WO2013047614A1 - Élément de conversion photoélectrique, cellule photoélectrochimique et colorant à complexe métallique utilisé dans l'élément de conversion photoélectrique - Google Patents

Élément de conversion photoélectrique, cellule photoélectrochimique et colorant à complexe métallique utilisé dans l'élément de conversion photoélectrique Download PDF

Info

Publication number
WO2013047614A1
WO2013047614A1 PCT/JP2012/074779 JP2012074779W WO2013047614A1 WO 2013047614 A1 WO2013047614 A1 WO 2013047614A1 JP 2012074779 W JP2012074779 W JP 2012074779W WO 2013047614 A1 WO2013047614 A1 WO 2013047614A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
ring
photoelectric conversion
integer
Prior art date
Application number
PCT/JP2012/074779
Other languages
English (en)
Japanese (ja)
Inventor
達也 薄
征夫 谷
小林　克
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201280046948.XA priority Critical patent/CN103828122B/zh
Priority to KR1020147007091A priority patent/KR101890006B1/ko
Publication of WO2013047614A1 publication Critical patent/WO2013047614A1/fr

Links

Images

Classifications

    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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

Definitions

  • the present invention relates to a photoelectric conversion element, a photoelectrochemical cell, and a metal complex dye used therefor.
  • N719 etc. are developed as a ruthenium complex pigment
  • the photoelectric conversion element using this shows high photoelectric conversion efficiency at the beginning of use.
  • the decrease in photoelectric conversion efficiency after use is large, and there is a problem in improving durability.
  • low yield and weak absorption in the visible region remain as problems.
  • even the technique described in Patent Document 2 is not sufficient in performance, and further realization of high IPCE at a long wavelength and improvement in conversion efficiency are desired.
  • the present invention is excellent in photoelectric conversion characteristics, has little deterioration in photoelectric conversion characteristics even after long-term use, has excellent durability, and has a high IPCE (incident photo-to-current efficiency) at a long wavelength.
  • An object is to provide an electrochemical cell and a metal complex dye used therefor.
  • the present inventors have conducted intensive studies in view of the above problems.
  • the above problem has been solved by the following means.
  • dye is a metal complex pigment
  • M represents a metal atom.
  • L 1 represents a ligand represented by the following formula (L1).
  • L 2 represents a ligand represented by the following formula (L2).
  • X represents a monodentate ligand.
  • m1 and m2 each represent 1.
  • mX represents 0 or 1.
  • CI represents the counter ion when a counter ion is required to neutralize the charge.
  • Za, Zb and Zc each independently represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
  • Ring B represents a nitrogen-containing aromatic ring having 5 or more members.
  • Ring A and Ring C each independently represent any of the following formulas (L2-1) to (L2-11).
  • a represents 0 or 1;
  • V represents a substituent having a positive ⁇ p value according to the Hammett rule.
  • the Hammett's rule ⁇ p of the substituent V of at least one of them is less than 0.54.
  • n represents an integer of 1 or more. When n is 2 or more, the ⁇ p value is evaluated by the sum of n V ⁇ p values. ]
  • V and n are synonymous with V and n in Formula (L2).
  • * represents a bond.
  • R represents a substituent, and m represents an integer of 0 or more.
  • L 1 is represented by the following formula (L1-1).
  • a 1 to A 3 each independently represents an acidic group.
  • R 1 to R 3 each independently represents a substituent.
  • b1 to b3 and c1 to c3 each independently represent an integer of 0 or more. However, not all of c1 to c3 are 0.
  • ⁇ 3> The photoelectric conversion element according to ⁇ 1> or ⁇ 2>, wherein the ring B is represented by the following formula (L2-21) or (L2-22).
  • R x represents a substituent.
  • R y represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • da represents an integer of 0 to 5.
  • La represents a conjugated chain.
  • db represents an integer of 0-2.
  • dc represents an integer of 0 to 4.
  • * represents a bond.
  • ⁇ 4> The photoelectric conversion device according to ⁇ 3>, wherein R y is a heterocyclic group.
  • ⁇ 5> The ring A and the ring C according to any one of ⁇ 1> to ⁇ 4>, wherein the ring A and the ring C are any one of the formulas (L2-2) to (L2-6) and (L2-9) Photoelectric conversion element.
  • ⁇ 6> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 5>, wherein at least one of the Vs includes a heterocyclic group.
  • ⁇ 7> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 6>, wherein the acidic group included in at least one of Za, Zb, and Zc is a carboxyl group.
  • ⁇ 8> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 7>, wherein the metal atom represented by M is a ruthenium atom.
  • ⁇ 9> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 8>, wherein the photoreceptor layer further contains a dye represented by the following formula (2).
  • Mz represents a metal atom.
  • L 3 represents a ligand represented by the following formula (L3).
  • L 4 represents a ligand represented by the following formula (L4).
  • Y represents a monodentate or bidentate ligand.
  • m3 represents an integer of 0-2.
  • m4 represents an integer of 1 to 3.
  • mY represents an integer of 0-2.
  • CI represents a counter ion when a counter ion is required to neutralize the charge.
  • R a represents a substituent.
  • R b represents an alkyl group or an aromatic ring group.
  • e1 and e2 each independently represents an integer of 0 to 5.
  • L c and L d each independently represent a conjugated chain.
  • e3 represents 0 or 1.
  • f represents an integer of 0 to 3.
  • g represents an integer of 0 to 3. ]
  • Zd, Ze, and Zf each independently represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. h represents 0 or 1; However, at least one of the rings formed by Zd, Ze, and Zf has an acidic group.
  • ⁇ 10> A photoelectrochemical cell comprising the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A metal complex dye having a structure represented by the following formula (1).
  • M represents a metal atom.
  • L 1 represents a ligand represented by the following formula (L1).
  • L 2 represents a ligand represented by the following formula (L2).
  • X represents a monodentate ligand.
  • m1 and m2 each represent 1.
  • mX represents 0 or 1.
  • CI represents the counter ion when a counter ion is required to neutralize the charge.
  • Za, Zb and Zc each independently represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
  • Ring B represents a nitrogen-containing aromatic ring having 5 or more members.
  • Ring A and Ring C each independently represent any of the following formulas (L2-1) to (L2-11).
  • a represents 0 or 1;
  • V represents a substituent having a positive ⁇ p value according to the Hammett rule.
  • the Hammett's rule ⁇ p of the substituent V of at least one of them is less than 0.54.
  • n represents an integer of 1 or more. When n is 2 or more, the ⁇ p value is evaluated by the sum of n V ⁇ p values. ]
  • V and n are synonymous with V and n in Formula (L2).
  • * represents a bond.
  • R represents a substituent, and m represents an integer of 0 or more.
  • aromatic ring is used to mean an aromatic ring and a heterocycle (aromatic heterocycle and non-aromatic heterocycle), and may be monocyclic or multicyclic.
  • the carbon-carbon double bond may be any of E type and Z type in the molecule.
  • each substituent or ligand, etc. May be the same as or different from each other. Further, when a plurality of substituents and ligands are close to each other, they may be connected to each other or condensed to form a ring.
  • the photoelectric conversion element and the photoelectrochemical cell of the present invention are excellent in photoelectric conversion characteristics, have little deterioration in photoelectric conversion characteristics even after long-term use, have excellent durability, and have a long wavelength IPCE (Incident Photo-to-to- Current Efficiency) is high.
  • IPCE Incident Photo-to-to- Current Efficiency
  • the metal complex dye of the present invention is useful as a sensitizing dye used in the photoelectric conversion element and the photoelectrochemical cell.
  • FIG. 2 is a cross-sectional view schematically showing a dye-sensitized solar cell produced in Example 1.
  • FIG. 3 is a cross-sectional view schematically showing a dye-sensitized solar cell produced in Example 2.
  • FIG. 1 is a cross-sectional view schematically showing a dye-sensitized solar cell produced in Example 1.
  • the metal complex dye of the present invention has a tricyclic ligand and a specific bicyclic ligand with respect to the central metal, and thus, in a photoelectric conversion element, a high IPCE is obtained even in a long wavelength region exceeding 800 nm. Demonstrating high photoelectric conversion efficiency and higher durability.
  • the reason for this includes unexplained points, but can be explained as follows, including estimation.
  • the durability was improved by using a bidentate or higher ligand instead of the monodentate ligand NCS which is usually used as a ligand. This is presumed to be that the elimination of the ligand was suppressed and the ligand exchange was suppressed by the polydentate ligand formation.
  • the d-orbital level of the central metal was adjusted by improving the N-position donor property in relation to the structure of the nitrogen-containing heterocycle, which led to the improvement of the above performance.
  • the present invention will be described in detail with a focus on preferred embodiments of the present invention.
  • the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1.
  • the conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5.
  • the photoreceptor layer 2 has semiconductor fine particles 22 and a dye 21, and at least a part of the dye 21 is adsorbed on the semiconductor fine particles 22 (the dye is in an adsorption equilibrium state, and partly charge transfer).
  • the conductive support 1 on which the photoreceptor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.
  • the light-receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer (semiconductor film) 2 including semiconductor fine particles 22 adsorbed with a dye 21 coated on the conductive support.
  • a photosensitive layer (semiconductor film) 2 including semiconductor fine particles 22 adsorbed with a dye 21 coated on the conductive support.
  • Light incident on the photoreceptor layer (semiconductor film) 2 excites the dye.
  • the excited dye has high energy electrons. Therefore, the electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the conductive support 1 by diffusion. At this time, the molecule of the dye 21 is an oxidant.
  • Excitation awakened by the oxidized dye in the electrolyte reducing agent e.g., I -
  • the light receiving electrode 5 functions as a negative electrode of the battery.
  • the photoelectric conversion element of this embodiment has a photoreceptor layer having a layer of semiconductor fine particles on which a dye described later is adsorbed on a conductive support. At this time, a part of the dye dissociated in the electrolyte may be present.
  • the photoreceptor layer is designed according to the purpose, and may be a single layer structure or a multilayer structure. Since the photosensitive layer of the photoelectric conversion element of the present embodiment contains semiconductor fine particles adsorbed with a specific dye, the sensitivity is high, and high photoelectric conversion efficiency can be obtained when used as a photoelectrochemical cell. .
  • the upper and lower sides of the photoelectric conversion element do not need to be defined in particular, but in this specification, based on what is illustrated, the support body serving as the light receiving side with the counter electrode 4 side as the upper (top) direction
  • the side of 1 is the lower (bottom) direction.
  • M M represents a metal atom.
  • M is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.
  • Za, Zb and Zc each independently represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
  • the 5-membered or 6-membered ring formed by Za, Zb and Zc may be substituted or unsubstituted, and may be monocyclic or condensed.
  • Za, Zb and Zc are preferably atoms in which the ring atoms are selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, and the atom includes a hydrogen atom and a substituent including a halogen atom.
  • the group may be substituted.
  • the ring formed by Za, Zb and Zc is more preferably an aromatic ring.
  • an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed.
  • a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed.
  • an imidazole ring or a pyridine ring is more preferable.
  • the acidic group is a substituent having a dissociative proton, and examples thereof include a carboxyl group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group, and a group having any one of these, Preferred is a carboxyl group or a group having this.
  • the acidic group may take a form of releasing a proton and dissociating, or may be a salt. Although it does not specifically limit as a counter ion when it becomes a salt, For example, the example of the positive ion in the following counter ion CI is mentioned.
  • the acidic group may be a group bonded through a linking group.
  • a carboxyvinylene group, a dicarboxyvinylene group, a cyanocarboxyvinylene group, a carboxyphenyl group, and the like may be mentioned as preferable examples. it can.
  • the acidic group mentioned here and its preferable range may be called acidic group Ac.
  • L 1 is preferably represented by the following formula (L1-1).
  • a 1 , A 2 and A 3 each independently represents an acidic group.
  • a 1 , A 2 , and A 3 are preferably those exemplified as the acidic group Ac.
  • R 1 to R 3 each independently represents a substituent.
  • substituent of R 1 to R 3 include the substituent T described later.
  • R 1 to R 3 are preferably an alkyl group, a heteroaryl group, an aryl group, a heteroaryl group via a vinyl group, or an aryl group via a vinyl group.
  • ⁇ B1 to b3, c1 to c3 b1, b3 and c1, c3 each independently represents an integer of 0 to 4, and b2, c2 each independently represents an integer of 0 to 3.
  • c1 to c3 are not all 0.
  • L 1 is represented by the following formula (L1-2).
  • R 7 , R 8 and R 9 each independently represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or an acidic group. At least one of R 7 , R 8 and R 9 is an acidic group.
  • the acidic group is preferably a group exemplified for the acidic group Ac.
  • L 2 (Formula (L2)) L 2 is represented by the following formula (L2).
  • ⁇ V V represents a substituent having a positive ⁇ p value according to the Hammett rule.
  • the Hammett's rule ⁇ p of the substituent V of at least one of them is less than 0.54.
  • the ⁇ p value of V is preferably 0.05 or more, more preferably 0.10 or more. There is no particular upper limit to the ⁇ p value, but it is practical that it is 1 or less.
  • the ⁇ p value of V is preferably 0.05 or more, and more preferably 0.10 or more.
  • the ⁇ p value of the substituent is the value of Corwin Hansch, A. et al. LEO and R.M. W. TAFT, “A Survey of Hammett Substitute Students and Resonance and Field Parameters”, Chem. Rev. 91, 165 to 195 (1991). Further, the ⁇ p value of the substituent V of the exemplified compound is shown together with the description of the exemplified compound described later.
  • the ⁇ p value of V is preferably 0.05 or more, where the sum of ⁇ p values of a plurality of substituents V present in the same heterocycle is 0.05 or more. Is preferred. However, evaluation is performed for each heterocycle, and V substituted for another heterocycle is not evaluated as the sum but evaluated with each ⁇ p value.
  • At least one of V is a substituent containing a heterocyclic group.
  • This improves ⁇ and increases IPCE.
  • Preferred heterocyclic rings in the above heterocyclic groups are thiophene, furan, pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and benzo condensed ring thereof. , Triazine, and the like.
  • ⁇ N n represents an integer of 1 or more. n is preferably 1 to 5, and more preferably 1 to 3.
  • Ring A, Ring C Ring A and ring C are represented by any of the following formulas (L2-1) to (L2-11).
  • V has the same meaning as V in the above formula (L2)
  • n has the same meaning as n in the above formula (L2)
  • the preferred range is also the same.
  • * Represents a bond (position bonded to ring B).
  • R represents a substituent
  • m represents an integer of 0 or more.
  • the upper limit of m is “substitutable number ⁇ 1” in each formula, and is 2 if formula L2-1.
  • the plurality of R may be the same or different.
  • Examples of R include a substituent T described later, and an alkyl group, an aryl group, and a heterocyclic group are preferable.
  • R and V mean substitution at any position of the entire condensed ring. It is meant to include those that are joined. It is preferable that the ring A and the ring C are the formulas (L2-2) to (L2-6) or (L2-9).
  • Ring B represents a nitrogen-containing aromatic ring having 5 or more members, preferably 5 to 14 members, which may have a substituent. Ring B may have a substituent or may be unsubstituted, and may be monocyclic or condensed.
  • the ring-constituting atom of ring B is preferably an atom selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, and the atom is substituted with a substituent including a hydrogen atom or a halogen atom May be.
  • Ring B is preferably an aromatic ring.
  • ring B is a 5-membered ring, an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferable, and when it is a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferable.
  • Ring B is preferably represented by the following formula (L2-21) or (L2-22).
  • R x represents a substituent.
  • substituent in R x include a substituent of the substituent T described later.
  • R y represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • R y is preferably an aryl group or a heterocyclic group.
  • R y is a heterocyclic group
  • the heterocyclic ring in the heterocyclic group is thiophene, furan, pyrrole, selenophene, and a benzo condensed ring thereof, and those in which two or more of these rings are condensed or linked; More preferred are thienothiophene, dithienothiophene, dithienocyclopentane, dithienosilole, and the like.
  • ⁇ Da, db, dc da represents an integer of 0 to 5.
  • db represents an integer of 0-2.
  • dc represents an integer of 0 to 4.
  • ⁇ L a La represents a conjugated chain, and when da is 2 to 5, the plurality of conjugated chains may be the same or different from each other.
  • Conjugated chain of L a for example, can be exemplified an arylene group, a conjugated chain consisting of at least one ethenylene group and an ethynylene group.
  • the conjugated chain (arylene group, heteroarylene group, ethenylene group) may be unsubstituted or substituted.
  • the substituent is preferably an alkyl group, and more preferably methyl.
  • L a is preferably in the range of 2 to 6 conjugated chain carbon, thiophenediyl, ethenylene, butadienylene, ethynylene, butadiynylene, more preferably methylethenylene or dimethyl et tennis alkylene, particularly preferably ethenylene or butadienylene, ethenylene most preferable.
  • each double bond may be E-type or Z-type, or a mixture thereof.
  • ⁇ A a represents 0 or 1;
  • Ligand X X represents a monodentate ligand.
  • X is, for example, an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group,
  • monodentate ligands selected from the group consisting of carbonyl, dialkyl ketone, carbonamide, thiocarbonamide
  • the ligand X contains an alkyl part, an alkenyl part, an alkynyl part, an alkylene part, etc., these may be linear or branched, and may be substituted or unsubstituted. Further, when an aryl moiety, a heterocyclic moiety, a cycloalkyl moiety and the like are included, they may be substituted or unsubstituted, and may be monocyclic or condensed.
  • Counter ion CI CI in Formula (1) represents a counter ion when a counter ion is required to neutralize the charge.
  • a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the dye.
  • the metal complex dye represented by the formula (1) of the present invention may be dissociated and have a negative charge due to the substituent having a dissociable group. In this case, the charge of the entire metal complex dye represented by the formula (1) becomes electrically neutral due to CI.
  • the counter ion CI is a positive counter ion
  • the counter ion CI is an inorganic or organic ammonium ion (eg, tetraalkylammonium ion, pyridinium ion, etc.), phosphonium ion (eg, tetraalkylphosphonium ion, alkyltriphenylphosphonium ion). Etc.), alkali metal ions or protons.
  • the counter ion CI is a negative counter ion
  • the counter ion CI may be an inorganic anion or an organic anion.
  • a halogen anion eg, fluoride ion, chloride ion, bromide ion, iodide ion, etc.
  • substituted aryl sulfonate ion eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion, etc.
  • aryl disulfone Acid ions for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.
  • alkyl sulfate ions for example, methyl sulfate ion
  • sulfate ions thiocyanate ions
  • an ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.
  • the present invention is not limited thereto.
  • the ligand, especially the ligand in L 2 is coordinated to a metal atom, that is, an atom coordinated by an anion is represented by an anion, it is not necessarily coordinated by an anion.
  • the metal complex dye omits a counter ion, but does not need a counter ion but can hold an arbitrary counter ion.
  • the metal complex dye represented by the general formula (1) of the present invention can be easily synthesized according to the method shown in the examples or the same.
  • Metal complex dye represented by formula (2) In the photoelectric conversion element and the photoelectrochemical cell of the present invention, in addition to the metal complex dye represented by the general formula (1) of the present invention, it is preferably used in combination with another metal complex dye. By using together with other metal complex dyes, the mutual adsorption state can be controlled, and higher photoelectric conversion efficiency and durability than each can be achieved. As other metal complex dyes, metal complex dyes represented by the following formula (2) are preferable.
  • Metal atom Mz Mz is synonymous with M in Formula (1).
  • L 3 represents a bidentate ligand represented by the following formula (L3).
  • ⁇ M3 m3 represents an integer of 0-2. m3 is preferably 1 or 2, and more preferably 1. When m3 is 2, two L 3 may be the same or different.
  • ⁇ Ac Ac represents an acidic group. When a plurality of Ac are present, these may be the same or different. Ac is synonymous with Ac in Formula (1), and a preferable range is also the same. Ac may be substituted on the pyridine ring or any atom of the substituent.
  • R a represents a substituent, and when a plurality of R a are present, these may be the same as or different from each other.
  • R a is preferably an alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acyl group, sulfonamido group, acyloxy group, carbamoyl group, An acylamino group, a cyano group or a halogen atom, more preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a halogen atom, particularly preferably an alkyl group.
  • R b represents an alkyl group or an aromatic ring group.
  • the aromatic ring group is preferably an aromatic ring group having 6 to 30 carbon atoms, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl and the like.
  • the heterocyclic (heterocyclic) group is preferably a heterocyclic group having 1 to 30 carbon atoms such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, 3-indolyl and A combination of two or more rings of these groups (condensed or linked).
  • the electron donating group is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group or a hydroxy group, and an alkyl group, an alkoxy group, an amino group or a hydroxy group.
  • a group is more preferable, and an alkyl group is particularly preferable.
  • ⁇ E1, e2 e1 and e2 are each independently an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2.
  • L c and L d L c and L d each independently represent a conjugated chain, and examples thereof include a conjugated chain composed of at least one of an arylene group, a heteroarylene group, an ethenylene group, and an ethynylene group.
  • the conjugated chain (arylene group, heteroarylene group) may be unsubstituted or may have a substituent.
  • the substituent is preferably an alkyl group, and more preferably methyl.
  • L c and L d are each independently preferably a conjugated chain having 2 to 6 carbon atoms, more preferably thiophenediyl, ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene, or dimethylethenylene, and ethenylene or butadienylene. Is particularly preferred, and ethenylene is most preferred. L c and L d may be the same or different, but are preferably the same. When the conjugated chain includes a carbon-carbon double bond, each double bond may be E-type or Z-type, or a mixture thereof.
  • ⁇ E3 e3 represents 0 or 1.
  • f on the right side of the page is preferably 1 or 2
  • f on the right side of the page is preferably 0 or 1.
  • the total sum of f is preferably an integer of 0-2.
  • ⁇ G g represents an integer of 0 to 3, and a plurality of g may be the same as or different from each other. g is preferably an integer of 0 to 2.
  • ⁇ F f represents an integer of 0 to 3.
  • a plurality of f may be the same as or different from each other.
  • m3 in the formula (2) is preferably 2 or 3, and more preferably 2.
  • f on the left side of the paper surface is preferably 0 or 1
  • f on the right side of the paper surface is preferably an integer of 0 to 2.
  • the ligand L 3 in the formula (2) is preferably represented by the following general formula (L3-1), (L3-2) or (L3-3).
  • Ra in —N (Ra) (Ra) may be a hydrogen atom.
  • e4 represents an integer of 0 to 4.
  • L 4 represents a bidentate or tridentate ligand represented by the following formula (L4).
  • Zd, Ze and Zf represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring.
  • h represents 0 or 1; However, at least one of the rings formed by Zd, Ze, and Zf has an acidic group.
  • ⁇ M4 m4 represents an integer of 1 to 3, and preferably 1 or 2. When m4 is 2 or more, a plurality of L 4 are may be the same or different from each other.
  • ⁇ Zd, Ze, Zf Zd, Ze, and Zf are synonymous with Za, Zb, and Zc of Formula (1).
  • ⁇ H h represents 0 or 1; h is preferably 0, and L 4 is preferably a bidentate ligand.
  • the ligand L 4 is preferably represented by any of the following formulas (L4-1) to (L4-8), and the formulas (L4-1), (L4-2), (L4-4), Or is more preferably represented by (L4-6), particularly preferably represented by formula (L4-1) or (L4-2), and particularly preferably represented by formula (L4-1). .
  • Ac represents an acidic group or a salt thereof.
  • Ac is preferably the above-mentioned acidic group Ac.
  • i is 2 or more, a plurality of Ac may be the same as or different from each other.
  • Ra is synonymous with the thing in Formula (1).
  • R a substituted on the N position may be a hydrogen atom.
  • i represents the number (integer) of carbon positions which can be substituted by 0 or more.
  • a plurality of i may be the same as or different from each other. The number of possible substitutions is shown in parentheses next to the formula number. When a plurality of R a are present, these may be connected to each other or condensed to form a ring.
  • the substituent R a is shown by extending the bond to a predetermined aromatic ring, but is not limited to those substituted on the aromatic ring. That is, for example, in Formula L4-1, Ac and R a are substituted on the pyridine ring on the left side of the page, but these may be substituted on the pyridine ring on the right side of the page.
  • Y represents a monodentate or bidentate ligand.
  • mY represents the number of ligands Y.
  • mY represents an integer of 0 to 2, and mY is preferably 1 or 2.
  • mY is preferably 2.
  • mY is preferably 1.
  • the plurality of Y may be the same as or different from each other, and the plurality of Y may be connected to each other.
  • Ligand Y is preferably acyloxy group, thioacylthio group, acylaminooxy group, dithiocarbamate group, dithiocarbonate group, trithiocarbonate group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, A ligand coordinated by a group selected from the group consisting of an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand composed of a halogen atom, carbonyl, 1,3-diketone or thiourea.
  • a ligand or a ligand comprising a halogen atom or a 1,3-diketone most preferably a ligand coordinated by a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group Or a ligand consisting of 1,3-diketone
  • the ligand Y contains an alkyl part, an alkenyl part, an alkynyl part, an alkylene part, etc., they may be linear or branched and may be substituted or unsubstituted.
  • an aryl moiety, a heterocyclic group moiety, a cycloalkyl moiety and the like may be substituted or unsubstituted, and may be monocyclic or condensed.
  • Y is a bidentate ligand
  • Y is an acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithio
  • a ligand composed of urea is preferable.
  • Y is a monodentate ligand
  • Y is a ligand coordinated by a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, and an arylthio group, or A ligand composed of a halogen atom, carbonyl, dialkyl ketone, or thiourea is preferred.
  • Counter ion CI CI in Formula (2) represents a counter ion when a counter ion is required to neutralize the charge. It is synonymous with CI in Formula (1), and its preferable range is also the same.
  • the metal complex dye represented by the formula (2) preferably has at least one or more interlocking groups that bind or adsorb to the surface of the semiconductor fine particles. It is more preferable to have 1 to 6 bonding groups in the metal complex dye, and it is particularly preferable to have 1 to 4 bonding groups. Examples of the linking group include the aforementioned Ac.
  • the metal complex dye represented by the formula (2) preferably used in the present invention is shown below, but the present invention is not limited thereto.
  • the dye in the following specific example includes a ligand having a proton dissociable group
  • the ligand may be dissociated as necessary to release a proton (H + ). These are also included.
  • the metal complex dye represented by the formula (2) can be easily synthesized by a method cited in Japanese Patent Application Laid-Open No. 2001-291534, the method described in the document, or a method according to these methods.
  • the maximum absorption wavelength in the solution is preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm. is there.
  • at least a metal complex dye represented by the formula (1) and a metal complex dye represented by the formula (2) are used to emit light in a wide range of wavelengths. By using it, high conversion efficiency can be ensured.
  • ⁇ Substituent T> In this specification, about the display of a compound (a complex and a pigment
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent T. Further, in the present specification, the term "only described as a substituent" refers to this substituent T, and each group, for example, an alkyl group is only described. Preferred ranges and specific examples of the corresponding group of the substituent T are applied.
  • substituent T examples include the following.
  • An alkyl group preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.
  • Alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.
  • cycloalkyl groups preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • cycloalkenyl group preferably having 5 to 20
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
  • a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc.
  • Cyclohexyloxycarbonyl, etc. aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.)
  • amino groups preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls
  • An acyl group (preferably having 1 to 20 carbon atoms such as acetyl, cyclohexylcarbonyl, benzoyl, etc.), an acyloxy group (preferably having 1 to 20 carbon atoms such as acetyloxy, cyclohexylcarbonyl, etc.) Xy, benzoyloxy and the like), carbamoyl groups (preferably having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl carbamoyl groups are preferred, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc. ),
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide having 0 to 20 carbon atoms) Groups such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc., alkylthio groups (preferably having 1 to 20 carbon atoms, for example, Methylthio, ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopen
  • a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted by alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxyl group , Cyano group, nitro group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, sulfo group, phosphonyl group, phosphoryl group, boric acid group, more
  • a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
  • the photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 on which the dye of the present invention is adsorbed. This dye may be partially dissociated in the electrolyte.
  • the photoreceptor layer 2 may be designed according to the purpose and may have a multilayer structure. As described above, since the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.
  • the electrolyte used for the photoelectric conversion element 10 of the present invention includes, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.) as an oxidation-reduction pair, alkyl viologen (for example, a combination of methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) and a reduced form thereof, a combination of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and an oxidized form thereof, divalent and trivalent iron.
  • iodine and iodide for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.
  • a combination of a complex for example, a red blood salt and a yellow blood salt
  • a combination of a divalent and a trivalent cobalt complex and the like can be given.
  • a combination of iodine and iodide is preferred.
  • iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.
  • the iodine content in the electrolyte used in the photoelectric conversion element 10 of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass with respect to the entire electrolyte. .
  • the electrolyte used in the photoelectric conversion element 10 of the present invention may contain a solvent.
  • the solvent content in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less of the entire electrolyte.
  • a charge transport layer containing a hole conductor material may be used.
  • the hole conductor material 9,9'-spirobifluorene derivatives and the like can be used.
  • an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated.
  • a hole transport material that functions as a p-type semiconductor can be used as the hole transport layer.
  • an inorganic or organic hole transport material can be used as a preferred hole transport layer.
  • the inorganic hole transport material include CuI, CuO, and NiO.
  • the organic hole transport material include high molecular weight materials and low molecular weight materials, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane.
  • organic polysilanes are preferable because, unlike conventional carbon-based polymers, ⁇ electrons delocalized along the main chain Si contribute to photoconduction and have high hole mobility (Phys. Rev. B, 35, 2818 (1987)).
  • a photosensitive layer 2 in which a dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1.
  • the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.
  • the conductive support 1 glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal.
  • the conductive support 1 is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or polymer material coated with a conductive metal oxide can be used as the conductive support 1, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of glass or polymer material support. When a transparent conductive support is used, light is preferably incident from the support side.
  • polymer material preferably used examples include triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy.
  • a surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in JP-A-2002-260746 is improved.
  • a metal support can also be preferably used.
  • examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.
  • a photosensitive layer 2 in which a dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1.
  • the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution.
  • the semiconductor fine particles prepared using the specific surfactant are applied.
  • the semiconductor fine particle dispersion having a solid content other than the semiconductor fine particles of 10% by mass or less of the whole of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately. Quality semiconductor fine particle coating layer can be obtained.
  • semiconductor fine particle dispersions can be prepared by depositing fine particles in a solvent and using them as they are when synthesizing semiconductors. Or a method of pulverizing and grinding mechanically using a mill or a mortar.
  • the dispersion solvent one or more of water and various organic solvents can be used.
  • the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
  • a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used in a small amount as a dispersion aid.
  • these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support.
  • the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.
  • the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.
  • the viscosity of the dispersion is preferably 10 to 300 N ⁇ s / m 2 at 25 ° C. More preferably, it is 50 to 200 N ⁇ s / m 2 at 25 ° C.
  • a regular coating such as a roller method or a dip method can be used as an application method.
  • an air knife method, a blade method, etc. can be used as a metering method.
  • the preferred thickness of the entire semiconductor fine particle layer is 0.1 ⁇ m to 100 ⁇ m.
  • the thickness of the semiconductor fine particle layer is further preferably 1 ⁇ m to 30 ⁇ m, and more preferably 2 ⁇ m to 25 ⁇ m.
  • the amount of the semiconductor fine particles supported per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g.
  • the method for forming the film by applying the fine particle dispersion is not particularly limited, and a known method may be applied as appropriate.
  • the total amount of the dye 21 used is preferably from 0.01 mmol to 100 mmol, more preferably from 0.1 mmol to 50 mmol, particularly preferably from 0.1 mmol to 10 mmol, per 1 m 2 of the support. In this case, it is preferable that the usage-amount of the pigment
  • the amount of the dye 21 adsorbed on the semiconductor fine particles 22 is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.
  • the counter electrode 4 functions as a positive electrode of the photoelectrochemical cell.
  • the counter electrode 4 is usually synonymous with the conductive support 1 described above, but a support for the counter electrode is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity.
  • the material for the counter electrode 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.
  • the structure of the counter electrode 4 is preferably a structure having a high current collecting effect. Preferred examples include JP-A-10-505192.
  • the light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light.
  • Preferred examples of the tandem type configuration include those described in JP-A Nos. 2000-90989 and 2002-90989.
  • a light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided.
  • Preferable examples include those described in JP-A-2002-93476.
  • a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent reverse current due to direct contact between the electrolyte and the electrode.
  • Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.
  • a spacer or a separator In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator.
  • a preferable example is JP-A-2001-283941.
  • Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.
  • Metal complex dye 1 was prepared according to the scheme shown below.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography.
  • 310 ml of DMF (N, N-dimethylformamide) and 3.17 g of KSCN were added and reacted at 160 ° C. for 8 hours.
  • the solvent was distilled off under reduced pressure, 100 ml of acetone and 100 ml of 1.0 M aqueous sodium hydroxide solution were added, and the mixture was heated to reflux for 24 hours.
  • the resulting crystals were collected by filtration, added with a small amount of methanol, and purified with a Sephadex LH-20 column.
  • the obtained metal complex dye 1 was adjusted with a 340 ⁇ mol / l tetrabutylammonium hydroxide methanol solvent so that the dye concentration was 17 ⁇ mol / l, and was measured with an ultraviolet-visible spectrophotometer (UV-2400-PC, manufactured by Shimadzu Corporation). When the spectral absorption measurement was performed, the maximum absorption wavelength was 685 nm.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography.
  • 210 ml of DMF and 2.11 g of KSCN were added and reacted at 160 ° C. for 8 hours.
  • the solvent was distilled off under reduced pressure, 67 ml of acetone and 67 ml of 1.0 M aqueous sodium hydroxide solution were added, and the mixture was heated to reflux for 24 hours.
  • the resulting crystals were collected by filtration, added with a small amount of methanol, and purified with a Sephadex LH-20 column.
  • the obtained metal complex dye 81 was subjected to spectral absorption measurement under the same measurement conditions as those for metal complex dye 1, and the maximum absorption wavelength was 680 nm.
  • the dye of the formula (1) of the present invention used in the experiment was prepared.
  • dye represented by Formula (1) of this invention was prepared with reference to the method quoted in patent 4576494 and the said gazette.
  • Example 1 Various pastes for forming the semiconductor layer or light scattering layer of the semiconductor electrode constituting the photoelectrode were prepared, and dye-sensitized solar cells were prepared using this paste.
  • a paste for forming a semiconductor layer or a light scattering layer of a semiconductor electrode constituting a photoelectrode was prepared with the composition shown in Table 4 below. In the following preparation, TiO 2 was put in a medium and stirred to prepare a slurry, and a thickener was added thereto and kneaded to obtain a paste.
  • TiO 2 particles 1 anatase, average particle size; 25 nm TiO 2 particles 2: anatase, average particle size; 200 nm Rod-like TiO 2 particles S1: anatase, diameter: 100 nm, aspect ratio: 5 Rod-like TiO 2 particles S2: anatase, diameter: 30 nm, aspect ratio: 6.3 Rod-like TiO 2 particles S3: anatase, diameter: 50 nm, aspect ratio: 6.1 Rod-like TiO 2 particles S4: anatase, diameter: 75 nm, aspect ratio: 5.8 Rod-like TiO 2 particles S5: anatase, diameter: 130 nm, aspect ratio: 5.2 Rod-like TiO 2 particles S6: anatase, diameter; 180 nm, aspect ratio: 5 Rod-like TiO 2 particles S7: anatase, diameter; 240 nm, aspect ratio: 5 Rod-like TiO 2 particles S8: anatase, diameter: 110 n
  • FIG. 1 A photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5 described in Japanese Patent Laid-Open No. 2002-289274 is prepared by the following procedure, and further, using the photoelectrode, FIG. A 10 mm ⁇ 10 mm scale dye-sensitized solar cell 1 having the same configuration as that of the dye-sensitized solar cell 20 except for the photoelectrode shown in FIG. A specific configuration is shown in FIG. 2 attached to the drawings of the present application. In FIG.
  • 41 is a transparent electrode
  • 42 is a semiconductor electrode
  • 43 is a transparent conductive film
  • 44 is a substrate
  • 45 is a semiconductor layer
  • 46 is a light scattering layer
  • 40 is a photoelectrode
  • 20 is a dye-sensitized solar cell.
  • CE is a counter electrode
  • E is an electrolyte
  • S is a spacer.
  • a transparent electrode in which a fluorine-doped SnO 2 conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the SnO 2 conductive film, a paste 2 described above by screen printing and then dried. Then, it baked on the conditions of 450 degreeC in the air. Furthermore, by repeating this screen printing and baking using the paste 4, a semiconductor electrode having the same configuration as the semiconductor electrode 42 shown in FIG.
  • dye was made to adsorb
  • an iodine-based redox solution containing iodine and lithium iodide as a platinum electrode (thickness of Pt thin film; 100 nm) having the same shape and size as the above-described photoelectrode as a counter electrode and electrolyte E was prepared. Furthermore, a DuPont spacer S (trade name: “Surlin”) having a shape matched to the size of the semiconductor electrode was prepared, and as shown in FIG. 3 described in JP-A-2002-289274, a photoelectrode 40, counter electrode CE, and spacer S were opposed to each other, and the above electrolyte was filled therein to complete a dye-sensitized solar cell.
  • a DuPont spacer S (trade name: “Surlin”) having a shape matched to the size of the semiconductor electrode was prepared, and as shown in FIG. 3 described in JP-A-2002-289274, a photoelectrode 40, counter electrode CE, and spacer S were opposed
  • Rate of descent ( ⁇ L) ( ⁇ i ⁇ g ) / ( ⁇ i )
  • ⁇ L is less than 5%
  • A: ⁇ L is 5% or more and less than 10%
  • B: ⁇ L is 10% or more and less than 15%
  • C: ⁇ L is 15% or more
  • Table 5 shows the results obtained. Shown in ⁇ 7.
  • the comparative dyes used are the following dyes.
  • pastes 1 to 14 other than the above paste 2 were performed for pastes 1 to 14 other than the above paste 2, and it was confirmed that good performance was obtained with the dye of the present invention.
  • the pastes 10 and 13 showed high performance in photoelectric conversion efficiency and durability.
  • Example 2 A dye-sensitized solar cell having the same configuration as that shown in FIG. 1 described in JP 2010-218770 A was produced by the following procedure. A specific configuration is shown in FIG. 3 attached to the drawings of the present application.
  • 51 is a transparent substrate
  • 52 is a transparent conductive film
  • 53 is a barrier layer
  • 54 is an n-type semiconductor electrode
  • 55 is a p-type semiconductor layer
  • 56 is a p-type semiconductor film
  • 57 is a counter electrode (57a is a counter electrode) Projecting part).
  • a transparent conductive oxide (TCO) glass substrate in which SnO 2 : F (fluorine-doped tin oxide) as a transparent conductive film 52 is formed on a transparent glass plate as a transparent substrate 51 of 20 mm ⁇ 20 mm ⁇ 1 mm by CVD is prepared. did. Next, 5 ml of a solution in which Ti [OCH (CH 3 ) 2 ] 4 and water were mixed at a volume ratio of 4: 1 was mixed with 40 ml of an ethyl alcohol solution adjusted to pH 1 with hydrochloride, and the TiO 2 precursor was mixed. A solution was prepared.
  • this solution was spin-coated on a TCO glass substrate at 1000 rpm and sol-gel synthesis was performed, followed by heating at 78 ° C. for 45 minutes under vacuum, and annealing at 450 ° C. for 30 minutes to form a titanium oxide thin film A barrier layer (53) consisting of was formed.
  • a slurry was prepared.
  • the titanium oxide particles were uniformly dispersed using a homogenizer at a ratio of 10% by mass with respect to 100% by mass of the mixed solvent.
  • a solution in which ethyl cellulose as a viscosity modifier is dissolved in ethanol so as to have a concentration of 10% by mass and an alcohol-based organic solvent (terpineol) are added to the titanium oxide slurry prepared above, and again And homogeneously dispersed with a homogenizer. Thereafter, alcohol other than terpineol was removed with an evaporator and mixed with a mixer to prepare a paste-like titanium oxide particle-containing composition.
  • the composition of the prepared titanium oxide particle containing composition made the titanium oxide particle containing composition 100 mass%, the titanium oxide particle was 20 mass%, and the viscosity modifier was 5 mass%.
  • the titanium oxide particle-containing composition thus prepared was applied on the barrier layer 53 formed above so as to form a predetermined pattern by screen printing, dried at 150 ° C., and then in an electric furnace. By heating to 450 ° C., a laminate in which the n-type semiconductor electrode 54 was laminated on the TCO glass substrate was obtained. Next, this laminate was immersed in a zinc nitrate (ZnNO 3 ) solution overnight, and then heated at 450 ° C. for 45 minutes for surface treatment. Thereafter, the surface-treated laminate was immersed in an ethanol solution (concentration of the dye: 3 ⁇ 10 ⁇ 4 mol / L) using various dyes shown in Tables 5 to 7 and allowed to stand at 25 ° C. for 40 hours. Then, the dye was adsorbed inside the n-type semiconductor electrode 54.
  • ZnNO 3 zinc nitrate
  • a copper plate having a thickness of 1 mm was washed with 1 M hydrochloric acid, and further washed with absolute ethanol, and then heated in the atmosphere at 500 ° C. for 4 hours to obtain a CuO nanowire having a maximum diameter of 100 nm and a height of 10 ⁇ m (protrusion 57a ) Was grown.
  • This copper plate was sealed with iodine crystals in a sealed container and heated in a thermostatic bath at 60 ° C. for 1 hour to produce a counter electrode 57 having a thin CuI layer (p-type semiconductor film 56) coated on the surface. Then, the counter electrode 57 was pressed against the laminated body produced above from the p-type semiconductor layer 55 side and laminated.
  • the initial photoelectric conversion efficiency of the dye-sensitized solar cell thus prepared was tested in the same manner as in Example 1. As a result, it was confirmed that the products using the metal complex dye of the present invention can obtain good performance and improvement effect.
  • Example 3 The CdSe quantum dotization process was performed on the photoelectrode by the following method, and a dye-sensitized solar cell shown in FIG. 4 was prepared using an electrolyte using a cobalt complex.
  • FTO glass (1) manufactured by Nippon Sheet Glass Co., Ltd. Surface resistance: 8 ⁇ sq ⁇ 1
  • the titanium (IV) bis (acetylacetonate) diisopropoxide ethanol solution was sprayed 16 times on the surface, and 450 ° C. for 30 minutes. It baked above.
  • a transparent layer of about 2.1 ⁇ m with 20 nm-TiO 2 and a light scattering layer of about 6.2 ⁇ m with 60 nm-TiO 2 (manufactured by Showa Titanium Co., Ltd.) were laminated by screen printing, and later with a TiCl 4 aqueous solution. Processing was performed to prepare an FTO / TiO 2 film.
  • the FTO / TiO 2 film was immersed in a 0.03M Cd (NO 3 ) 2 ethanol solution for 30 seconds in a glove bag under an inert gas atmosphere, and then continuously immersed in a 0.03M selenide ethanol solution for 30 seconds. Soaked. Then, it wash
  • Selenide (Se 2 ⁇ ) was adjusted in the system by adding 0.068 g of NaBH 4 (to a concentration of 0.060M) to a 0.030M SeO 2 ethanol solution in an Ar or N 2 atmosphere.
  • Electrolyte using cobalt complex (0.75 M Co (o-phen) 3 2+ , 0.075 M Co (o-phen) 3 3+ , 0.20 M LiClO 4 acetonitrile / ethylene carbonate (4: 6 / v: v) Solution) is injected into the gap 3 between the electrodes through a hole previously formed on the side of the counter electrode, and then the hole is closed by heat with a binel (DuPont) sheet and a thin glass slide to form a dye-sensitized solar cell. A cell 10 was produced.
  • the cobalt complex added to the electrolyte was prepared by the method described in Chemical Communications, 46, 8788-8790 (2010).
  • the initial photoelectric conversion efficiency of the dye-sensitized solar cell thus prepared was tested in the same manner as in Example 1. As a result, it was confirmed that the products using the metal complex dye of the present invention can obtain good performance and improvement effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention porte sur un élément de conversion photoélectrique qui a une structure stratifiée dans laquelle une couche photosensible ayant une fine couche de particules semi-conductrices sur laquelle un colorant est adsorbé, une couche de transfert de charges et une contre-électrode sont agencées au-dessus d'un corps de support conducteur, le colorant dans ledit élément de conversion photoélectrique étant un colorant à complexe métallique qui est représenté par la formule (1). ML1 m1L2 m2XmX.CI (1). (Dans la formule (1), M représente un atome métallique; L1 représente un ligand représenté par la formule (L1); L² représente un ligand représenté par la formule (L2); X représente un ligand monodentate; chacun de m1 et m2 représente 1; mX représente 0 ou 1; et CI représente un contre-ion dans des cas où un contre-ion est nécessaire pour neutraliser la charge électrique. (Dans la formule (L1), chacun de Za, Zb et Zc représente indépendamment un groupe atomique non métallique nécessaire pour former un noyau à cinq éléments ou à six éléments. A cet égard, au moins l'un des noyaux formés par Za, Zb et Zc a un groupe acidique.) (Dans la formule (L2), le noyau B représente un noyau aromatique à teneur en azote à au moins cinq éléments; chacun du noyau A et du noyau C représente un noyau aromatique à teneur en azote ayant une structure spécifique; a représente 0 ou 1; V représente un substituant ayant une constante de substituant de Hammet positive σp; et un représente un nombre entier de 1 ou plus.)
PCT/JP2012/074779 2011-09-26 2012-09-26 Élément de conversion photoélectrique, cellule photoélectrochimique et colorant à complexe métallique utilisé dans l'élément de conversion photoélectrique WO2013047614A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280046948.XA CN103828122B (zh) 2011-09-26 2012-09-26 光电转换元件、光电化学电池及其中所使用的金属络合物色素
KR1020147007091A KR101890006B1 (ko) 2011-09-26 2012-09-26 광전 변환 소자, 광 전기 화학 전지 및 이에 사용되는 금속 착물 색소

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-208549 2011-09-26
JP2011208549 2011-09-26
JP2012211586A JP5689861B2 (ja) 2011-09-26 2012-09-25 光電変換素子、光電気化学電池およびこれに用いられる金属錯体色素
JP2012-211586 2012-09-25

Publications (1)

Publication Number Publication Date
WO2013047614A1 true WO2013047614A1 (fr) 2013-04-04

Family

ID=47995645

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/074779 WO2013047614A1 (fr) 2011-09-26 2012-09-26 Élément de conversion photoélectrique, cellule photoélectrochimique et colorant à complexe métallique utilisé dans l'élément de conversion photoélectrique

Country Status (4)

Country Link
JP (1) JP5689861B2 (fr)
KR (1) KR101890006B1 (fr)
CN (1) CN103828122B (fr)
WO (1) WO2013047614A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014156953A1 (fr) * 2013-03-25 2014-10-02 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à colorant, et colorant complexe métallique utilisé dans ceux-ci
WO2014168163A1 (fr) * 2013-04-12 2014-10-16 富士フイルム株式会社 Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible
WO2015002081A1 (fr) * 2013-07-05 2015-01-08 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à colorant, colorant complexe métallique, ligand, solution de colorant, électrode à adsorption de colorant, et procédé pour fabriquer une cellule solaire à colorant
EP2980816A4 (fr) * 2013-03-25 2016-06-01 Fujifilm Corp Colorant complexe métallique, élément de conversion photoélectrique, cellule solaire à colorant, et solution de colorant contenant un colorant complexe métallique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106463273B (zh) * 2014-07-07 2019-01-15 富士胶片株式会社 光电转换元件、色素增感太阳能电池、金属络合物色素、色素溶液、以及三联吡啶化合物或其酯化物
JP6204591B2 (ja) * 2014-07-07 2017-09-27 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、およびターピリジン化合物またはそのエステル化物
CN104231661B (zh) * 2014-08-29 2017-06-06 中国工程物理研究院化工材料研究所 环金属配体染料、染料敏化电极和太阳能电池
WO2016052192A1 (fr) * 2014-09-29 2016-04-07 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à colorant, colorant au complexe métallique et solution de colorant

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001291534A (ja) * 2000-01-31 2001-10-19 Fuji Photo Film Co Ltd 光電変換素子および光電池ならびに金属錯体色素
JP2004296170A (ja) * 2003-03-26 2004-10-21 Mitsui Chemicals Inc 光電変換素子用材料、光電変換素子ならびにルテニウム錯体化合物
JP2007277166A (ja) * 2006-04-07 2007-10-25 Ube Ind Ltd ターピリジル配位子を含む金属錯体原料およびその製造方法
JP2009051999A (ja) * 2007-08-29 2009-03-12 National Institute Of Advanced Industrial & Technology 色素及びそれを用いた色素増感太陽電池
JP2009067976A (ja) * 2007-09-17 2009-04-02 Jsr Corp 色素、色素増感太陽電池及びその製造方法
US20100258175A1 (en) * 2009-04-10 2010-10-14 Yun Chi Panchromatic photosensitizers and dye-sensitized solar cell using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH674596A5 (fr) 1988-02-12 1990-06-15 Sulzer Ag

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001291534A (ja) * 2000-01-31 2001-10-19 Fuji Photo Film Co Ltd 光電変換素子および光電池ならびに金属錯体色素
JP2004296170A (ja) * 2003-03-26 2004-10-21 Mitsui Chemicals Inc 光電変換素子用材料、光電変換素子ならびにルテニウム錯体化合物
JP2007277166A (ja) * 2006-04-07 2007-10-25 Ube Ind Ltd ターピリジル配位子を含む金属錯体原料およびその製造方法
JP2009051999A (ja) * 2007-08-29 2009-03-12 National Institute Of Advanced Industrial & Technology 色素及びそれを用いた色素増感太陽電池
JP2009067976A (ja) * 2007-09-17 2009-04-02 Jsr Corp 色素、色素増感太陽電池及びその製造方法
US20100258175A1 (en) * 2009-04-10 2010-10-14 Yun Chi Panchromatic photosensitizers and dye-sensitized solar cell using the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014156953A1 (fr) * 2013-03-25 2014-10-02 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à colorant, et colorant complexe métallique utilisé dans ceux-ci
JP2014209588A (ja) * 2013-03-25 2014-11-06 富士フイルム株式会社 光電変換素子、色素増感太陽電池およびこれに用いる金属錯体色素
EP2980816A4 (fr) * 2013-03-25 2016-06-01 Fujifilm Corp Colorant complexe métallique, élément de conversion photoélectrique, cellule solaire à colorant, et solution de colorant contenant un colorant complexe métallique
US9953768B2 (en) 2013-03-25 2018-04-24 Fujifilm Corporation Metal-complex dye, photoelectric conversion element, dye-sensitized solar cell, and dye solution containing metal-complex dye
WO2014168163A1 (fr) * 2013-04-12 2014-10-16 富士フイルム株式会社 Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible
JP2014207156A (ja) * 2013-04-12 2014-10-30 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、色素吸着電極および色素増感太陽電池の製造方法
WO2015002081A1 (fr) * 2013-07-05 2015-01-08 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à colorant, colorant complexe métallique, ligand, solution de colorant, électrode à adsorption de colorant, et procédé pour fabriquer une cellule solaire à colorant
JP2015029074A (ja) * 2013-07-05 2015-02-12 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素、配位子、色素溶液、色素吸着電極および色素増感太陽電池の製造方法

Also Published As

Publication number Publication date
KR20140068985A (ko) 2014-06-09
JP5689861B2 (ja) 2015-03-25
CN103828122B (zh) 2016-08-17
JP2013084593A (ja) 2013-05-09
KR101890006B1 (ko) 2018-08-20
CN103828122A (zh) 2014-05-28

Similar Documents

Publication Publication Date Title
JP5245001B2 (ja) 光電変換素子、光電気化学電池およびこれに用いる金属錯体色素
JP5689861B2 (ja) 光電変換素子、光電気化学電池およびこれに用いられる金属錯体色素
JP5782349B2 (ja) 光電変換素子及び光電気化学電池、これらに用いられる色素
JP5925541B2 (ja) 光電変換素子用金属錯体色素、光電変換素子、色素増感太陽電池、色素増感太陽電池用色素吸着組成液、色素増感太陽電池用半導体電極および色素増感太陽電池の製造方法
JP5784443B2 (ja) 光電変換素子及び光電気化学電池、並びにこれに用いられる金属錯体色素
JP5809870B2 (ja) 光電変換素子、光電気化学電池、及びそれらに用いられる色素
JP5992581B2 (ja) 光電変換素子及び光電気化学電池、並びにこれに用いられる金属錯体色素
WO2014168163A1 (fr) Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible
JP2012188401A (ja) 金属錯体の製造方法及び金属錯体組成物
JP5788779B2 (ja) 光電変換素子及び光電気化学電池
JP5788817B2 (ja) 光電変換素子及び色素増感太陽電池
WO2015002081A1 (fr) Élément de conversion photoélectrique, cellule solaire à colorant, colorant complexe métallique, ligand, solution de colorant, électrode à adsorption de colorant, et procédé pour fabriquer une cellule solaire à colorant
JP6204603B2 (ja) 光電変換素子、色素増感太陽電池、金属錯体色素および色素溶液
JP6005682B2 (ja) 光電変換素子、色素増感太陽電池およびこれに用いる金属錯体色素
JP5789506B2 (ja) 光電変換素子及び色素増感太陽電池
JP2013077449A (ja) 光電変換素子及びこれを用いた光電気化学電池
JP5636341B2 (ja) 光電変換素子、光電気化学電池、及びそれらに用いられる色素
JP2013175468A (ja) 光電変換素子、光電気化学電池およびこれに用いる金属錯体色素
JP2016063154A (ja) 光電変換素子、色素増感太陽電池、ルテニウム錯体色素および色素溶液

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12836899

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20147007091

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12836899

Country of ref document: EP

Kind code of ref document: A1