WO2016000828A2 - Matières carbonées dimères et leur utilisation dans des dispositifs photovoltaïques organiques - Google Patents

Matières carbonées dimères et leur utilisation dans des dispositifs photovoltaïques organiques Download PDF

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WO2016000828A2
WO2016000828A2 PCT/EP2015/001369 EP2015001369W WO2016000828A2 WO 2016000828 A2 WO2016000828 A2 WO 2016000828A2 EP 2015001369 W EP2015001369 W EP 2015001369W WO 2016000828 A2 WO2016000828 A2 WO 2016000828A2
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accordance
group
carbon material
fullerene
carbon
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WO2016000828A3 (fr
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Bob SCHROEDER
Iain Mcculloch
James Durant
Li ZHE
Shahid ASHRAF
Marie-Béatrice Madec
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Solvay Sa
Imperial Innovations Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/616—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety polycyclic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
    • 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
    • H10K85/10—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
    • 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 is related to carbon materials and their use in organic photovoltaic devices.
  • OCV organic photovoltaic
  • OPV devices usually consist of a multi-layer structure, featuring a blend of electron donor and electron acceptor material.
  • a common acceptor material frequently used in OPV devices is a molecule known as [6, 6]-Phenyl-C6i -butyric acid methyl ester or PCBM.
  • each phase of a donor/acceptor system of an OPV device should be in the range of the exciton diffusion length i.e. the distance travelled by the electron-hole pairs before recombination.
  • the phase separation that occurs during the active layer formation depends on a variety of parameters such as the individual solubility of the polymers in the solvent used, their interaction with the substrate surface, the layer thickness, the method of deposition and the drying and annealing conditions.
  • 10.1038/ncomms3227 describe the performance enhancement of fullerene-based solar cells by light processing.
  • Light soaking of the device is described to cause a dimerization of the PCBM thereby leading to a better retained photo-conversion compared to the devices stored in the dark. It has been observed that when exposed to light for various durations and also heat, the photoactive film is showing no sign of crystallization of PCBM and the properties of the device are not degraded.
  • this method compared to the reticulation method has the advantage that no additional chemicals are necessary, the disadvantage is the fact that the dimerization achieved is only temporary and reverts when the device is no longer light soaked.
  • a further object of the present invention is to combine the carbon materials in accordance with the present invention with known acceptor materials and the use of the carbon materials or of such compositions in OPV devices.
  • Figure 1 shows the different reaction steps of synthesis of Example 1 in a reaction scheme
  • Figure 2 shows the number density of PCBM crystallites formed in blend films with various concentrations of carbon material (PCB)2C2 in
  • Figure 3 shows optical and AFM images of cast films without and with
  • Figure 4 shows the initial device performance in terms of current density of a solar cell with and without addition of a carbon material in accordance with the present invention as part of the donor/acceptor system
  • Figure 5 shows the degradation at 85°C thermal stress in nitrogen atmosphere of the device performance in terms of normalized PCE of a solar cell with and without addition of a carbon material in accordance with the present invention as part of the donor/acceptor system and
  • Figures 6 to 16 show the structures of preferred donor polymers suitable in the organic photovoltaic devices in accordance with the present invention.
  • the present invention concerns a carbon material either of general
  • A, A', A" and A'" which may be the same or different, are derived from fullerenes or fullerene derivatives,
  • B is a C1 -C30 divalent group
  • B' is a C2-C30 trivalent group
  • B" is a C2-C30 tetravalent group.
  • a and A' can be identical to each other, and are preferably [6,6] Phenyl-C61 -propylene group represented by the following structure
  • A, A' and A" can be identical to each other, and are preferably a [6,6] Phenyl-C61 -propylene group represented by the following structure
  • A, A', A" and A'" can be identical to each other, and are preferably a [6,6] Phenyl-C61 -propylene group represented by the following structure
  • B is advantageously a C1-C30 hydrocarbylene or a C2-C30
  • B is advantageously derivable from a diol of formula OH-B-OH.
  • B' is advantageously (i) a C2-C30 trivalent group comprising carbon atoms and hydrogen atoms as sole carbon atoms, or (ii) a C2-C30 trivalent group obtained by replacing at least one carbon atom by a heteroatom in a C2- C30 trivalent group comprising carbon atoms and hydrogen atoms as sole carbon atoms.
  • B' is preferably derivable from a triol of formula B(OH) 3 .
  • B" is advantageously (i) a C2-C30 tetravalent group comprising carbon atoms and hydrogen atoms as sole carbon atoms or (ii) a C2-C30 tetravalent group obtained by replacing at least one carbon atom by a heteroatom in a C2-C30 tetravalent group comprising carbon atoms and hydrogen atoms as sole carbon atoms.
  • B" is preferably derivable from a tetrol of formula B(OH) .
  • the carbon materials in accordance with the present invention are characterized by the general structure (I)
  • a and A' which may be the same or different, are derived from fullerenes or fullerene derivatives and
  • B is a C2-C30 alkylene group, a C6-C30 arylene group, a C2-C30 alkyleneoxyalkylene group or a C6-C30 aryleneoxyarylene group.
  • A, A', A" and A'" are derived from fullerenes or fullerene derivatives.
  • fullerene is intended to denote any molecule composed entirely of carbon in the form of a hollow sphere, ellipsoid, tube or many other shapes.
  • fullerenes have been described in the literature, e.g. buckyball clusters, nanotubes (carbon nanotubes) and megatubes, to name only a few representatives.
  • Spherical fullerenes are called buckyballs and cylindrical fullerenes are referred to as nanotubes or carbon nanotubes.
  • Fullerenes are similar in structure to graphite, which is composed of stacked graphene sheets of linked hexagonal rings.
  • the smallest member of the buckyballs is C20, which is an unsaturated version of dodecahedrane.
  • the most popular representative of buckyballs is C60 or buckminsterfullerene.
  • Buckminsterfullerene is the smallest fullerene molecule containing pentagonal and hexagonal rings in which no two pentagons share an edge.
  • the structure of C60 is a truncated icosahedron resembling an association football ball of the type made of 20 hexagons and 12 pentagons with the carbon atom at the vertices of each polygon and a bond along each polygon edge.
  • the C60 molecule has two bond lengths.
  • the 6:6 ring bonds (between two hexagons) can be considered double bonds and are shorter than the 6:5 bonds (between a hexagon and a pentagon).
  • Nanotubes also referred to as carbon nanotubes are cylindrical fullerenes.
  • Carbon nanotubes may be single walled or multi-walled, i.e. they may have one cylindrical wall or a multiplicity of cylindrical walls. Respective products are known to the skilled person and have been described in the literature as SWCNT (single walled carbon nanotubes) or MWCNT (multi-walled carbon nanotubes).
  • carbon nanotubes similar to ideal graphite, comprise only hexagons but no pentagons.
  • nanotubes may have an unlimited length whereas spherical fullerenes are always closed shapes.
  • Fullerene derivatives have been the subject of intense research in the recent years. To increase the reactivity of fullerenes active groups have been attached to the surface. Whereas fullerenes are stable, they are not totally unreactive. The characteristic reaction of fullerenes is an electrophilic addition at 6, 6-double bonds which reduces angle strain by changing sp 2 -hybridized carbons into sp 3 - hybridized ones.
  • any type of fullerene or fullerene derivative is suitable as structural element A, A', A" or A'" in the carbon materials of the present invention.
  • A, A', A" and A'"; in particular, A and A' in formula (I) may be the same or different and preferably are the same.
  • fullerenes of various types may be combined in the carbon materials of the present invention.
  • buckyballs and in particular buckminsterfullerene C60 or C / o-fullerene or their derivatives are preferred as monodentate groups A, A', A" or A'".
  • buckminsterfullererie derivative with active groups attached to the surface which has been used as electron acceptor in OPV devices, is Phenyl-C61 -butyric acid methyl ester (generally known and referred to hereinafter as PCBM or sometimes ⁇ - ⁇ ) which is represented by the following structure
  • a and/or A' can be derived from said preferred fullerene.
  • the monodentate group A or A' or A" or A'" is obtained from PCBM in this case by removing the carboxylic acid ester group and is thus represented by the following structure
  • PC71 BM Phenyl-Cn -butyric acid methyl ester
  • ps are also suitable and are commonly referred to as Bis-PC62BM and respectively Bis-C72BM.
  • B is a C2-C30 alkylene group, a C6-C30 arylene group, a C2-C30 alkyleneoxyalkylene group or a C6-C30 aryleneoxyarylene group.
  • Preferred groups B are alkylene and alkyleneoxyalkylene groups.
  • alkylene group is intended to denote a group (CH2)n, wherein n represents an integer of from 2 to 30, preferably of from 2 to 18.
  • n represents an integer of from 2 to 30, preferably of from 2 to 18.
  • one or both hydrogen atoms may be replaced by Ci to C 18 alkyl groups.
  • ethylene, propylene, butylene, hexylene, octylene, decylene, dodecylene and octadodecylene may be mentioned here.
  • alkyleneoxyalkylene is intended to denote alkylene groups with one or more oxygen atoms inserted between two alkylene units, in particular alkylene groups with one or more oxygen atoms inserted between two -CH2- units.
  • suitable alkyleneoxyalkylene groups are groups -(-CH2-O-CH2-H with n being an integer of from 1 to 15, -(-CH2-CH2-O)n-(CH 2 )n"- with n' and n" being an integer of from 1 to 10, and any divalent group having at least two -CH2- units which are linked through an oxygen atom in the main chain.
  • One or both hydrogen atoms of any of the CH2 groups may be replaced by a Ci to C 18 alkyl group.
  • aryiene group is intended to denote any group derived from a C& to C30 aromatic compound providing two bonding positions at an aromatic ring to be linked to the oxygen atoms as depicted in the structure (I).
  • suitable examples are phenylene, naphthylene, anthracenylene, to name only a few examples, phenylene being preferred and p-phenylene being much preferred.
  • the aromatic ring may be substituted or unsubstituted.
  • aryleneoxyarylene is intended to denote groups derived from aryiene groups wherein two or more aromatic rings as defined for aryiene groups are linked through an oxygen atom.
  • a representative exam le would be
  • the first step in a suitable process is the conversion of the methyl ester PCBM into the free acid, phenyl-C6i -butyric acid (hereinafter referred to as PCBA).
  • PCBA phenyl-C6i -butyric acid
  • This can be achieved by reacting PCBM with a mixture of hydrochloric acid and acetic acid in a suitable aromatic solvent, e.g. toluene at a temperature in the range of from 0°C to 50 °C.
  • a suitable aromatic solvent e.g. toluene
  • the yield of the apid PCBA is good and normally reaches 70 -90 °/ 0j more preferably 85-90 % of the free acid.
  • a first alternative is the reaction of PCBA with thionyl chloride in the solid phase to convert PCBA into the respective acid chloride of PCBA :
  • PCBA can also be converted into the carbon materials in accordance with the present invention through a Steglich esterification reaction which is well known to the skilled person.
  • the Steglich Esterification is a mild reaction, which allows the conversion of sterically demanding and acid labile substrates in accordance with the following general reaction scheme
  • DCC represents dicyclohexyl carbodiimide and DMAP represents 4-N,N-dimethylaminopyridine (these two components can be replaced by other chemicals having the same effect and function).
  • the reaction sequence for PCBA conversion comprises two reaction steps.
  • the free acid PCBA is reacted with a dialcohol HO- B-OH (where B is as defined above) to the respective ester
  • B is as defined above.
  • B stands for an ethylene (-CH2-CH2), a butylene -(CH2)4-, a hexylene -(CH 2 )6- or an octylene -(CH2)e- group or an alkyleneoxyalkylene group -(CH2-0-CH2)n- with n being an integer of from
  • reaction product of the first Steglich esterification step has a higher solubility than the respective acid chloride obtained as described above in the other variant and this improves the yield of the desired product significantly compared to the first route.
  • triol B'(OH)3 or tetrol B"(OH) 4 respectively in the above two proposed reaction schemes, namely the scheme including the reaction with the acid chloride of PCBA and the scheme including Steglich esterification reactions, and, if needed, modifying the reaction conditions in a suitable manner adopted to the reactants.
  • trimethylolpropane can be a suitable triol while pentaerythritol can be a suitable tetrol.
  • DCC dicyclohexyl carbodiimide
  • DMAP 4-N,N- dimethylaminopyridine
  • A, B, B' and B" have the same meanings as respectively A, B, B' and B" used for defining the carbon material. It goes without saying that when a diol is used, a carbon material of general structure (I) is obtained; when a triol is used, a carbon material of general structure (lb) is obtained; when a tetrol is used, a carbon material of general structure (lc) is obtained.
  • the carbon materials in accordance with the present invention may advantageously be used to improve the morphological stability of fullerenes or fullerene derivatives in donor/acceptor systems in OPV devices, in particular in so called bulk heterojunction (BHJ) devices, with fullerenes or fullerene derivatives as electron acceptors.
  • BHJ bulk heterojunction
  • the carbon materials in accordance with the present invention may be used as such or they may be mixed in accordance with a preferred embodiment with electron acceptors selected from fullerene or fullerene derivatives different from structures (I), (lb) and (lc) which are commonly used in respective donor/acceptor systems in OPV devices.
  • compositions which comprise a carbon material of structure (I), (lb) or (lc) in accordance with the present invention and a fullerene or fullerene derivative of general structure (II)
  • a * -C( O)-O-R' (II) wherein A* may have the meaning as defined for A in claim 1 and R' is a Ci-Ci8-alkyl group.
  • a particularly preferred fullerene derivative in such compositions is PCBM as defined above.
  • the weight ratio of the carbon material of structure (I), (lb) or (lc) and the material of structure (II) is not subject to particular limitations but in certain cases amounts of material of structure (I), (lb) or (lc) based on the combined weight of material of structure (I), (lb) or (lc) and material of structure (II) in the range of from 1 to 50 %, preferably of from 2 to 40 % particularly preferred in the range of from 4 to 30 % have proved to provide some advantages.
  • amounts of material of structure (I), (lb) or (lc) not exceeding 20 wt%, based on the combined weight of material of structure (I), (lb) or (lc) and material of structure (II), have shown to provide advantages.
  • a particulary preferred composition comprises the dimer of PCBM as shown above in structure (III) in combination with the corresponding PCBM monomer itself.
  • the carbon materials of the present invention or the compositions as defined above are suitable for use as electron acceptors in organic electronic devices, preferably in combination with a donor material in so called bulk heterojunction (BHJ) solar cells.
  • BHJ bulk heterojunction
  • Conjugated polymer based electron donor materials have been mainly used as electron donor materials for the manufacture of bulk heterojunction OPV devices in the literature.
  • the energy bandgaps and HOMO and LUMO energy levels of such polymers are the most important parameters influencing the performance of the polymer solar cells. Photon flux density of the solar spectrum is highest in the wavelength range from red to near infrared and thus suitable polymers should absorb light efficiently in this area in order to get the best results. Thus, the polymers should have low bandgaps and high absorption coefficients.
  • the best investigated strategy to reduce the energy bandgap of conjugated polymers is to increase quinoid structures in the conjugated polymer backbone. The quinoid form distributes pi-electrons through the polymer main chain by transforming double bonds into single bonds and synchronously single bonds into double bonds.
  • the quinoid structure Due to the fact that the quinoid structure has a higher ground state energy than the aromatic form, polymers showing a high tendency to form a quinoid structure exhibit usually smaller energy bandgaps. In addition, the quinoid form enables more effective derealization of pi-electrons along the polymer backbone which increases the planarity of the polymer.
  • Figures 6 to 16 show the structures of preferred donor polymers suitable in the organic photovoltaic devices in accordance with the present invention.
  • n represents an integer of at least 2 denoting the number of repeat units contained in the preferred donor polymers.
  • the main disadvantage of P3HT is its large bandgap and its high LUMO level, which are detrimental to a good near IR photon absorption. Thus, there have been attempts to narrow the bandgap and to downshift the HOMO level compared to P3HT.
  • PCDTBT carbazole and benzothiadiazole
  • the optical bandgap of this polymer is 1.88 eV with a low-lying HOMO energy level of -5.50 eV.
  • CPDT cyclopenta[2,1-b;3,4-b']dithiophene
  • DTS dithieno[3,2- b:2',3'-d]silole
  • PCPPTBT and PSBTBT show small bandgaps of appr. 1.5 eV due to the strong intra-molecular donor-acceptor interactions.
  • the performance of PCPDTBT based devices can be further enhanced significantly by adding 3% 1 ,8-diiodooctane (DIO) as a processing additive to tune the morphology, whereas no comparable effect is observed for PSBTBT.
  • DIO diiiodooctane
  • DPP diketopyrrolopyrrole
  • OPV OPV in 2008
  • the electron-withdrawing effect of the lactam units causes the chromophore to have a high electron affinity and thus, it can be used as a strong electron-withdrawing unit.
  • a low bandgap polymer PDPP3T shown in Figure 9
  • the polymer shows a very low bandgap of 1.31 eV and a deep HOMO level of -5.17 eV.
  • TPD thieno[3,4- c ]pyrrole-4,6-dione
  • PBDT-TPD A first polymer wherein this acceptor unit was combined with BDT is PBDT-TPD (structure shown in Figure 12).
  • the polymer shows a bandgap of 1 .81 eV and a deep HOMO level of -5.57 eV.
  • TPD was copolymerized with the DTS unit and a polymer PDTS-TPD (structure shown in Figure 13) with a bandgap of 1.73 eV was obtained.. Further optimi-zation on this structure was reported by Reynolds et al.
  • Still another preferred donor polymer suitable in the organic photovoltaic devices in accordance with the present invention is PBDT-DTffBT the structure of which is shown in Figure 14.
  • PBDTT-DPP structure shown in Figure 15
  • BDTT thienylbenzodithiophene
  • P3HT its structural analogs with the hexyl groups replaced by butyl, oetyl or decyl groups, PCDTBT, PCPDTBT, PCPDTTBTT (Poly[2,6-(4,4-bis-(2- ethylhexyl)-4H-cyclopenta [2,1- ⁇ ;3,4- ⁇ '] dithiophene)-alt-4, 7(2,1 ,3-benzo- thiadiazole)] and in particular P3HT and its structural analogs and PCDTBT are particularly preferred donor polymers for the organic photovoltaic devices. All these preferred polymers are commercially available from Solaris Chem Inc.
  • Another embodiment of the present invention is an organic photovoltaic device comprising a carbon material or a composition in accordance with the present invention as acceptor material.
  • Preferred OPV devices are so called bulk heterojunction devices.
  • donor and acceptor materials are intimately mixed to form a three dimensional interpenetrating network.
  • the majority of bulk heterojunction devices comprise at least one component which is a polymer semiconductor, usually a conjugated polymer as described above.
  • the bicontinuous network of donor and acceptor is organized on a nanometer scale thereby providing a large interface area so that the excitons created can reach a donor/acceptor interface within their diffusion length.
  • Particularly preferred OPV devices in accordance with the present invention are solar cells.
  • the carbon materials or compositions in accordance with the present invention can be advantageously used in bulk heterojunction OPV devices to provide increased stability and performance compared to the prior art devices of the respective type.
  • Acetic acid (150 ml) and HCI (60 ml) were added to a solution of PCBM (1 mmol) dissolved in 150 ml of toluene.
  • the biphasic solution was heated to reflux under vigorous stirring for 12 hours. After reaction the solution was cooled to room temperature and the fine black solid was filtered off. The recovered solid was washed with water, methanol, toluene and diethyl ether. The blackish solid was collected and dried under reduced pressure.
  • the recovered crude product was purified by column chromatography on silica gel using a mixture of toluene:pyridine (95:5) as mobile phase. The recovered fractions were concentrated and precipitated into cold methanol. The title compound was recovered as a brown solid after filtration.
  • the diols used corresponded to the general formula HO-(CH2)n-OH with n being 2, 4, 6 or 8.
  • n 6: Yield 32%.
  • PCDTBT is a high performing amorphous polymer with a glass transition temperature (T g ⁇ 106°C) in neat films, which is below the temperatures used here for examination of thermal stability.
  • FIG. 3 shows AFM images of e) PCDTBT: PCBM as-cast blend films; f) PCDTBT:PCBM:(PCB) 2 C 2 (20%) as-cast films; g) PCDTBT:PCBM blend films after thermal annealing at 85°C for 1 h; and h) PCDTBT: PCBM :(PCB) 2 C 2 (20%) blend films after thermal annealing at 85°C for 1 h on PEDOTPSS ((Poly(3,4-ethylenedioxythiophene/ polystyrene sulfonate) substrates (scale bar is 5.7 pm).
  • PEDOTPSS Poly(3,4-ethylenedioxythiophene/ polystyrene sulfonate
  • a substrate layer of transparent indium tin oxide (ITO) was spin coated with a hole transport layer of PEDOT:PSS (Poly(3,4- ethylenedioxythiophene/polystyrene sulfonate), then annealed above 150 °C prior to the spin coating of the photoactive layer made of a PCDTBT:PCM + dimer mixture with various content of (PCB)2C2-
  • PEDOT:PSS Poly(3,4- ethylenedioxythiophene/polystyrene sulfonate)
  • PCB PCB2C2C2
  • a cathode made of a calcium underlayer with a thickness of 20 nm and a layer of aluminum with a thickness of 100 nm was finally deposited on the photoactive layer via thermal evaporation under reduced pressure.
  • a standardized thermal stress of 85 °C was applied for various periods of time.
  • Figure 4 shows the results through a comparison of the initial J-V characteristics of optimized conventional PCDTBT: PCBM devices containing different weight percentages of (PGB)2C2 prior to thermal stability test (left graph), while Figure 5 shows degradation of solar cell PCE as a function of time at 85°C thermal stress in nitrogen atmosphere of optimized conventional PCDTBT: PCBM devices containing different weight percentages of (PCB)2C2.
  • the power conversion efficiency degrades much faster in the device without dimer, i.e. the addition of the dimer leads to a significantly improved stability of the device.
  • the device performance decreases by 20 % within the first 25 minutes, whereas the same reduction in performance is only observed after 2000 minutes in the device with the dimer added. It is thus apparent that the device thermal stability can be enhanced by at least one order of magnitude.

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Abstract

Cette invention concerne une matière carbonée de structure générale (I) A-C(=O)-O-B-O-C(=0)-A' (I) où A et A' qui peuvent être identiques ou différents sont dérivés d'un fullerène ou de dérivés de fullerènes et B est un lieur divalent C1-C30 et des homologues supérieurs de ladite matière de carbonée comportant respectivement un lieur central de type B et, fixés à celui-ci, trois ou quatre fullerènes ou dérivés de fullerènes du type A. Des compositions comprenant lesdites matières et leur utilisation dans des dispositifs photovoltaïques organiques sont en outre décrites.
PCT/EP2015/001369 2014-07-04 2015-07-06 Matières carbonées dimères et leur utilisation dans des dispositifs photovoltaïques organiques WO2016000828A2 (fr)

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