 H 5 ) -CH 2 -, or -CH 2 -CH (C 2 H 5 ) - or a mixture of such groups
• Pe represents a pentyl group, preferably isopentyl or isoamyl
• Cyclo represents a cyclohexyl group.
• Bu represents a butyl group, preferably n-butyl or tert-butyl
• EtBu represents an ethylbultyl group.
• Potentially useful compounds as solvents for the S2 fraction according to the present invention are the compounds described in Examples 1 and 3 of Application WO2009 / 092795.
• each of R 9 , R 0 , R and R 2 which are identical or different, is:
• alkyl group linear or branched, optionally cyclized in whole or in part, preferably Ci-Ce, and more preferably C 1 -C 4 , or
• a ' is a divalent group of formula -CH 2 -CH 2 - (CHR 4 ) z - (CHR 3 ) x - (CHR 4 ) y - where:
• x is an integer greater than 0,
• y is an average integer greater than or equal to 0,
• R 3 which may be identical or different, is a C 1 -C 6 alkyl group, preferably C 1 -C 4 , and
• each of the R 14 which may be identical or different, is a hydrogen atom or a CC 6 alkyl group, preferably a dC 4 alkyl group.
• the groups R 8 , R 9 , R 10 and R 11 which may be identical or different, are preferably chosen from methyl, ethyl, propyl (n-propyl), isopropyl, n-butyl, isobutyl, n-pentyl and amyl groups. isoamyl, hexyl, cyclohexyl. They are preferably identical.
• the groups R 14 can in particular be linear, branched or cyclic.
• R 2 , R 3 , R 4 and R 5 are identical and selected from methyl, ethyl, n-propyl, or isobutyl.
• Examples of compounds of formula (II-3) suitable for forming the S 2 fraction of the solvent S used in the context of the present invention are the compounds of the following formula:
• R 5 is alkyl, aryl, alkylaryl, or arylalkyl, linear or branched, cyclic or noncyclic, -C 36, for example, DC 20 (typically methyl, ethyl or propyl); and
• the group A "represents a linear or branched alkyl group preferably comprising from 2 to 6 carbon atoms, for example 4 carbon atoms.
• each of R 6 and R 17 group is alkyl, aryl, alkylaryl, or arylalkyl, linear or branched, cyclic or noncyclic, -C 36, for example Ci-C 20 (typically a group methyl, ethyl or propyl); and
• the group A '" represents a linear or branched alkyl group preferably comprising from 2 to 6 carbon atoms, for example 4 carbon atoms.
• the fraction S2 used in the case of the pair PCBM / P3HT is constituted by a mixture comprising by weight relative to the total weight of the mixture:
• the method of the invention opens the possibility of implementing a large panel of solvents in steps (A) and (B). This possibility makes it possible in many cases to avoid the use of solvents having a negative impact on the environment by substituting them with more interesting solvents, for example from biological materials or biomass, or with a low impact on the environment. the environment.
• the fraction S2 used in the case of the pair PCBM / P3HT may advantageously consist of one or more solvents chosen from the following commercial solvents: Rhodiasolv RPDE; Rhodiasolv Iris; Rhodiasolv DEE; the Rhodiasolv ADMA 810.
• step (A) the deposition of the solution on all or part of the surface may be carried out according to any means known per se.
• An interesting method, which leads at the end of step (B) to obtaining a photovoltaic coating of controlled and homogeneous thickness is to perform the deposition of step (A) by centrifugal coating (also known under its English name "spin coating") namely by applying the solution containing the compounds C N and C P on the rotated support.
• spin coating also known under its English name "spin coating”
• Another possibility is to perform the graded scallop deposition of the solution on the surface of the coating, typically using a microcalibrated blade.
• the operating temperature of step (A) is chosen so as not to affect the stability of the compounds in the presence and to maintain the solubility of the compounds C N and C P within the solution S as well as the immiscibility of these compounds C N and C P.
• the operating temperature of step (A) is preferably between 5 and 10 ° C, most often between 10 and 70 ° C. It can also be conducted at room temperature.
• the preparation of the solution S used in step (A) can be conducted at a higher temperature than that of step (A), for example between 40 and 80% by weight, in particular so as to allow optimal solvation of the compounds
• Step (B) of evaporation of the solvent S can be carried out as well by allowing the solvent to evaporate on its own by activating this evaporation, for example by heating the surface (at a temperature which is not susceptible to to affect neither the stability of the C N and C P compounds nor their immiscibility), and / or by placing the surface provided with the deposit produced in step (A) under a vacuum or under a carrier gas stream ( N 2 stream for example) capable of driving the solvent S.
• N 2 stream for example
• the subject of the present invention is the supports provided with a photovoltaic type coating of the type obtained (namely obtained or obtainable) according to the method described above in the present description.
• the subject of the invention is the use of the method of the invention for producing photovoltaic cells.
• the photovoltaic coating is generally deposited on an anode (generally an anode transparent to visible radiation, for example ITO, advantageously a layer of ITO deposited on a plastic sheet).
• the anode may be pre-coated with a layer of conductive material.
• the photovoltaic coating according to the invention is deposited (by implementing steps (A) and (B), and preferably (C)), then a cathode is deposited on the photovoltaic coating (for example in the form of a metal overlay, for example an aluminum overlay)
• Photovoltaic cells comprising an organic photovoltaic coating based on a P3HT / PCBM mixture
• Organic photovoltaic cells were prepared by implementing the method of the invention for producing the organic organic layer. More specifically, these cells were prepared under the conditions described below.
• a layer of PEDOT: PSS charge collection layer with a thickness of 40 nm (obtained by spin coating then ground / gel texturing) was deposited.
• a photovoltaic coating was produced under the conditions of the present invention.
• P3HT and PCBM were dissolved in ortho-xylene so as to obtain a solution comprising 1% by weight of P3HT and 1% by weight of PCBM in ortho-xylene (ortho-xylene). xylene playing the role of fraction S1). This solution was stirred at 70 ° C to obtain complete solvation of P3HT and PCBM.
• reaction medium was then cooled to 1 ° C. and then 84.22 g of 98% by weight sulfuric acid were added. The reaction medium was then brought to reflux and was maintained under these conditions for 3 hours.
• the solution comprising the P3HT / PCBM mixture in the thus obtained S1 / S2 mixture was deposited by spin coating, with a plate rotation speed at 700 rpm for 1 minute at room temperature (25 ° C).
• a thin layer of aluminum (approximately 100 nm thick) was then deposited as a cathode on the coating thus produced.

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