WO2010136178A1 - Préparation d'un composé colorant et un procédé pour préparer celui-ci - Google Patents

Préparation d'un composé colorant et un procédé pour préparer celui-ci Download PDF

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WO2010136178A1
WO2010136178A1 PCT/EP2010/003179 EP2010003179W WO2010136178A1 WO 2010136178 A1 WO2010136178 A1 WO 2010136178A1 EP 2010003179 W EP2010003179 W EP 2010003179W WO 2010136178 A1 WO2010136178 A1 WO 2010136178A1
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dye
compound
group
linker
dye compound
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PCT/EP2010/003179
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English (en)
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Peter Holliman
Sarah Rugen-Hankey
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Corus Uk Limited
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Publication of WO2010136178A1 publication Critical patent/WO2010136178A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

  • This invention relates to a linker compound, a dye regenerating compound, a dye compound and a method for the chemical synthesis of the dye compound
  • the invention further relates to the use of the dye compound in a photovoltaic device and a dye sensitised solar cell comprising said dye compound
  • a typical DSC may consist of a bottom electrode which is electrically conducting or is coated with a transparent conducting oxide onto which a metal oxide is deposited and subsequently sensitized with a dye
  • An optically transparent top electrode which forms a counter electrode, is also coated with a transparent conducting oxide and further surface modified with a layer of platinum or carbon
  • the top and bottom electrodes are then sealed together using either a thermoplastic polymer (e g Surlyn®, Du Pont) or with a glue (e g an epoxy resin) to form a space in which an electrolyte comprising a redox couple is housed
  • the most successful DSCs to date comprise a ruthenium bipy ⁇ dyl or a terpyridyl dye as a sensitiser and can possess solar-to-electric power conversion efficiencies of up to 10-11%
  • ruthenium-based sensitisers are expensive to produce partly due the cost of the raw materials but also because purification of the dye is a time consuming and sensitive process
  • the ruthenium bipyridyl dyes also possess poor light harvesting efficiencies in the infrared and blue regions of the electromagnetic spectrum Efforts to extend the spectral response of ruthenium based dyes into the infrared region (by exchanging bipyridyl ligands for terpyridyl ligands) have tended to also increase recombination processes as well
  • DSCs may be sensitised with symmetrical or unsymmet ⁇ cal phthalocyanine dyes (pc-dyes) that offer a cost-effective alternative to both ruthenium-based DSCs and other solid state photovoltaic devices
  • pc-dyes symmetrical or unsymmet ⁇ cal phthalocyanine dyes
  • DSCs sensitised with phthalocyanine dyes also display improved light harvesting efficiencies in regions of the electromagnetic spectrum where ruthenium-based sensitisers are less efficient
  • DSCs sensitised with symmetrical and unsymmetrical phthalocyanine dyes currently possess unimpressive power conversion efficiencies compared to their ruthenium based counterparts
  • the low efficiency of DSCs incorporating pc-dyes relates to 1 ) pc-dye insolubility, which due to complications associated with dye purification reduces dye purity and in turn dye uptake on the metal oxide, 2) lack of directionality in the donor- acceptor characteristics of the excited state in conjunction with the anchoring group to the metal oxide, can lead to inefficient electron transfer from the lowest unoccupied molecular orbital (LUMO) of the excited dye to the conduction band of the metal oxide and 3) slow regeneration of the dye from its excited state
  • LUMO lowest unoccupied molecular orbital
  • Phthalocyanine compounds may be synthesised from four phthalonitrile (1 ,2-d ⁇ cyanobenzene) components and/or their derivatives, which cyclise together at elevated temperatures to form a phthalocyanine ring
  • the resulting phthalocyanine compounds comprise reactive groups within the dye's interior that are capable of binding metals
  • Phthalocyanines can also be produced with exterior groups that are capable of interacting with the external environment either by using a de ⁇ vatised phthalonitrile precursor or by derivatising the phthalocyanine after it is formed It is important to note that phthalocyanine compounds that have not been de ⁇ vatised prior to or after cyclisation are typically insoluble and exist as phthalocyanine pigments, whereas denvatised phthalocyanine compounds are generally more soluble due to disruption of ⁇ - ⁇ stacking interactions within the crystal lattice and so exist as phthalocyanine dyes The nature of the exterior groups is critical to the success of the phthalocyanine dye when they are used in dye sens
  • Azaporphynnes are a class of compound closely related to phthalocyanines and may be synthesised from four fumaronitrile components and/or their derivatives, which cyclise together at elevated temperatures to form a macrocycle
  • Both azaporphynnes and phthalocyanines have a core macrocycle consisting of four sets of five membered N-containing heterocycles, which are N-bndged together into a ring with inward pointing N atoms The difference is that phthalocyanines have an additional phenyl ring attached to each five membered corner heterocyclic ring
  • JP-A-2008274082 aims to provide a tetraphenylporphyrin derivative having a plurality of silicon- containing substituents at the phenyl groups at the meso position, to provide a porphyrin complex, and to provide dye-sensitized solar cells using them as dyes
  • a tetraphenylporphyrin derivative is provided by using a method (the so-called Lindsey method) comprising cyclizing a silicon-containing-substituent-containing benzaldehyde derivative, a carboxylic-ester-containing benzaldehyde derivative, and pyrrole by dehydrative condensation in the presence of an acid catalyst and chemically oxidizing the product of cyclisation
  • US2009/0101200 discloses a photoelectric conversion material comprising a fullerene derivative
  • EP1104431 discloses metallocenyl-phthalocyanines or metal complexes thereof as recording materials for use in optical recording media, wherein the metallocene radical(s) are bound via a bridge unit in the phthalocyanine's four phenyl rings.
  • GB2426760 discloses ferrocenyl phthalocyanines and their use in optical recording media, particularly for recordable compact disc.
  • pc phthalocya ⁇ ine
  • a dye compound consisting of four cyclically linked components, the four components comprising at least one linker compound, wherein the at least one linker compound is selected from a first linker compound or a second linker compound, the first linker compound having an aromatic carboxylic acid or an alkyl ester thereof, the aromatic group being bonded to fumaronitrile, and the second linker compound having an aromatic carboxylic acid or an alkyl ester thereof, the aromatic group being bonded to phthalo ⁇ itrile.
  • the dye may be anchored to the metal oxide through one chemisorption interaction, but two chemisorption interactions provide higher DSC efficiencies.
  • the carboxylic acid groups associated with the first linker compound and the second linker compound are also optimally spaced to provide good electron injection into the conduction band of the metal oxide which will further improve DSC efficiency.
  • the linker group comprises the aromatic carboxylic acid or alkyl ester thereof attached directly to the phthalonitrile or fumaronitrile moiety via a single carbon-carbon bond (See figures 1 and
  • Such a linker group provides improved electron transfer within the molecule either to the metal oxide semiconductor or back from the redox couple.
  • aromatic carboxylic acids or alkyl esters thereof which are attached indirectly, that is, via an ether linkage, thioether linkage or via two or more carbon-carbon bonds are not able to facilitate electron transfer to the same extent.
  • carboxyl esters have been hydrolysed to yield carboxylic acids that interact with the metal oxide.
  • the invention is not restricted to dye compounds comprising aromatic carboxylic acids or the alkyl ester thereof; it is also possible to use sulfonates or phosphonates to anchor the dye compound to the metal oxide surface providing aromatic sulfonic esters or aromatic phosphonic esters are used in lieu of carboxylic esters.
  • dye compounds which have not been derivatised prior to being cyclically linked may be derivatised in sulphuric acid or phosphoric acid to make sulfonated or phosphonated derivatives.
  • X is hydrogen or a halogen
  • Y is selected from the group consisting of Fe, Ti, Ni and Co, preferably Fe.
  • DSC dye sensitized solar cells
  • charge separation is achieved differently from conventional p-n junction solar cells such as those based on silicon where charge separation is localised across the p-n junction.
  • charge separation is achieved by electron injection from the excited state of the dye into the conduction band of a metal oxide after which the electron travels around a circuit. The circuit is only completed by the electron reaching the counter electrode and reducing the redox couple in the electrolyte which, in turn, reduces the excited state of the dye to regenerate the dye.
  • dye regeneration is a relatively slow process compared to the other steps in the DSC cycle of operation.
  • the speed of dye regeneration is considerably increased because the metallocene group is able to act as a redox centre capable of interacting with a redox couple in the electrolyte.
  • the redox couple used by the inventor is an iodide/triiodide redox couple.
  • other electrolytes including Co 2+ /Co 3+ , ionic liquids (e.g. imidazolium derivatives), gel electrolytes (e.g. L-valine) or solid electrolytes (e.g.
  • OMeTAD 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene or CuI or CuSCN) can also be used.
  • metallocenes have been used as a redox centre in this preferred embodiment, metallocene may be substituted for other chemical groups such as thiocyanides or iodine, which will also facilitate dye regeneration.
  • a dye compound has been provided further comprising a solubilising compound having an alkyl group or an alkyl ether group, wherein the alkyl group of 1 to 20 carbon atoms is bonded to phthalonitrile, the alkyl group preferably being a tert-alkyl group, and the alkyl ether group of 1 to 20 carbon atoms is bonded to phthalonitrile, the alkyl ether group preferably being a tert-alkyl ether group.
  • the alkyl group or alkyl ether group is bonded directly to the phthalonitrile moiety (see figures 3-6 and 8-9).
  • solubilising compounds reduces unfavourable dye aggregation and increases the solubility of the dye compound, thus dye purity and dye uptake onto the metal oxide is improved.
  • solubilising compounds comprising alkyl or alkyl ether groups exert a +l inductive effect which pushes electron density into the ring formed by the cyclically linked components and enhances electron injection into the metal oxide.
  • the use of tert-alkyl groups or tert-alkyl ether groups magnifies the +l effect, pushing more electrons in the ring.
  • Other solubilising compounds comprising N-donors would also enhance electron injection into the metal oxide and could be used as an alternative to solubilising compounds comprising alkyl groups or alkyl ether groups.
  • a dye compound has been provided wherein the aromatic carboxylic acid is benzoic acid.
  • the carboxylic acid group of benzoic acid is able to anchor the dye compound to the metal oxide surface.
  • the high electron density and electron delocalisation associated with the aromatic ring is expected to promote electron injection into the metal oxide.
  • the presence of the aromatic ring also contributes to the optimised spatial arrangement of the carboxylic acids which further improves the efficiency of the electron injection into the metal oxide.
  • a dye compound wherein the alkyl ester thereof is a methyl ester.
  • the presence of the methyl ester means that the carboxylic acid analogue is protected and unable to hydrogen bond with other fumaronitrile and/or phthalonitrile derivatives and/or other reactive compounds that could cause unwanted side reactions that reduce product yield during cyclisation of the four components. It is preferable to use a methyl ester since it will form a good leaving group once protonated during acidic hydrolysis
  • a dye compound wherein the dye compound is asymmetrical
  • a dye compound could comprise three solubilising compounds (electron donor) and the linker compound having carboxylic acids (electron acceptor)
  • This asymmetric dye compound will exhibit a 'push and pull' which will increase the efficiency of a DSC since electron density is directed towards the carboxylic acid groups that are bonded to the metal oxide
  • asymmetrical dye compounds are easily prepared and can be prepared from a statistical mix of the desired precursors
  • Figures 4, 5 and 6 relate to such a compound, which was synthesised from a 3 1 mixture of a solubilising group and a linker group in which an aromatic carboxylic acid or alkyl ester thereof is bonded directly to fumaronitrile
  • Figures 8 and 9 also show compounds that were synthesised in a 3 1 statistical mix to provide an asymmetrical dye
  • Figure 8 shows the preparation of an asymmetrical metallated dye compound comprising three solubilising compounds
  • an asymmetrical phthalocya ⁇ ine dye may be defined as a dye which comprises a linker compound and a dye regenerating compound or a solubilising compound preferably in a ratio of 3 1 or 2 2 (the molecule being asymmetrical when attached to a metal oxide surface in this instance) and more preferably in a ratio of 1 3
  • an asymmetrical dye can comprise at least one linker compound, a dye regenerating compound and a solubilising compound in a ratio of 1 1 2, 1 2 1 or 2 1 1
  • the term asymmetrical can also be understood to mean unsym metrical
  • dye compounds that host these metals display fluorescent properties, which give rise to enhanced excited state lifetimes and improved electron injection into the metal oxide Zinc exhibits the best fluorescent properties and therefore better electron injection into the metal oxide
  • dye compounds that do not host a metal are still fully functional and could be used in DSC and other photovoltaic devices
  • the dye compounds having an aromatic carboxylic acid or the alkyl ester thereof and which host zinc absorb electromagnetic radiation in the infrared region of the electromagnetic spectrum where ruthenium-bipyridyl complexes are much less efficient as is shown hereinafter in Fig 8.
  • dye compounds hosting a metal and having aromatic carboxylic acids absorb radiation to a greater extent compared to their alkyl ester analogues.
  • metal dye compounds as above are particularly suited to dye sensitised solar cells they may also be used in other photovoltaic devices such as in a p-n junction type design using a different electrode such as gold. They are also suited to photodynamic therapy, tagging, fluorescent imaging and water treatment.
  • a method for the chemical synthesis of a dye compound wherein the four components are stirred in a reaction vessel and heated to a temperature in the range of 80"C to 160°C, preferably 100°C to 150°C, and more preferably 130°C to 140°C. It was found that the four components did not cyclically link if temperatures below 80 ° C were used. In contrast, the four components did cyclically link if higher temperatures above 160°C were used, but the resulting dye compounds were obtained in low yield. The use of temperatures between 100°C and 150°C enabled dye compounds to be synthesised in high yield which was improved further if temperatures between 130'C to 140 0 C were employed.
  • a chemical synthesis of a dye compound wherein the dye compound is reacted with a metal containing compound.
  • a metal containing compound for example, an esterified dye compound is added to a reaction vessel and is dissolved in a suitable solvent; this solution is stirred and heated for approximately 3 hours before the solvent is removed under reduced pressure to yield a residue which is subsequently purified using column chromatography.
  • the presence of the metal extends the lifetime of electrons in an excited state and improves electron injection into the metal oxide and thus overall DSC efficiency.
  • a chemical synthesis of a dye compound wherein the esterified first linker compound and/or the esterified second linker compound is subjected to a hydrolysis treatment.
  • a hydrolysis treatment to provide a first linker compound and/or a second linker compound having carboxylic acid groups enables the dye compound to be anchored to the metal oxide surface, improve electron injection into the conduction band of the metal oxide and enhance electromagnetic radiation absorption in the infrared region of the electromagnetic spectrum; all of which improves DSC efficiency.
  • the hydrolysis treatment is performed by adding the dye compound having alkyl ester groups to a reaction vessel and dissolving the dye compound in a mixture of solvents such as THF and methanol; potassium hydroxide is added to this solution, which is then heated to reflux for approximately 5 hours. Thereafter, the solution is cooled to room temperature and the solvent mixture removed under reduced pressure.
  • solvents such as THF and methanol
  • a first suspension is formed when the remaining solution is acidified using dilute hydrochloric, the first suspension is then filtered to obtain a solid which is washed with water The solid is then dissolved in another solvent such dichloromethane to form a second suspension, which is heated to reflux for approximately 1 hour The second suspension is filtered and dried to yield the linker compound having carboxylic acid groups
  • this method describes an acid catalysed hydrolysis treatment it is also possible to hydrolyse the ester groups using a base catalysed hydrolysis treatment
  • a dye compound wherein the first linker compound and/or the second linker compound comprises aromatic carboxylate groups
  • the dye compound comprising the first linker compound and/or the second linker compound having carboxylic acid groups enables the dye compound to be anchored to the metal oxide surface, improve electron injection into the conduction band of the metal oxide and enhance electromagnetic radiation absorption in the infrared region of the electromagnetic spectrum, all of which improve DSC efficiency
  • a linker compound comprising an aromatic carboxylic acid or an alkyl ester thereof, the aromatic group being bonded to either fumaronitrile or phthalonit ⁇ le
  • Linker compounds as above have several advantages, namely, the preparation of such compounds is relatively straightforward in that the synthesis does not require numerous synthetic and/or purification steps and the cost of the corresponding reagents is inexpensive
  • the preparation of linker compounds comprising alkyl ester groups means that the carboxylic acid analogue is protected and unable to hydrogen bond with other fumaronitrile and/or phthalonit ⁇ le derivatives and/or other reactive compounds that could cause unwanted side reactions that reduce product yield
  • deprotecting the carboxylic acid through hydrolysis is a straightforward process as described above
  • a dye regenerating compound comprising the general formula
  • the dye regenerating compound is able to act as a redox centre capable of interacting with a redox couple such as iodide/triodide Therefore, the dye regenerating compound can be used as a component of a dye compound for use in a dye sensitised solar cell so that dye regeneration is improved and the overall efficiency of the dye sensitised solar cell increases
  • a dye compound consisting of four cyclically linked components, the four components comprising at least one linker compound and at least one dye regenerating compound wherein the dye regenerating compound has the general formula
  • X is hydrogen or a halogen
  • Y is selected from the group consisting of Fe, Ti, Ni and Co, preferably Fe
  • a dye compound for use in a photovoltaic device and in particular a dye sensitised solar cell is advantageous due to their ease of synthesis, ease of purification, high chemical stability, high physical stability, low cost and non toxic nature
  • such dye compounds can be modified easily to optimise their electrical and optical properties, for this reason the dye compound could also be used for optoelectronic applications such as light emitting diodes and optical switches
  • the dye compound is particularly suited for use in a dye sensitised solar cell since it has the ability to link strongly and efficiently inject electrons into the metal oxide
  • the dye compound is also able to recombine with electrons from the electrolyte redox couple in order to complete the electrical circuit
  • the dye compound can be optimised for dying the metal oxide surface, i e rapid and high partitioning onto the metal oxide
  • the use of the dye compound in a dye sensitised solar cell also enables electromagnetic radiation to be absorbed across as wide a part
  • the first electrode comprising a conductive substrate may be fluoride-doped tin oxide on a glass substrate or a metal substrate such as titanium, stainless steel or mild steel which may be deformed using processes such as forming operations, metal embossing, coining, engraving, profiling, laser, marking, pressing, machining, mechanical grinding or hydroforming.
  • metal substrates may be surface modified whilst maintaining the desirable bulk properties of the metal substrate.
  • metal substrates may be surface modified with an electrically insulating coating and/or a protective conductive coating by printing, sputter deposition, plasma deposition, chemical vapour deposition (CVD) or physical vapour deposition (PVD) processes, sol-gel, electrochemical (masking) deposition processes or lamination.
  • the electrically insulating coating is preferably organic, resistant against the electrolyte and resistant to temperatures in the range of 200-600°C. Suitable materials include polyimide.
  • the protective conductive coating could be TiN or Ti and should prevent rust, reactive degradation of the metal substrate and prevent the removal of iodine and iodide components from the electrolyte, which would be detrimental to the DSC efficiency.
  • the protective conductive coating should also be resistant to high temperatures employed when sintering the metal oxide for example.
  • the metal oxide is a wide band gap metal oxide such SnO 2 or ZnO or TiO 2, which should have a thickness between 5 and 20 ⁇ m.
  • the metal oxide is activated using a heat treatment known as sintering, which is used to increase the surface area of the metal oxide so that the maximum amount of the dye compound or a mixture of dye compounds can be chemisorbed onto the metal oxide surface; the chemisorption of multiple dyes onto the metal oxide results in capture of a wider range of wavelengths in the solar spectrum, increasing the efficiency of the DSC.
  • sintering a heat treatment known as sintering, which is used to increase the surface area of the metal oxide so that the maximum amount of the dye compound or a mixture of dye compounds can be chemisorbed onto the metal oxide surface; the chemisorption of multiple dyes onto the metal oxide results in capture of a wider range of wavelengths in the solar spectrum, increasing the efficiency of the DSC.
  • sealant materials such as Surlyn which is a thermoplastic polymer. Care is taken avoid exposure to air and to prevent the electrolyte from drying out, both of which will be detrimental to DSC efficiency.
  • Figure 1 shows the chemical formula of a first linker compound according to the invention.
  • Figure 1a shows the chemical formula of a first linker compound according to the invention wherein R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl)
  • Figure 2 shows the chemical formula of a dye regenerating compound according to the invention
  • Figure 3 shows the chemical formula of a solubilising compound according the invention
  • Figure 4 shows the preparation of a dye compound comprising aromatic alkyl ester groups
  • Figure 4a shows the preparation of a dye compound comprising aromatic alkyl ester groups wherein R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl) In the example shown, R is pentyl
  • Figure 5 shows the preparation of a dye compound that hosts a metal such as zinc
  • Figure 5a shows the preparation of a dye compound that hosts a metal such as zinc wherein R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl) In the example shown, R is pentyl
  • Figure 6 shows the preparation of a dye compound that hosts a metal such as zinc and comprises aromatic carboxylic acid groups
  • Figure 6a shows the preparation of a dye compound that hosts a metal such as zinc and comprises aromatic carboxylic acid groups
  • R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl) In the example shown, R is pentyl
  • Figure 7 shows the preparation of a symmetrical dye compound having four linker compounds wherein each linker compound comprises two aromatic carboxylic acid groups bonded directly to fumaronitrile
  • Figure 7a shows the preparation of a symmetrical dye compound having four linker compounds wherein each linker compound comprises two aromatic carboxylic acid groups bonded directly to fumaronitrile
  • R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl) In the example shown, R is pentyl
  • Figure 8 shows the preparation of an asymmetrical metallated dye compound comprising three solubilising compounds and one linker compound comprising two aromatic carboxylic acid groups bonded directly to phthalonitrile.
  • Figure 8a shows the preparation of an asymmetrical metallated dye compound comprising three solubilising compounds and one linker compound comprising two aromatic carboxylic acid groups bonded directly to phthalonitrile.
  • R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl). In the example shown, R is pentyl.
  • Figure 9 shows the preparation of a metallated dye compound comprising three solubilising compounds wherein each solubilising compound comprises two alkyl ether groups directly bonded to phthalonitrile, and one linker compound comprising two aromatic carboxylic acid groups bonded directly to phthalonitrile.
  • R denotes an alkyl group which is not confined to but typically is between one and five carbons in length (methyl to pentyl). In the example shown, R is pentyl.
  • Figure 10 shows the absorption properties of dye compound according to the invention.
  • Figure 11 shows the absorption properties of a conventional ruthenium bipyridyl dye (N719) and a dye compound according to the invention.
  • a reaction vessel was charged with 4-iodophthalonitrile (1 g, 3.9 mmol), 4- (methoxycarbonylphenyl)boronic acid (0.92 g, 5.1 mmol), anhydrous toluene (10 ml), paladium (II) acetate (20 mg), 2-(2',6 l -dimethoxybiphenyl)dicyclohexylphosphine (20 mg) and potassium phosphate (1.46 g, 6.9 mmol) under inert conditions. Thereafter, the contents of the reaction vessel were heated to 90 0 C for approximately 24 hours.
  • reaction vessel contents of the reaction vessel were then washed with water (2 x 25 ml) and the combined organic layers dried over magnesium sulphate and reduced to dryness to obtain a residue.
  • the residue was placed on alumina and eluted with ethyl acetate and petroleum spirit (70:40) to yield off white solid.
  • a reaction vessel was charged with 4,5-Dichlorophthalonitrile (0.18 g, 0.9 mmol), 4- (methoxycarbonylphenyl)boronic acid (0.5 g, 2.8 mmol), anhydrous toluene (10 ml), Paladium (II) acetate (20 mg), 2-(2',6'-dimethoxybiphenyl)dicyclohexylphosphine (20 mg) and potassium phosphate (0.8 g, 3.8 mmol) under inert conditions. Thereafter, the contents of the reaction vessel were heated to 90 °C for 24 hours.
  • reaction solution The contents of the reaction solution were then washed with water (2 x 25 ml) and the combined organic layers dried over magnesium sulphate and reduced to dryness to obtain a residue. The residue was then recrystalised from ethyl acetate to yield off white crystals.
  • reaction vessel The contents of the reaction vessel were allowed to warm to room temperature and were kept stirred for approximately 16 hours. Thereafter, water (20 ml) was added and extracted with dichloromethane (3 x 20 ml). The combined organic layers were dried over magnesium sulfate and reduced to dryness under reduced pressure to obtain a crude product. The crude product was placed on alumina and eluted with diethyl ether ; petroleum spirit (55:45) to yield red crystals.
  • reaction vessel The contents of the reaction vessel were allowed to warm to room temperature and were kept stirred for approximately 2 hours before heating to approximately 90 0 C for 12 hours. Thereafter, water (20 ml) was added and extracted with dichloromethane (3 x 20 ml). The combined organic layers were dried over magnesium sulfate and reduced to dryness under reduced pressure to obtain a crude product. The crude product was placed on alumina and eluted with diethyl ether ; petroleum spirit (55:45) to yield red crystals.
  • reaction vessel The contents of the reaction vessel were allowed to warm to room temperature and were kept stirred for approximately 2 hours before heating to approximately 90 °C for 12 hours. Thereafter, water (20 ml) was added and extracted with dichloromethane (3 x 20 ml). The combined organic layers were dried over magnesium sulfate and reduced to dryness under reduced pressure to obtain a crude product. The crude product was placed on alumina and eluted with diethyl ether ; petroleum spirit (55:45) to yield red crystals.
  • a reaction vessel was charged with f-butylphthalonitrile (0.5 g, 2.7 mmol), Di-(4- methylbenzoate)-fumaronitrile (0.31 g, 0.9 mmol), anhydrous pentan-1-ol (10 ml) and Diaza(1 ,3)bicyclo[5.4.0]undecane (DBU) (0.07 g, 0.5 mmol) under inert conditions.
  • the contents of the reaction vessel were then heated to reflux for approximately 20 hours.
  • the solvent was removed under reduced pressure to yield a blue/green residue which was placed on alumina and eluted with petroleum spirit ; ethyl acetate (85 : 1 ) to yield a dark blue solid.
  • Example 9 Preparation of 2,9,16-tri-(terf-butyl)- 23,24-di(4-carboxyl) phthalocyanine Zinc 2,9,16-tri-(terf-butyl)- 23,24-di(4-methylbenzoate) phthalocyanine Zinc in THF (10 ml), methanol (5 ml) and 30% potassium hydroxide (15 ml) were placed in a reaction vessel, heated to reflux for 7 hours and then left to stir at room temperature for a further 16 hours. The organic residue was removed and the aqueous layer was acidified to pH 2 by the addition of HCI and then filtered. The filtrate was then washed with water and dried. The remaining solid was suspended in dichloromethane (30 ml) and stirred at reflux for 1 hour. The suspension was then filtered and the solid dried to afford a dark green solid (0.03 g, 64.5 %).
  • n-pentanol (10 ml) was placed in a reaction vessel and 4-(1-Bromoferrocene)-5- chlorophthalonitrile and 4,5-bis(4-methoxycarbonylphenyl)phthalonitrile were added under inert conditions thereto.
  • Zinc acetate dehydrate and DBU were added and the contents of the reaction vessel were heated to approximately 130 °C for 16 hours. Thereafter, the solvent was removed under reduced pressure to yield 2,9,16-(tetra-1-bromoferrocene)-3,10,17-chloro- 23,24-bis(4-methoxycarboxyphenyl) phthalocyanine zinc(ll) as a residue.
  • the residue was subsequently purified by flash chromatography using ethyl acetate as the eluting solvent.
  • reaction vessel was charged with f-butylphthalonitrile (0.5 g, 2.7 mmol), 4,5-bis(4- methoxycarbonylphenyl)phthalonitrile (0.35 g, 0.9 mmol), anhydrous pentan-1-ol (10 ml) and DBU (0.07 g, 0.5 mmol) under inert conditions. Thereafter the contents of the reaction vessel were heated to reflux for approximately 20 hours.
  • Example 16 Preparation of 2,9,16 - tri-(ferf-butyl) - 23,24- bis(4-ethoxycarboxyphenyl) phthalocyanine Zinc.
  • Example 17 Preparation of 2,9,16 - tri-(fert-butyl) - 23,24- bis(4-carboxyphenyl) phthalocyanine zinc after hydrolysis.
  • Example 18 Preparation of 2,3,7,8,12,13,17,18- octa(4-methylbenzoate)-5,10,15,20- tetrazaporphyrin zinc.
  • Example 19 Preparation of 2,3,7,8,12,13,17,18-octa(benzoate)-5,10,15,20-tetrazaporphyrin zinc.
  • Example 20 Preparation of 2,3,9,10,16,17 - nonoxy - 23,24- bis(4-methoxycarboxyphenyl) phthalocyanine .
  • a three-necked round bottomed flask was charged with 4,5-dinonoxyphthalonitrile (0.5 g, 1.2 mmol), 4,5-bis(4-methoxycarbonylphenyl)phthalonitrile (0.16 g, 0.4 mmol), anhydrous pentan-1- ol (10 ml) and DBU (0.07 g, 0.5 mmol) under an argon atmosphere.
  • the solution was then heated to reflux for 20 hours.
  • the solvent was removed under vacuum and the blue/green residue was placed on to alumina and the product eluted with petroleum spirit and ethyl acetate 1 : 1 mix to yield a dark blue solid (0.168 g, 8.0 % ).
  • Example 21 Preparation of 2,3,9,10,16,17 - nonoxy - 23,24- bis(4-methoxycarboxyphenyl) phthalocyaninato zinc.
  • Example 22 Preparation of 2,3,9,10,16,17 - nonoxy - 23,24- bis(4-carboxyphenyl) phthalocyanine zinc .
  • Figure 10 shows the differences in absorption behaviour between non-metallated phthalocyanines, metallated phthalocyanines wherein the linker compound is protected with an aromatic alkyl ester and metallated phthalocyanines wherein the linker compound is unprotected and comprises carboxylic acids. It is apparent from this figure that all of the phthalocyanine compounds absorb radiation in the infrared region and the blue region of the electromagnetic spectrum. The differences in absorbance are attributed to the differences in chemical structure. For example, metallated phthalocyanines that are deprotected exhibit the highest absorbance in the infrared region with an absorbance of 2.2, whereas the non- metallated and protected phthalocyanine compounds have an absorbance of 1.9 and 1.7 respectively.
  • Figure 11 shows the difference in absorption properties for a ruthenium bipyridyl dye (N719) and a phthalocyanine dye compound that is representative of dye compounds according to the invention (examples 7-17 and 18-22).
  • Figure 11 clearly shows that conventional ruthenium bipyridyl dyes have a very low absorbance in the infrared region of the electromagnetic spectrum relative to the phthalocyanine dyes. It'is apparent that at a wavelength of 608 nm the phthalocyanine dyes have an absorbance of approximately 0.9 whereas at the same wavelength the ruthenium bipyridyl dyes have an absorbance of approximately 0.3. This effect is further magnified at higher wavelengths.
  • phthalocyanine dyes in accordance with the invention shall increase the overall efficiency of dye sensitised solar cells when they are chemisorbed onto the metal oxide.
  • Table 1 shows the short circuit current (l sc in mA cm '2 ), the open circuit voltage (V O c in V), the fill factor (FF as a fraction of an ideality of 1.0) and the efficiency ( ⁇ as %) for dye compounds prepared according to examples 9, 17, 19 and 22. N719 is included as a reference.
  • the phthalocyanine dyes show lower V O c values compared to N719 which, at this point in time, is believed to reflect the different energy levels of these dyes along with some issues of electron recombination and dye coverage; both of the latter are known to reduce V O c-
  • the l S c values are also lower for the phthalocyanine dyes compared to N719 which, in part, reflects the fact that the electrolyte used was optimised for N719.
  • the values in Table 1 are presented as minimum efficiencies for these dyes

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Abstract

La présente invention concerne un composé colorant constitué de quatre composants cycliquement liés, les quatre composants comprenant au moins un composé lieur. Selon l'invention, l'au moins un composé lieur est choisi parmi un premier composé lieur et un deuxième composé lieur, le premier composé lieur ayant un acide carboxylique aromatique ou un ester d'alkyle de celui-ci, le groupe aromatique étant lié au fumaronitrile, et le deuxième composé lieur ayant un acide carboxylique aromatique ou un ester d'alkyle de celui-ci, le groupe aromatique étant lié au phtalonitrile.
PCT/EP2010/003179 2009-05-26 2010-05-26 Préparation d'un composé colorant et un procédé pour préparer celui-ci WO2010136178A1 (fr)

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WO2012017874A1 (fr) * 2010-08-03 2012-02-09 富士フイルム株式会社 Colorant complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique
WO2012017868A1 (fr) * 2010-08-03 2012-02-09 富士フイルム株式会社 Colorant à base de complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique
JP2013241502A (ja) * 2012-05-18 2013-12-05 Nippon Steel & Sumikin Chemical Co Ltd フタロシアニン色素並びにフタロシアニン色素を用いた色素増感太陽電池及び光電変換素子
KR20200109795A (ko) * 2019-03-14 2020-09-23 동우 화인켐 주식회사 광산란 수지 조성물, 이를 이용하여 제조된 산란층 및 화상표시장치

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012017874A1 (fr) * 2010-08-03 2012-02-09 富士フイルム株式会社 Colorant complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique
WO2012017868A1 (fr) * 2010-08-03 2012-02-09 富士フイルム株式会社 Colorant à base de complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique
JPWO2012017868A1 (ja) * 2010-08-03 2013-10-03 富士フイルム株式会社 金属錯体色素、光電変換素子及び光電気化学電池
JP5620496B2 (ja) * 2010-08-03 2014-11-05 富士フイルム株式会社 金属錯体色素、光電変換素子及び光電気化学電池
JP2013241502A (ja) * 2012-05-18 2013-12-05 Nippon Steel & Sumikin Chemical Co Ltd フタロシアニン色素並びにフタロシアニン色素を用いた色素増感太陽電池及び光電変換素子
KR20200109795A (ko) * 2019-03-14 2020-09-23 동우 화인켐 주식회사 광산란 수지 조성물, 이를 이용하여 제조된 산란층 및 화상표시장치
KR102472457B1 (ko) 2019-03-14 2022-12-01 동우 화인켐 주식회사 광산란 수지 조성물, 이를 이용하여 제조된 산란층 및 화상표시장치

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