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CN103124774A - Metal complex dye, photoelectric conversion element and photoelectrochemical cell - Google Patents

Metal complex dye, photoelectric conversion element and photoelectrochemical cell Download PDF

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Publication number
CN103124774A
CN103124774A CN2011800378132A CN201180037813A CN103124774A CN 103124774 A CN103124774 A CN 103124774A CN 2011800378132 A CN2011800378132 A CN 2011800378132A CN 201180037813 A CN201180037813 A CN 201180037813A CN 103124774 A CN103124774 A CN 103124774A
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Prior art keywords
general formula
ring
metal complex
complex dye
group
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CN2011800378132A
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CN103124774B (en
Inventor
薄达也
小林克
木村桂三
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Fujifilm Corp
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Fujifilm Corp
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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
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
    • 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
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
    • 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
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0676—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having nitrogen atom(s) linked directly to the skeleton
    • 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
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
    • 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
    • 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
    • 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
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • 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

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

Abstract

A metal complex dye represented by general formula (1). In the general formula (1), R11 to R14 each represents a substituent, wherein at least one is an acidic group. a11 to a14 each represents a positive integer of 1 or more. M represents a metal, a metal oxide, or a metal chloride. A to D each represents an aromatic ring. Of the aromatic rings A to D, the aromatic ring having an acidic group represents a diphenylbenzene ring, a naphthalene ring, a phenyl naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, a pentacene ring, a thiazolyl benzene ring, an imidazolyl benzene ring, a 1,3,4-thiadiazolyl benzene ring, a 3-thiazolyl naphthalene ring, a benzothiazole ring, a pi electron-deficient heteroaromatic ring, or a benzene ring or a naphthalene ring to which a pi-electron deficient heteroaromatic ring is bonded.

Description

Metal complex dye, photo-electric conversion element and photoelectrochemical cell
Technical field
The present invention relates to that a kind of efficiency of conversion is high, the metal complex dye of excellent in te pins of durability, photo-electric conversion element and photoelectrochemical cell.
Background technology
Photo-electric conversion element is for various optical sensors, duplicating machine, solar cell etc.In this photo-electric conversion element, use metal photo-electric conversion element, use semi-conductive photo-electric conversion element, use the photo-electric conversion element of pigment dyestuff or pigment or variety of ways such as photo-electric conversion element that they are combined practical.Wherein, utilize the solar cell of sun power of non-exhaustion as not needing fuel, and utilize inexhaustible clean energy person, its real practical making us is extremely expected.Wherein, the research and development that silicon is solar cell have been carried out since previous always.The treatment of policy of various countries is also arranged and universal.But silicon is inorganic materials, naturally there is the limit aspect turnout and molecular modification.
Therefore, carry out just energetically the research of dye-sensitized solar cell.Especially, the lattice Rachel (Graetzel) of the Lausanne Polytechnics of Switzerland etc. is developed the chromatopexis that will the comprise ruthenium complex dye-sensitized solar cell on the surface of porous titania thin films, and has realized the efficiency of conversion identical with non-crystalline silicon.Thus, dye-sensitized solar cell is subject to the attracting attention of investigator in the world quickly.
Record this technology of a kind of application in patent documentation 1, use the dye-sensitized photo-electric conversion element that obtains the semiconductor microactuator particle of sensitizing by the ruthenium complex pigment.But, when the ruthenium complex pigment is used alone as sensitizing agent, price is high, and ruthenium exist to be supplied with the problems such as property is troubling.
Record the metal complex dye of a kind of porphyrin or tetraazatetradecane porphyrin (porphyrazine) skeleton in patent documentation 2.But, in this metal complex dye, use lanthanon, yttrium etc. to be difficult to the metal obtained.In addition, these metals are worrying at secure context.
Record the metal complex dye of the porphyrin skeleton that a kind of aromatic nucleus with carboxyl is pyrazine ring or quinoxaline ring in patent documentation 3.But the special band of the Soret of porphyrin skeleton pigment (Soretband) absorbs script in visibility region, therefore by by the special band of Soret long wavelengthization, also little for the effect of its performance boost.
And then the efficiency of conversion that photo-electric conversion element must be initial is high, after life-time service, the decline of efficiency of conversion less and excellent in te pins of durability.But, on the weather resistance this point, in patent documentation 2 and patent documentation 3, the photo-electric conversion element of record does not claim fully.
The prior art document
Patent documentation
Patent documentation 1: No. 5463057 specification sheets of United States Patent (USP)
Patent documentation 2: Japanese Patent Laid-Open 2000-357543 communique
Patent documentation 3: Japanese Patent Laid-Open 2009-132657 communique
Summary of the invention
The technical task that invention will solve
Problem of the present invention is to provide a kind of metal complex dye, and its photoabsorption wave band is wide, when for photo-electric conversion element and photoelectrochemical cell, can form photo-electric conversion element and the photoelectrochemical cell of efficiency of conversion and excellent in te pins of durability.And then another problem of the present invention is to provide photo-electric conversion element and the photoelectrochemical cell of a kind of efficiency of conversion and excellent in te pins of durability.
Solve the technique means of problem
The inventor etc. have carried out making great efforts research in view of described problem.Its result, find to possess at least 1 aromatic nucleus with acidic groups by the metal complex dye of phthalocyanine frame, the special band of the Soret in ultraviolet region long wavelengthization, and the photoabsorption wave band that can carry out opto-electronic conversion enlarges.And then, find that the volume ratio of the aromatic nucleus have the aromatic nucleus of acidic groups and not have acidic groups is larger, use thus the photo-electric conversion element of this metal complex dye and the weather resistance of photoelectrochemical cell to promote.The present invention is the invention completed according to these discoveries.
In phthalocyanine compound, if with lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) be positioned at any one mode with aromatic nucleus position of acidic groups and carry out molecular designing, electron injection efficiency promotes, and efficiency of conversion uprises.Supposition is in the phthalocyanine compound of so design, and the conjugation at the aromatic nucleus position by making to have LUMO extends or the aromatic nucleus position has the electrophilic heterocycle, and the energy level of LUMO descends, and the photoabsorption wave band enlarges.
According to the present invention, provide following means.
<1 > a kind of metal complex dye is characterized in that: by following general formula (1), meaned.
[changing 1]
General formula (1)
(in general formula (1), R 11～R 14mean substituting group, wherein at least 1 means acidic groups.A11～a14 means the positive integer more than 1.M means metal, metal oxide or metal chloride.A～D means aromatic nucleus.Among the aromatic nucleus of described A～D, aromatic nucleus with acidic groups means phenylbenzene phenyl ring, naphthalene nucleus, phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, pentacene ring, thiazolyl phenyl ring, imidazolyl phenyl ring, 1,3,4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, benzothiazole ring, the assorted aromatic nucleus of the not enough system of π-electron or bond have phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of the not enough system of π-electron)
<2 > according to described<1 > described metal complex dye, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the aromatic nucleus with acidic groups is phenyl ring or the naphthalene nucleus that the assorted aromatic nucleus of the not enough system of π-electron or bond have the assorted aromatic nucleus of the not enough system of π-electron.
<3 > according to described<1 > or<2 > described metal complex dye, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the quantity with aromatic nucleus of acidic groups is 1 or 2.
<4 > according to described<1 > to<3 > the middle described metal complex dye of any one, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the aromatic nucleus that does not have acidic groups is independently respectively phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, thiphene ring or thionaphthene ring.
<5 > according to described<1 > to<4 > the middle described metal complex dye of any one, it is characterized in that: in general formula (1), described acidic groups is carboxyl.
<6>according to described<1>to<5 in the described metal complex dye of any one, it is characterized in that: in general formula (1), beyond described acidic groups by R 11～R 14represented substituting group is independent respectively is alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, alkyl silyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio or aryl silyl, heteroaryl silyl.
<7 > according to described<1 > to<6 > the middle described metal complex dye of any one, it is characterized in that: in general formula (1), a11～a14 is independently respectively 1～4 integer.
<8 > according to described<1 > to<7 > the middle described metal complex dye of any one, it is characterized in that: in general formula (1), M is copper, zinc, tin, nickel, iron, cobalt, silicon, palladium, chloro-aluminium, magnesium, gallium, titanyl oxygen or vanadium oxygen oxygen.
<9 > according to described<1 > to<8 > the middle described metal complex dye of any one, it is characterized in that: by general formula (1), represented metal complex dye is by following general formula (8) or the represented metal complex dye of general formula (9).
[changing 2]
Figure BDA00002803131000041
General formula (8) general formula (9)
(in general formula (8) and general formula (9), A～D means aromatic nucleus.A 1and A 2mean independently respectively acidic groups.D 1～D 3mean independently respectively alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, alkyl silyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio or aryl silyl, heteroaryl silyl.A21～a22 means the integer more than 1.D21～d23 means the positive integer more than 1.M means metal, metal oxide or metal chloride)
<10 > a kind of pigment for use with photoelectric conversion element is characterized in that: comprise according to described<1 > to<9 > the middle described metal complex dye of any one.
<11 > a kind of photo-electric conversion element is characterized in that: comprise photoreceptor layers, this photoreceptor layers has according to described<1 > to<9 > the middle described metal complex dye of any one and semiconductor microactuator particle.
<12 > according to described<11 > described photo-electric conversion element, it is characterized in that: described photoreceptor layers and then contain by the represented metal complex dye of following general formula (2).
Mz (LL 1) m1(LL 2) m2(X) m3cI general formula (2)
[in general formula (2), Mz means atoms metal, LL 1two teeth that expression is represented by following general formula (3) or the dentate of three teeth, LL 2two teeth that expression is represented by following general formula (4) or the dentate of three teeth.X means by selecting free acyloxy, the acyl sulfenyl, the sulfo-acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, the thiocarbamate base, dithiocarbamate groups, the thiocarbonic acid SOH ester group, the dithiocarbonic acid ester group, the trithiocarbonic acid ester group, acyl group, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form carrys out the dentate of single tooth or two teeth of coordination, or select free halogen atom, carbonyl, dialkyl ketone, 1, the 3-diketone, benzamide, single tooth in the cohort that thiobenzamide and thiocarbamide form or the dentate of two teeth.M1 means 0～3 integer, when m1 is 2 when above, and LL 1can be identical, also can be different.M2 means 1～3 integer, when m2 is 2 when above, and LL 2can be identical, also can be different.M3 means 0～3 integer, and when m3 is 2 when above, X can be identical, also can be different, and X also can be linked each other.CI is illustrated in general formula (2), in and electric charge and counter ion while needing counter ion.
[changing 3]
Figure BDA00002803131000051
general formula (3)
In general formula (3), R 21and R 22mean independently respectively acidic groups.R 23and R 24mean independently respectively substituting group, R 25and R 26mean independently respectively alkyl, aryl or heterocyclic radical.D1 and d2 mean respectively 0～5 integer.L 1and L 2mean independently respectively to comprise the conjugated chain of at least 1 in the cohort that the heterocyclic radical that selects free vinylidene, ethynylene and divalence forms.A1 and a2 mean respectively 0～3 integer independently, when a1 is 2 when above, and R 21can be identical, also can be different, when a2 is 2 when above, R 22can be identical, also can be different.B1 and b2 mean respectively 0～3 integer independently, when b1 is 2 when above, and R 23can be identical, also can be different, and R 23can mutually link and form ring.When b2 is 2 when above, R 24can be identical, also can be different, and R 24can mutually link and form ring.When b1 and b2 are 1 when above, R 23with R 24can link and form ring.D3 means 0 or 1.
[changing 4]
general formula (4)
In general formula (4), Za, Zb and Zc mean to form respectively the non-metallic atom group of 5 Yuans rings or 6 Yuans rings independently, and c means 0 or 1.Wherein, at least 1 in the formed ring of Za, Zb and Zc has acidic groups]
<13 > according to described<11 > or<12 > described photo-electric conversion element, it is characterized in that: have by described photoreceptor layers, charge transfer body and to electrode with this sequential lamination the structure on the electroconductibility supporter.
<14 > according to described<11 > to<13 > the middle described photo-electric conversion element of any one, it is characterized in that: described metal complex dye is adsorbed on described semiconductor microactuator particle.
<15 > a kind of photoelectrochemical cell is characterized in that: comprise according to described<11 > to<14 > the middle described photo-electric conversion element of any one.
The effect of invention
The metal complex dye of the application of the invention, can provide that a kind of efficiency of conversion is high, the photo-electric conversion element of excellent in te pins of durability and photoelectrochemical cell.
Suitable to accompanying drawing, and make described feature of the present invention and advantage and other features and advantage become clearer and more definite according to following record.
The accompanying drawing explanation
Fig. 1 is the sectional view that schematically shows the preferred example of photo-electric conversion element of the present invention.
Embodiment
With reference to the graphic preferred example to photo-electric conversion element of the present invention, describe.
As shown in Figure 1, photo-electric conversion element 10 comprises electroconductibility supporter 1, and sequentially the photoreceptor layers 2 of configuration, charge transfer body layer 3 reach electrode 4 on electroconductibility supporter 1.Form and be subject to optoelectronic pole 5 with photoreceptor layers 2 by described electroconductibility supporter 1.This photoreceptor layers 2 has conductive particle 22 and sensitizing coloring matter 21, and at least a portion of pigment 21 is adsorbed on (pigment also can become the adsorption equilibrium state, and a part is present on charge transfer body layer) on conductive particle 22.The electroconductibility supporter 1 that is formed with photoreceptor layers 2 in photo-electric conversion element 10 as active electrode performance function.Make this photo-electric conversion element 10 can be used for the battery use of working by external circuit 6, operate thereby can be used as photoelectrochemical cell 100.
Being subject to optoelectronic pole 5 is to comprise electroconductibility supporter 1 and be configured in the electrode of photoreceptor layers (semiconductor layer) 2 that absorption on electroconductibility supporter 1 has the semiconductor microactuator particle 22 of pigment 21.The light be incident upon in photoreceptor layers 2 is excited pigment.Excite pigment to there is the electronics that energy is high.Therefore, this electronics is sent to the conduction band of semiconductor microactuator particle 22 from pigment 21, and then arrives electroconductibility supporter 1 by diffusion.Now, the molecule of pigment 21 becomes oxysome.Electronics one side on electrode is worked and is simultaneously reverted to the pigment oxidation body by external circuit 6, as photoelectrochemical cell, plays a role thus.Now, be subject to optoelectronic pole 5 to carry out work as the negative pole of this battery.
Moreover, photo-electric conversion element up and down also can not special stipulation, but in this manual, if according to illustrated photo-electric conversion element, the side to electrode 4 that will become sensitive side is made as the direction at top (top), the side of electroconductibility supporter 1 is made as to the direction of bottom (bottom).
Photo-electric conversion element of the present invention has photoreceptor layers on the electroconductibility supporter, and this photoreceptor has the Porous semiconductor microactuator particle layer that absorption has pigment described later.Photoreceptor layers is to design according to purpose, can be that individual layer forms, and can be also that multilayer forms.Pigment in photoreceptor layers can be a kind of, also can mix multiple pigment and form, but at least a kind of use metal complex dye described later wherein.In the photoreceptor of photo-electric conversion element of the present invention, comprise the semiconductor microactuator particle that this pigment adsorbs, light sensitivity is high, when as photoelectrochemical cell, can obtain high conversion efficiency.
Below, to being described by the represented metal complex dye of following general formula (1) of using in photo-electric conversion element of the present invention.
[changing 5]
Figure BDA00002803131000081
General formula (1)
In general formula (1), R 11～R 14mean substituting group, wherein at least 1 means acidic groups.A11～a14 means the positive integer more than 1.M means metal, metal oxide or metal chloride.A～D means aromatic nucleus.So-called " M means metal chloride ", refer to that the chloride ion coordination is on central metal herein.In addition, so-called acidic groups, except the acidic groups such as carboxyl itself, can be also to replace via concatenating group the person of forming in the scope that obtains desired effect, comprises that this concatenating group is called acidic groups.
In general formula (1), A～D means aromatic nucleus.Described aromatic nucleus can be the aromatic hydrocarbons ring, can be also heteroaromatic.
Aromatic hydrocarbons ring as A, B, C and the D of general formula (1), the monocycle that preferably carbon number is 6～30 or the aromatic hydrocarbons ring of two rings, the aromatic hydrocarbons ring of the monocycle that more preferably carbon number is 6～20 or two rings, and then the aromatic hydrocarbons ring of the monocycle that more preferably carbon number is 6～12 or two rings.Concrete example as the aromatic hydrocarbons ring, can enumerate: phenyl ring, cyclohexyl biphenyl, 1,3-phenylbenzene phenyl ring, anthracene nucleus, naphthalene nucleus, 1-phenyl naphthalene nucleus, 2-phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, ring in the wrong, Sanya phenyl ring (triphenylene ring), benzo anthracene nucleus (tetraphene ring), pyrene ring, pentacene ring, Pi ring, perylene ring etc.In the present invention, as the aromatic hydrocarbons ring of A, B, C and the D of general formula (1), particularly preferably phenyl ring and naphthalene nucleus.Described aromatic hydrocarbons ring can have substituting group, as substituting group, can enumerate substituting group T described later.
As heterocycle structure, preferably contain Sauerstoffatom, nitrogen-atoms, sulphur atom and/or selenium atom as heteroatomic heteroaromatic.Concrete example as heteroaromatic, can enumerate: furan nucleus, pyrrole ring, thiphene ring, imidazole ring, pyrazole ring, triazole ring, triazine ring, indole ring, the indazole ring, purine skeleton, thiazoline ring, thiazole ring, Thiadiazole, the thionaphthene ring, the thienothiophene ring, the bithiophene ring, the oxazoline ring, the oxazole ring, the oxadiazoles ring, the phthalazines ring, the naphthyridines ring, the cinnolines ring, the pyridine ring of talking endlessly, coffee quinoline ring, tetrazole ring, the benzoglyoxaline ring, the benzoxazoles ring, the benzothiazole ring, the benzotriazole ring, four benzazole rings, the π-electron deficiency is heteroaromatic, it is the phenyl ring of heteroaromatic or naphthalene nucleus etc. that bond has the π-electron deficiency.So-called π-electron deficiency is heteroaromatic, refers to the complete unsaturated heterocycle that contains heteroatoms and have the position of π-electron deficiency, as heteroatoms, and the preferred nitrogen atom.Particularly, as its mother nucleus structure, can enumerate the pyridine, quinoline, isoquinoline 99.9, acridine, indolizine, the coffee pyridine that contain 1 nitrogen-atoms, the pyridazine that contains 2 nitrogen-atoms, pyrimidine, pyrazine, quinazoline, quinoxaline, 1,5-naphthyridines, azophenlyene, the symmetrical triazine that contains 3 nitrogen-atoms, asymmetric triazine, the pterin that contains 4 nitrogen-atoms etc.In the present invention, preferably 5 Yuans rings or the heteroaromatic of 6 Yuans rings, also can so that with other rings ring that contracts.As heteroaromatic, more preferably quinoxaline ring, thiphene ring, pyridine ring, pyrazine ring, thiazole ring, thienothiophene ring, benzothiazole ring.
As substituting group T, for example can enumerate: (alkyl that particularly preferably carbonatoms is 1～8, for example can enumerate methyl to alkyl for the alkyl that preferably carbonatoms is 1～20, the alkyl that more preferably carbonatoms is 1～12, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, positive hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), (preferably carbonatoms is 2～20 to thiazolinyl, and more preferably carbonatoms is 2～12, and particularly preferably carbonatoms is 2～8, for example can enumerate vinyl, allyl group, crotyl, 3-pentenyl etc.), (preferably carbonatoms is 2～20 to alkynyl, and more preferably carbonatoms is 2～12, and particularly preferably carbonatoms is 2～8, for example can enumerate propargyl, 3-pentynyl etc.), (preferably carbonatoms is 6～30 to aryl, and more preferably carbonatoms is 6～20, and particularly preferably carbonatoms is 6～12, for example can enumerate phenyl, xenyl, naphthyl etc.), (preferably carbonatoms is 0～20 to the amino that is substituted or is unsubstituted, and more preferably carbonatoms is 0～10, and particularly preferably carbonatoms is 0～6, for example can enumerate amino, methylamino-, dimethylamino, diethylin, dibenzyl amino etc.),
(preferably carbonatoms is 1～20 to alkoxyl group, and more preferably carbonatoms is 1～12, and particularly preferably carbonatoms is 1～8, for example can enumerate methoxyl group, oxyethyl group, butoxy etc.), (preferably carbonatoms is 6～20 to aryloxy, and more preferably carbonatoms is 6～16, and particularly preferably carbonatoms is 6～12, for example can enumerate phenoxy group, 2-naphthyloxy etc.), (preferably carbonatoms is 1～20 to acyl group, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate ethanoyl, benzoyl, formyl radical, pivaloyl etc.), (preferably carbonatoms is 2～20 to alkoxy carbonyl, and more preferably carbonatoms is 2～16, and particularly preferably carbonatoms is 2～12, for example can enumerate methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferably carbonatoms is 7～20, and more preferably carbonatoms is 7～16, and particularly preferably carbonatoms is 7～10, such as enumerating phenyloxycarbonyl etc.), (preferably carbonatoms is 2～20 to acyloxy, and more preferably carbonatoms is 2～16, and particularly preferably carbonatoms is 2～10, for example can enumerate acetoxyl group, benzoyloxy etc.),
(preferably carbonatoms is 2～20 to acyl amino, and more preferably carbonatoms is 2～16, and particularly preferably carbonatoms is 2～10, for example can enumerate acetylamino, benzoyl-amido etc.), alkoxycarbonyl amino (preferably carbonatoms is 2～20, and more preferably carbonatoms is 2～16, and particularly preferably carbonatoms is 2～12, such as enumerating methoxycarbonyl amino etc.), aryloxycarbonyl amino (preferably carbonatoms is 7～20, and more preferably carbonatoms is 7～16, and particularly preferably carbonatoms is 7～12, such as enumerating phenyloxycarbonyl amino etc.), (preferably carbonatoms is 1～20 to sulfuryl amino, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate methylsulfonyl amino, benzenesulfonyl amino etc.), (preferably carbonatoms is 0～20 to sulfamyl, and more preferably carbonatoms is 0～16, and particularly preferably carbonatoms is 0～12, for example can enumerate sulfamyl, the methyl sulfamyl, the dimethylamino alkylsulfonyl, phenyl sulfamoyl base etc.), (preferably carbonatoms is 1～20 to carbamyl, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate carbamyl, methylcarbamoyl, the diethyl amino formyl radical, phenylamino formyl radical etc.),
(preferably carbonatoms is 1～20 to alkylthio, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate methylthio group, ethylmercapto group etc.), arylthio (preferably carbonatoms is 6～20, and more preferably carbonatoms is 6～16, and particularly preferably carbonatoms is 6～12, such as enumerating thiophenyl etc.), (preferably carbonatoms is 1～20 to alkylsulfonyl, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate methylsulfonyl, tosyl group etc.), (preferably carbonatoms is 1～20 to sulfinyl, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate methanesulfinyl, benzenesulfinyl etc.), (preferably carbonatoms is 1～20 to urea groups, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate urea groups, the methyl urea groups, phenyl urea groups etc.), (preferably carbonatoms is 1～20 to the phosphinylidyne amido, and more preferably carbonatoms is 1～16, and particularly preferably carbonatoms is 1～12, for example can enumerate diethyl phosphinylidyne amido, phenyl phosphinylidyne amido etc.), hydroxyl, sulfydryl, halogen atom (fluorine atom for example, the chlorine atom, bromine atoms, the iodine atom), cyano group, sulfo group, carboxyl, nitro, the hydroximic acid base, sulfino, diazanyl, imino-, (preferably carbonatoms is 1～30 to heterocyclic radical, and more preferably carbonatoms is 1～12, as heteroatoms, for example can enumerate nitrogen-atoms, Sauerstoffatom, sulphur atom, particularly, for example can enumerate imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl-, benzothiazolyl etc.), (preferably carbonatoms is 3～40 to silyl, and more preferably carbonatoms is 3～30, and particularly preferably carbonatoms is 3～24, for example can enumerate trimethyl silyl, triphenyl silyl etc.) etc.
Among described substituting group, the substituting group with hydrogen atom also can be removed hydrogen atom and further be replaced by described base.As this kind of functional group's example, can enumerate: alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkyl sulfonyl-amino carbonyl, aryl sulfonyl amino carbonyl.As its example, can enumerate: methyl sulphonyl aminocarboxyl, p-methylphenyl sulfonyl amino carbonyl, acetylamino alkylsulfonyl, benzoyl-amido alkylsulfonyl.
In addition, when thering is plural substituting group, can be identical, also can be different.In addition, in the situation that possible also can mutually link and form ring.
In general formula (1), by A～D among represented aromatic nucleus, aromatic nucleus with acidic groups is the phenylbenzene phenyl ring, naphthalene nucleus, the phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, the tetracene ring, the pentacene ring, the thiazolyl phenyl ring, the imidazolyl phenyl ring, 1, 3, 4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, the benzothiazole ring, the not enough system of π-electron assorted aromatic nucleus (preferred pyridine ring, pyrimidine ring, the pyridazine ring, the pyrazine ring, triazine ring, pyrazole ring, imidazole ring), bond has the not enough system of π-electron assorted aromatic nucleus (preferred pyridine ring, pyrimidine ring, the pyridazine ring, the pyrazine ring, triazine ring, pyrazole ring, imidazole ring) phenyl ring or naphthalene nucleus, preferably π-electron is not enough is assorted aromatic nucleus, bond has phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of the not enough system of π-electron.
In general formula (1), preferably by A～D among represented aromatic nucleus, the quantity with aromatic nucleus of acidic groups is 1 or 2.
In general formula (1), preferably by A～D among represented aromatic nucleus, not having the aromatic nucleus of acidic groups independent respectively is phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, thiphene ring or thionaphthene ring.
By R 11～R 14there is no particular restriction for represented acidic groups (substituting group with proton of dissociating property), can enumerate: carboxyl, phosphonate group, sulfo group, sulfonic group, hydroxyl, hydroximic acid base, phosphoryl or phosphono (phosphinyl), sulfino, sulfinyl, phosphinyl (phosphinyl), phosphono (phosphono), thiol group and alkylsulfonyl and their salt etc.There is no particular restriction for described salt, can be any of organic salt, inorganic salt.As representative example, can enumerate: the salt such as alkalimetal ion (lithium, sodium, potassium etc.), alkaline-earth metal ions (magnesium, calcium etc.), ammonium, alkylammonium (such as diethyl ammonium, TBuA etc.), pyridine, alkyl pyridine (such as picoline), guanidine, four alkane base Phosphonium.In general formula (1), when thering is a plurality of acidic groups, respectively can be identical, also can be different.
In the present invention, as described acidic groups, preferred carboxyl, sulfonic group, phosphoryl or phosphono, more preferably carboxyl.
In general formula (1), as beyond described acidic groups by R 11～R 14represented substituting group, can preferably enumerate: the alkyl (straight chain that preferably carbon number is 1～20, branch, the alkyl that is substituted or is unsubstituted of ring-type, as substituting group, can preferably enumerate n-hexyl, 2-ethyl-hexyl, tertiary octyl group, nonyl etc.), (aryl that is substituted or is unsubstituted that preferably carbon number is 6～20, as substituting group, can preferably enumerate alkyl to aryl, alkylamino, alkoxyl group, alkylthio etc.), (heterocyclic radical that is substituted or is unsubstituted that preferably carbon number is 3～20, as substituting group, can preferably enumerate alkyl to heterocyclic radical, alkylamino, alkoxyl group, alkylthio etc.), alkoxyl group (the straight chain that preferably carbon number is 1～20, branch, the alkoxyl group that is substituted or is unsubstituted of ring-type, as substituting group, can preferably enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), alkylthio (the straight chain that preferably carbon number is 1～20, branch, the alkylthio that is substituted or is unsubstituted of ring-type, as substituting group, can preferably enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), alkyl silyl (the straight chain that preferably carbon number is 1～20, branch, the alkyl silyl that is substituted or is unsubstituted of ring-type, as substituting group, can preferably enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (aryloxy that is substituted or is unsubstituted that preferably carbon number is 6～20, as substituting group, can preferably enumerate alkyl to aryloxy, alkylamino, alkoxyl group, alkylthio etc.), (heteroaryloxy that is substituted or is unsubstituted that preferably carbon number is 3～20, as substituting group, can preferably enumerate alkyl to heteroaryloxy, alkylamino, alkoxyl group, alkylthio etc.), (arylthio that is substituted or is unsubstituted that preferably carbon number is 6～20, as substituting group, can preferably enumerate alkyl to arylthio, alkylamino, alkoxyl group, alkylthio etc.), (heteroarylthio that is substituted or is unsubstituted that preferably carbon number is 3～20, as substituting group, can preferably enumerate alkyl to heteroarylthio, alkylamino, alkoxyl group, alkylthio etc.), or the aryl silyl (the aryl silyl that is substituted or is unsubstituted that preferably carbon number is 6～20, as substituting group, can preferably enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (the heteroaryl silyl that is substituted or is unsubstituted that preferably carbon number is 3～20, as substituting group, can preferably enumerate alkyl to the heteroaryl silyl, alkylamino, alkoxyl group, alkylthio etc.).
In general formula (1), a11～a14 means the integer more than 1.A11～a14 preferably means 1～4 integer, more preferably means 1 or 2.
In general formula (1), M means metal, metal oxide or metal chloride.As the concrete example of metal and metal oxide, can enumerate: copper (Cu), zinc (Zn), plumbous (Pb), nickel (Ni), tin (Sn), iron (Fe), silicon (Si), cobalt (Co), ruthenium (Ru), palladium (Pd), magnesium (Mg), vanadium (V), vanadium oxygen (V=O), titanyl (Ti=O) etc.In the present invention, preferably copper (Cu), zinc (Zn), plumbous (Pb), nickel (Ni), tin (Sn), silicon (Si), cobalt (Co), ruthenium (Ru), palladium (Pd), and vanadium oxygen (V=O).As the concrete example of metal chloride, can enumerate: aluminum chloride (Al-Cl), tin chloride (Sn-Cl 2), Manganous chloride tetrahydrate (Mn-Cl), titanium chloride (Ti-Cl 2), gallium chloride (Ga-Cl), indium chloride (In-Cl) etc.In the present invention, preferred tin chloride, aluminum chloride.
In the aromatic nucleus with acidic groups in the aromatic nucleus of described A～D, described aromatic nucleus preferably has 1～4 acidic groups, more preferably has 1～2 acidic groups.
The metal complex dye represented by general formula (1) is preferably by following general formula (8) or the represented metal complex dye of general formula (9).Among these metal complex dyes, more preferably by the represented metal complex dye of general formula (8).
[changing 6]
Figure BDA00002803131000131
General formula (8) general formula (9)
In general formula (8) and general formula (9), A, B, C, D, and A, the B of the implication of M and general formula (1), C, D, and M identical, preferably scope is also identical.
In general formula (8) and general formula (9), A 1and A 2mean independently respectively acidic groups, and respectively can be identical, also can be different.As the concrete example of acidic groups, can enumerate in general formula (1) as R 11～R 14the illustrated acidic groups of acidic groups, preferred scope is also identical.
In general formula (8) and general formula (9), D 1～D 3mean independently respectively alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, alkyl silyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio or aryl silyl, heteroaryl silyl.
In general formula (8) and general formula (9), a21～a22 means the integer more than 1.A21～a22 preferably means 1～4 integer, more preferably means 1 or 2.
In general formula (8) and general formula (9), d21～d23 means the integer more than 1.D21～d23 preferably means 1～4 integer, more preferably means 1～3.
By general formula (1), the represented metal complex dye maximum absorption wavelength (peak value of Q band) in solution is preferably in the scope in 500nm～1500nm, more preferably in the scope in 600nm～1200nm.In addition, the peak value of the special band of Soret is preferably in the scope in 200nm～600nm, more preferably in the scope in 300nm～500nm.
And then the photoabsorption wave band by general formula (1) under the above wavelength of the 400nm of represented pigment is preferably in the scope in 400nm～1500nm, more preferably in the scope in 400nm～1200nm.In addition, the wavelength difference of the peak value of Q band and the special peak value of being with of Soret is preferably in the scope in 100nm～400nm, more preferably in the scope in 150nm～350nm.
Below, the preferred concrete example of expression represented metal complex dye by general formula (1), but the present invention is not limited to following concrete example.
[changing 7]
Figure BDA00002803131000151
[changing 8]
Figure BDA00002803131000161
[changing 9]
Figure BDA00002803131000171
[changing 10]
Figure BDA00002803131000181
[changing 11]
Figure BDA00002803131000191
[changing 12]
Figure BDA00002803131000201
[changing 13]
Figure BDA00002803131000211
[changing 14]
[changing 15]
Figure BDA00002803131000231
[changing 16]
Figure BDA00002803131000241
[changing 17]
Figure BDA00002803131000251
[changing 18]
Figure BDA00002803131000261
[changing 19]
Figure BDA00002803131000271
[changing 20]
Figure BDA00002803131000281
[changing 21]
Figure BDA00002803131000291
[changing 22]
[changing 23]
Figure BDA00002803131000311
[changing 24]
[changing 25]
Figure BDA00002803131000331
[changing 26]
Figure BDA00002803131000341
[changing 27]
Figure BDA00002803131000351
[changing 28]
Figure BDA00002803131000361
[changing 29]
Figure BDA00002803131000371
[changing 30]
Figure BDA00002803131000381
[changing 31]
Figure BDA00002803131000391
Below, by general formula (1), the synthetic method of represented metal complex dye describes to of the present invention.But the present invention is not limited by these methods.
The metal complex dye represented by general formula (1) of the present invention, as shown in for example following flow process (I), can make Aromatic Dinitriles compound of more than two kinds and/or diimino azole compounds be reacted synthetic with the metal derivative represented by following general formula (5).Perhaps, as shown in following flow process (II), can, by after making Aromatic Dinitriles compound of more than two kinds and/or diimino pyrrole derivative and the metal derivative represented by general formula (6) being reacted, with the metal derivative represented by general formula (5), be reacted synthetic.But the present invention is not limited by these flow processs.
[changing 32]
[changing 33]
Figure BDA00002803131000402
In flow process (I) and flow process (II), R amean substituting group, R bmean the assorted aromatic nucleus of the not enough system of π-electron with acidic groups in flow process (I), mean acidic groups or with the not enough system of π-electron of the acidic groups aromatic nucleus of mixing in flow process (II).N1 and N2 mean the integer more than 1.The M implication is identical with the M of general formula (1).
To being described by the represented metal derivative of general formula (5).
General formula (5): M-(X ') e
In general formula (5), the implication of M is identical with the M of general formula (1).The dentate of the monovalencies such as X ' expression halogen atom, acetic acid ion, acetylacetone based, oxygen or divalence, e means 1～4 integer.
To being described by the represented metal derivative of general formula (6).
The f of general formula (6): M '-(Y)
In general formula (6), M ' expression basic metal, Y means the dentate of the monovalencies such as halogen atom, acetic acid ion, acetylacetone based, alcoholate, oxygen or divalence, f means 1～4 integer.
When making 2 kinds of Aromatic Dinitriles and/or diimino azole compounds react to synthesize metal complex dye of the present invention, there is no particular restriction for its ratio of mixture, but with molar ratio computing preferably 1: 4～4: 1.
In the reaction shown in flow process (I) and flow process (II), there is no particular restriction for the usage quantity of metal derivative and Aromatic Dinitriles, but with molar ratio computing preferably 1: 3～1: 6.
Reaction shown in flow process (I) and flow process (II) is carried out usually under the existence of solvent.There is no particular restriction for solvent, and can preferably use boiling point is more than 80 ℃, preferably the organic solvent more than 95 ℃.Such as enumerating: propyl carbinol, Pentyl alcohol, n-hexyl alcohol, hexalin, 2-methyl-1-pentene alcohol, 1-heptanol, 2-enanthol, 1-octanol, 2-Ethylhexyl Alcohol, benzylalcohol, ethylene glycol, propylene glycol, ethoxy ethanol, propoxy-ethanol, butyl cellosolve, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, tetramethylene sulfone, oil of mirbane, quinoline, urea etc.
There is no particular restriction for the usage quantity of solvent, but 1 quality of optimization aromatic dinitrile compound and/or diimino azole compounds doubly～100 quality doubly, more preferably 3 quality doubly～20 quality doubly.
In the reaction shown in flow process (I) and flow process (II), also can use catalyst.There is no particular restriction for catalyst, can enumerate 1,8-diaza-bicyclo [5.4.0]-7-hendecene (1,8-Diazabicyclo[5.4.0]-7-Undecene, DBU), ammonium molybdate etc.There is no particular restriction for the addition of catalyst, but with respect to 1 mole of Aromatic Dinitriles compound and/or diimino azole compounds, preferably 0.1 times mole～10 times moles, more preferably 0.5 times mole～2 times moles.
There is no particular restriction for the temperature of reaction of the reaction shown in flow process (I) and flow process (II), but preferably 80 ℃～300 ℃, more preferably 90 ℃～250 ℃, particularly preferably 110 ℃～230 ℃.If temperature of reaction is too low, speed of response becomes extremely slow, if temperature of reaction is too high, likely produces the decomposition of Aromatic Dinitriles compound and/or diimino azole compounds.
The reaction times of the reaction shown in flow process (I) and flow process (II), there is no particular restriction, but preferably 2 hours～20 hours, more preferably 5 hours～15 hours, particularly preferably 5 hours～10 hours.If the reaction times is too short, unreacting material increases, if the reaction times is long, likely produces the decomposition of Aromatic Dinitriles compound and/or diimino azole compounds.
The metal complex dye represented by general formula (1) of the present invention is synthetic as also can be as shown in following flow process (I ') or (flow process II ').
Particularly; can come in the following way to synthesize: make to comprise and have by Aromatic Dinitriles compound of more than two kinds and/or the diimino azole compounds of the Aromatic Dinitriles compound of the acidic groups (ester group) of protecting group protection and/or diimino azole compounds, reacted with the metal derivative represented by described general formula (5), then utilize the alkali-metal hydroxide salt represented by following general formula (7) that generated intermediate is hydrolyzed.Perhaps; can come in the following way to synthesize: make to comprise and have by the Aromatic Dinitriles compound of more than two kinds of the Aromatic Dinitriles compound of the acidic groups (ester group) of protecting group protection and/or diimino azole compounds and/or diimino pyrrole derivative, with after the metal derivative represented by described general formula (6) reacted; reacted with the metal derivative represented by described general formula (5), then utilize the alkali-metal hydroxide salt represented by following general formula (7) by generated intermediate hydrolysis.
[changing 34]
Figure BDA00002803131000421
[changing 35]
Figure BDA00002803131000431
In flow process (I ') and flow process (II '), R a' expression is by the acidic groups of protecting group protection, R a, R b, N1, N2 and the implication of M and the R of flow process (I) and flow process (II) a, R b, N1, N2 and M implication identical.
To being described by the represented compound of general formula (7).
General formula (7): M ' (OH) g
In general formula (7), M ' expression basic metal, g means 1～2 integer.
When making to comprise, have while being reacted to synthesize metal complex dye of the present invention by 2 kinds of Aromatic Dinitriles compounds of the Aromatic Dinitriles compound of the acidic groups (ester group) of protecting group protection and/or diimino azole compounds and/or diimino azole compounds; there is no particular restriction for its ratio of mixture, but with molar ratio computing preferably 1: 4～4: 1.
In the reaction shown in flow process (I ') and flow process (II '), there is no particular restriction for the usage quantity of metal derivative and Aromatic Dinitriles compound and/or diimino azole compounds, but with molar ratio computing preferably 1: 3～1: 6.
In the reaction shown in flow process (I ') and flow process (II '), there is no particular restriction for the usage quantity of alkali-metal hydroxide salt, but with respect to intermediate t mole, more than preferably using (t * N1) mole.
Reaction shown in flow process (I ') and flow process (II ') is carried out usually under the existence of solvent.There is no particular restriction for solvent, but the solvent that preferred described intermediate dissolves.Such as enumerating: pure series solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohols, or the ether series solvent such as dme, cyclopentyl methyl ether, tetrahydrofuran (THF), dioxan, the nitrile such as acetonitrile, propionitrile series solvent, or mixed solvent each other of these solvents or with the mixed solvent of water.In addition, also can make the mixed solvent of the hydrocarbon system solvents such as water or these solvents and toluene, dimethylbenzene, hexane, heptane.
There is no particular restriction for the usage quantity of solvent, but 1 quality of optimization aromatic dinitrile compound and/or diimino azole compounds doubly～100 quality doubly, more preferably 3 quality doubly～60 quality doubly.
There is no particular restriction for the temperature of reaction of the reaction shown in flow process (I ') and flow process (II '), but preferably 20 ℃～300 ℃, more preferably 40 ℃～200 ℃, particularly preferably 60 ℃～150 ℃.If temperature of reaction is too low, speed of response becomes extremely slow, if temperature of reaction is too high, likely produces and decomposes.
The reaction times of the reaction shown in flow process (I ') and flow process (II '), there is no particular restriction, but preferably 0.5 hour～100 hours, more preferably 2 hours～50 hours, particularly preferably 5 hours～40 hours.If the reaction times is too short, unreacting material increases, if the reaction times is long, likely produces and decomposes.
The product obtained by described reaction can, after the post-treating method according to common organic synthesis is processed, be made with extra care or not make with extra care and be made for metal complex dye of the present invention.For example, the product that can dissociating in the autoreaction system is made with extra care and metal complex dye of the present invention is provided, perhaps (for example will utilize recrystallize, column chromatography, gel permeation chromatography (SEPHADEXTMLH-20: Pharmacia (Pharmacia) is manufactured), high performance liquid chromatography (High Performance Liquid Chromatography, the operation of HPLC) etc. being made with extra care provides metal complex dye of the present invention after carrying out separately or combining and carry out.
Perhaps, can be after reaction finishes, heat up in a steamer the dereaction solvent, perhaps do not heat up in a steamer and pour out and neutralized to water or ice, the product that is not perhaps neutralized and dissociating is made with extra care and metal complex dye of the present invention is provided, the operation that perhaps will utilize recrystallize, column chromatography, HPLC etc. to be made with extra care provides metal complex dye of the present invention after carrying out separately or combining and carry out.
Perhaps, can be after reaction finishes, heat up in a steamer the dereaction solvent, perhaps do not heat up in a steamer and pour out and neutralized to water or ice, perhaps do not neutralized and not to utilizing the product that organic solvent/aqueous solution extracts make with extra care and metal complex dye of the present invention is provided, after perhaps utilizing operation that partial crystallization, column chromatography, HPLC are made with extra care to carry out separately or combine and carry out, provide metal complex dye of the present invention.
Moreover, in this manual, about the compound expression of (comprising complex compound, pigment), except this compound itself, also for comprising the implication of its salt, complex compound (beyond complex compound time), its ion.In addition, refer to and be included in the scope that obtains desired effect, the implication of with the form of regulation, being modified the compound formed.In addition, in this manual, about stating clearly, be not substituted the substituting group be unsubstituted, refer to that this base can have substituent implication arbitrarily.Do not state clearly the implication that is substituted the compound be unsubstituted like this too.As preferred substituting group, can enumerate described substituting group T.
Photo-electric conversion element of the present invention possesses the photoreceptor layers with metal complex dye and semiconductor microactuator particle.
About photo-electric conversion element of the present invention and use its photoelectrochemical cell, in the photoreceptor layers of described photo-electric conversion element, except metal complex dye of the present invention, can and use other pigments.There is no particular restriction for these other pigments, can enumerate by the represented dye compound of following general formula (2).
Mz (LL 1) m1(LL 2) m2(X) m3cI general formula (2)
Pigment coordination on atoms metal with structure of general formula (2) has dentate LL 1and/or dentate LL 2, and specific functional group X optionally, in the case of necessary, by CI, remain electric neutrality.
In general formula (2), Mz means atoms metal.Mz preferably can carry out the metal of four-coordination or hexa-coordinate, more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn or Zn, particularly preferably Ru, Os, Zn or Cu, most preferably Ru.X means by selecting free acyloxy, the acyl sulfenyl, the sulfo-acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, the thiocarbamate base, dithiocarbamate groups, the thiocarbonic acid SOH ester group, the dithiocarbonic acid ester group, the trithiocarbonic acid ester group, acyl group, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form carrys out the dentate of single tooth or two teeth of coordination, or select free halogen atom, carbonyl, dialkyl ketone, 1, the 3-diketone, benzamide, single tooth in the cohort that thiobenzamide and thiocarbamide form or the dentate of two teeth.
In general formula (2), dentate LL 1two teeth that expression is represented by following general formula (3) or the dentate of three teeth, preferably two tooth dentates.Mean dentate LL 1the m1 of the quantity integer that is 0～3, preferably 1～3, more preferably 1.When m1 is 2 when above, a plurality of LL 1can be identical, also can be different.Therefore, dentate LL 1and/or dentate LL 2coordination is on atoms metal Mz.
In following general formula (3), R 21and R 22mean independently respectively acidic groups, for example can enumerate: carboxyl, sulfonic group, hydroxyl, hydroximic acid base (the hydroximic acid base that preferably carbonatoms is 1～20, for example-CONHOH ,-CONCH 3oH etc.), (for example-OP (O) (OH) for phosphoryl 2deng) and phosphono (for example-P (O) (OH) 2deng) and their salt.Carboxyl, phosphono can be preferably enumerated, carboxyl and their salt can be more preferably enumerated.By R 21and R 22represented acidic groups also can be substituted on any carbon atom on pyridine ring.
[changing 36]
Figure BDA00002803131000461
general formula (3)
In general formula (3), R 23, R 24mean independently respectively substituting group.As described substituent concrete example, can enumerate: alkyl (alkyl that preferably carbonatoms is 1～20, for example methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group, heptyl, the 1-ethyl pentyl group, benzyl, the 2-ethoxyethyl group, 1-carboxymethyl etc.), thiazolinyl (thiazolinyl that preferably carbonatoms is 2～20, for example vinyl, allyl group, oleyl etc.), alkynyl (alkynyl that preferably carbonatoms is 2～20, for example ethynyl, the diacetylene base, phenylene-ethynylene etc.), cycloalkyl (cycloalkyl that preferably carbonatoms is 3～20, for example cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), aryl (aryl that preferably carbonatoms is 6～26, for example phenyl, the 1-naphthyl, the 4-p-methoxy-phenyl, the 2-chloro-phenyl-, 3-aminomethyl phenyl etc.), heterocyclic radical (heterocyclic radical that preferably carbonatoms is 2～20, for example 2-pyridyl, the 4-pyridyl, the 2-imidazolyl, the 2-benzimidazolyl-, the 2-thiazolyl, 2-oxazolyl etc.), alkoxyl group (alkoxyl group that preferably carbonatoms is 1～20, for example methoxyl group, oxyethyl group, isopropoxy, benzyloxy etc.), aryloxy (aryloxy that preferably carbonatoms is 6～26, for example phenoxy group, the 1-naphthyloxy, the 3-methylphenoxy, 4-methoxyphenoxy etc.), alkoxy carbonyl (alkoxy carbonyl that preferably carbonatoms is 2～20, for example ethoxy carbonyl, 2-ethyl hexyl oxy carbonyl etc.), amino (amino that preferably carbonatoms is 0～20, for example amino, N, the N-dimethylamino, N, the N-diethylin, the N-ethylamino, phenylamino etc.), sulfoamido (sulfoamido that preferably carbonatoms is 0～20, N for example, N-dimethyl methyl acid amides, N-phenyl-sulfamide etc.), acyloxy (acyloxy that preferably carbonatoms is 1～20, for example acetoxyl group, benzoyloxy etc.), carbamyl (carbamyl that preferably carbonatoms is 1～20, N for example, N-dimethylamino formyl radical, N-phenylamino formyl radical etc.), acyl amino (acyl amino that preferably carbonatoms is 1～20, for example acetylamino, benzoyl-amido etc.), cyano group, or halogen atom (fluorine atom for example, the chlorine atom, bromine atoms, iodine atom etc.).As described substituting group; preferred alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkoxy carbonyl, amino, acyl amino, cyano group and halogen atom, more preferably alkyl, thiazolinyl, heterocyclic radical, alkoxyl group, alkoxy carbonyl, amino, acyl amino and cyano group.
As dentate LL 1while containing alkyl, thiazolinyl etc., these bases can be the straight chain shapes, can be also branch-like, can be substituted, and also can be unsubstituted.In addition, as dentate LL 1while containing aryl, heterocyclic radical etc., these bases can be monocycles, can be also the contracting rings, can be substituted, and also can be unsubstituted.
In general formula (3), R 25and R 26mean independently respectively aryl or heterocyclic radical.As aryl, preferred carbonatoms be 6～30 aryl of (preferably 6～24, more preferably 6～18), such as enumerating: phenyl, substituted-phenyl, naphthyl, substituted naphthyl etc.As heterocyclic radical, preferably carbonatoms be 3～30 heterocyclic radical of (preferably 3～24, more preferably 3～16), for example can enumerate: 2-thienyl, 2-pyrryl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, 3-indyl).
R 25and R 26the heterocyclic radical that preferably there are 1～3 electron-donating groups, more preferably thienyl.This electron-donating group preferred alkyl, thiazolinyl, alkynyl, cycloalkyl, alkoxyl group, aryloxy, amino, acyl amino (above preferred example and R 23and R 24situation identical) or hydroxyl, more preferably alkyl, alkoxyl group, amino or hydroxyl, particularly preferably alkyl.R 25and R 26can be identical, also can be different, but preferably identical.
In general formula (3), R 25with R 26directly bond is on pyridine ring.R 25with R 26also can be via L 1and/or L 2and bond is on pyridine ring.
Herein, L 1and L 2mean independently respectively to comprise the conjugated chain of at least 1 in the cohort that the heterocyclic radical of vinylidene, the ethynylene that is substituted or is unsubstituted that choosing freely is substituted or is unsubstituted and the divalence that is substituted or is unsubstituted forms.When vinylidene has substituting group, this substituting group preferred alkyl, more preferably methyl.
L 1and L 2the conjugated chain that is independently preferably 2～6 for carbonatoms respectively, more preferably vinylidene, Aden's dialkylene, ethynylene, Aden's diynyl, methyl vinylidene or dimethyl vinylidene, particularly preferably vinylidene or Aden's dialkylene, most preferably vinylidene.L 1with L 2can be identical, also can be different, but preferably identical.Moreover when conjugated chain contains carbon-to-carbon double bond, each pair of key can be trans body, can be also the cis body, can be also their mixture.
In general formula (3), d1 and d2 mean respectively 0～5 integer, preferably 0～3 integer, more preferably 0～2 integer.
In general formula (3), d3 means 0 or 1, preferably 1.A1 and a2 mean respectively 0～3 integer independently.When a1 is 2 when above, R 21can be identical, also can be different, when a2 is 2 when above, R 22can be identical, also can be different.A1 preferably 0 or preferred 0～2 the integer of 1, a2.Especially, when d3 is 0, a2 preferably 1 or 2, and when d3 is 1, a2 preferably 0 or 1.A1 and a2 and preferred 0～2 integer.
B1 and b2 mean respectively 0～3 integer, preferably 0～2 integer independently.When b1 is 2 when above, R 23can be identical, also can be different, and can mutually link and form ring.When b2 is 2 when above, R 24can be identical, also can be different, and can mutually link and form ring.In addition, be 1 when above, R as b1 and b2 23with R 24can link and form ring.As the preferred example of formed ring, can enumerate: phenyl ring, pyridine ring, thiphene ring, pyrrole ring, cyclohexane ring, pentamethylene ring etc.
As dentate LL 1while having at least 1 acidic groups, the m1 in general formula (3) preferably 2 or 3, and more preferably 2.
In general formula (2), LL 2two teeth that expression is represented by following general formula (4) or the dentate of three teeth.LL 2preferred two tooth dentates.Mean dentate LL 2the m2 of the quantity integer that is 1～3, preferably 1 or 2.When m2 is 2 when above, LL 2can be identical, also can be different.
[changing 37]
Figure BDA00002803131000481
general formula (4)
In general formula (4), Za, Zb and Zc mean to form respectively the non-metallic atom group of 5 Yuans rings or 6 Yuans rings independently.Formed 5 Yuans rings or 6 Yuans rings can be substituted, also can be unsubstituted, and can be monocycle, can be also the contracting ring.Za, Zb and Zc preferably comprise carbon atom, hydrogen atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom and/or halogen atom, and are preferably formed aromatic ring.As the concrete example of 5 Yuans rings, can enumerate: imidazole ring, oxazole ring, thiazole ring or triazole ring.As the concrete example of 6 Yuans rings, be preferably formed pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring.Wherein, more preferably imidazole ring or pyridine ring.At least 1 in the formed ring of Za, Zb and Zc has acidic groups.As acidic groups, such as enumerating: carboxyl, sulfonic group, hydroxyl, hydroximic acid base, phosphoryl and phosphono (phosphinyl), sulfino, sulfinyl, phosphinyl, phosphono (phosphono), thiol group and alkylsulfonyl and their salt etc.Among these acidic groups, preferred carboxyl, phosphoryl or phosphono (phosphinyl), more preferably carboxyl.
Described acidic groups directly bond on Za, Zb or the formed ring of Zc, also can be via concatenating group bond on Za, Zb or the formed ring of Zc.There is no particular restriction for concatenating group, can enumerate: methylene radical, vinylidene, ethynylene, arylidene, inferior heteroaryl or concatenating group that these concatenating groups are combined etc.
In general formula (4), c means 0 or 1.C preferably 0.
When by the represented dentate LL of general formula (4) 2while containing alkyl, thiazolinyl etc., these bases can be the straight chain shapes, can be also branch-like, can be substituted, and also can be unsubstituted.In addition, work as LL 2while containing aryl, heterocyclic radical etc., these bases can be monocycles, can be also the contracting rings, can be substituted, and also can be unsubstituted.
In general formula (2), X means the dentate of single tooth or two teeth.The m3 that means the quantity of dentate X means 0～2 integer, and m3 preferably 1 or 2.When X is single tooth dentate, m3 preferably 2, and when X is two tooth dentates, m3 preferably 1.When m3 is 2, X can be identical, also can be different, and X also can link each other mutually.
Dentate X means by selecting the free acyloxy (acyloxy that preferably carbonatoms is 1～20, for example acetoxyl group, benzoyloxy, Whitfield's ointment, glycyl oxygen base, N, N-dimethyl glycyl oxygen base, inferior oxalyl group (OC (O) C (O) O-) etc.), acyl sulfenyl (the acyl sulfenyl that preferably carbonatoms is 1～20, such as acetylthio, benzoyl sulfenyl etc.), sulfo-acyloxy (the sulfo-acyloxy that preferably carbonatoms is 1～20, for example thioacetyl oxygen base (CH 3c (S) O-) etc.)), sulfo-acyl sulfenyl (the sulfo-acyl sulfenyl that preferably carbonatoms is 1～20, for example thioacetyl sulfenyl (CH 3c (S) S-), thiobenzoyl sulfenyl (PhC (S) S-) etc.)), acyl amino oxygen base (the acyl amino oxygen base that preferably carbonatoms is 1～20, for example N-methyl benzoyl amino oxygen base (PhC (O) N (CH 3) O-), acetylamino oxygen base (CH 3c (O) NHO-) etc.)), thiocarbamate base (the thiocarbamate base that preferably carbonatoms is 1～20, N for example, the N-diethyl sulfide is for carbamate groups etc.), dithiocarbamate groups (the dithiocarbamate groups that preferably carbonatoms is 1～20, N-phenyl dithiocarbamate groups for example, N, N-dimethyldithiocarbamate base, N, N-diethyldithiocarbamate base, N, N-dibenzyl aminodithioformic acid ester group etc.), thiocarbonic acid SOH ester group (the thiocarbonic acid SOH ester group that preferably carbonatoms is 1～20, such as ethylenebis dithiocarbamate carbonate group etc.), dithiocarbonic acid ester group (the dithiocarbonic acid ester group that preferably carbonatoms is 1～20, ethyl dithiocarbonic acid ester group (C for example 2h 5oC (S) S-) etc.), trithiocarbonic acid ester group (the trithiocarbonic acid ester group that preferably carbonatoms is 1～20, for example ethyl trithiocarbonic acid ester group (C 2h 5sC (S) S-) etc.), acyl group (the acyl group that preferably carbonatoms is 1～20, ethanoyl for example, benzoyl etc.), thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio (the alkylthio that preferably carbonatoms is 1～20, methane sulfenyl for example, ethylene sulfenyl etc.), arylthio (the arylthio that preferably carbonatoms is 6～20, thiophenyl for example, 1, 2-phenylene disulfide group etc.), alkoxyl group (the alkoxyl group that preferably carbonatoms is 1～20, such as methoxyl group etc.) and the aryloxy (aryloxy that preferably carbonatoms is 6～20, phenoxy group for example, quinoline-8-hydroxyl etc.) base in the cohort formed carrys out the dentate of single tooth or two teeth of coordination, or select free halogen atom (preferred chlorine atom, bromine atoms, iodine atom etc.), carbonyl (... CO), dialkyl ketone (the dialkyl ketone that preferably carbonatoms is 3～20, acetone ((CH for example 3) 2cO...) etc.), 1, (preferably carbonatoms is 3～20 1 to the 3-diketone, 3-diketone, for example methyl ethyl diketone (CH 3c (O...) CH=C (O-) CH 3), trifluoroacetylacetone (CF 3c (O...) CH=C (O-) CH 3), dipivaloylmethane (tC 4h 9c (O...) CH=C (O-) t-C 4h 9), phenyl phenacyl ketone (PhC (O...) CH=C (O-) Ph), 3-chloracetyl acetone (CH 3c (O...) CCl=C (O-) CH 3) etc.), benzamide (benzamide that preferably carbonatoms is 1～20, for example CH 3n=C (CH 3) O-,-OC (=NH)-C (=NH) O-etc.), thiobenzamide (thiobenzamide that preferably carbonatoms is 1～20, for example CH 3n=C (CH 3) S-etc.), and thiocarbamide (thiocarbamide that preferably carbonatoms is 1～20, for example NH (...)=C (S-) NH 2, CH 3n (...)=C (S-) NHCH 3, (CH 3) 2n-C (S...) N (CH 3) 2deng) single tooth or two tooth dentates in the cohort that forms.Moreover " ... " means coordinate bond.
Dentate X is preferably by selecting free acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, dithiocarbamate groups, the dithiocarbonic acid ester group, the trithiocarbonic acid ester group, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form carrys out the dentate of coordination, or selects free halogen atom, carbonyl, dentate in the cohort that 1,3-diketone and thiocarbamide form, more preferably by selecting free acyloxy, acyl amino oxygen base, dithiocarbamate groups, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, base in the cohort that cyano group and arylthio form carrys out the dentate of coordination, or selects free halogen atom, dentate in the cohort that 1,3-diketone and thiocarbamide form, particularly preferably by selecting free dithiocarbamate groups, thiocyanate groups, isothiocyanate group, base in cyanate ester based and cohort that isocyanate group forms carrys out the dentate of coordination, or the dentate in the cohort that selects free halogen atom and 1,3-diketone to form, most preferably by selecting free dithiocarbamate groups, base in the cohort that thiocyanate groups and isothiocyanate group form carrys out the dentate of coordination, or the dentate that comprises 1,3-diketone.
When dentate X contains alkyl, thiazolinyl, alkynyl, alkylidene group etc., these bases can be the straight chain shapes, can be also branch-like, can be substituted, and also can be unsubstituted.In addition, when dentate X contains aryl, heterocyclic radical, cycloalkyl etc., these bases can be substituted, and also can be unsubstituted, and can be monocycles, can be also the contracting rings.
When X is two tooth dentates; X preferably carrys out the dentate of coordination by the base in the cohort that selects free acyloxy, acyl sulfenyl, sulfo-acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, thiocarbamate base, dithiocarbamate groups, thiocarbonic acid SOH ester group, dithiocarbonic acid ester group, trithiocarbonic acid ester group, acyl group, alkylthio, arylthio, alkoxyl group and aryloxy to form; or the dentate in the choosing cohort that freely 1,3-diketone, benzamide, thiobenzamide and thiocarbamide form.
When X is single tooth dentate, X preferably carrys out the dentate of coordination by the base in the cohort that selects free thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio and arylthio to form, or the dentate in the cohort that selects free halogen atom, carbonyl, dialkyl ketone and thiocarbamide to form.
In general formula (2), CI mean in and electric charge and counter ion while needing counter ion.Usually, pigment is positively charged ion or negatively charged ion or the tangible ionic charge of no tool exists with ... metal, dentate and the substituting group in pigment.
Have the property of dissociating base etc. by substituting group, by general formula (2), represented pigment can dissociate and have negative charge.In the case, by general formula (2), the electric charge of represented pigment integral body becomes electric neutrality by CI.
When counter ion CI is positive counter ion, for example, as counter ion CI, can enumerate inorganic or organic ammonium ion (such as tetraalkyl ammonium ion, pyridinium ion etc.), alkalimetal ion and proton.
When counter ion CI is negative counter ion, counter ion CI can be inorganic anion, can be also organic anion.For example can enumerate: halide anion (fluoride ion for example, chloride ion, bromide ion, iodide ion etc.), substituted aryl azochlorosulfonate acid ion (tosic acid ion for example, p-chlorobenzenesulfonic acid ion etc.), aryl disulfonic ion (for example 1, 3-benzene disulfonic acid ion, 1, 5-naphthalene disulfonic acid ion, 2, 6-naphthalene disulfonic acid ion etc.), alkylsurfuric acid ion (such as methyl sulfate ion etc.), sulfate ion, thiocyanate ion, cross the chlorate ions, the Tetrafluoroboric acid ion, phosphofluoric acid ester ion, the picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion etc.And then, as the equalizing charge counter ion, can use other pigments with electric charge contrary with ionic polymers or pigment, also can use metel complex ion (for example two benzene-1,2-bis-mercaptan nickel (III) etc.).
Pigment with structure represented by general formula (2) has more than at least 1 the suitable bond base (interlocking group) for the surface of semiconductor microactuator particle.More preferably in pigment, there are 1～6 these bond bases, particularly preferably there are 1～4.In general formula (4), at least 1 in the formed ring of Za, Zb and Zc has acidic groups, and this acidic groups is as bond base performance function.Pigment with structure represented by general formula (2) also can have other bond bases different from described acidic groups.There is no particular restriction for this kind of bond base, can enumerate acidic groups, amino, sulfydryl, alkyl silyl etc.Wherein, preferred acidic base.
There is the dye compound of the structure represented by general formula (2) preferably by the represented compound of following general formula (10).
(A1) pru (B-a) is (B-c) general formula (10) (B-b)
In general formula (10), A1 means the dentate of single tooth or two teeth.As the concrete example of A1, can enumerate and select free Cl, SCN, H 2dentate in the cohort that the derivative of O, Br, I, CN, NCO and SeCN and beta-diketon class, oxalic acid and dithiocarbamic acid forms.As A1, preferred SCN or beta-diketon class.
In general formula (10), the integer that p is 0～3.P is 1～3 integer preferably.
In general formula (10), B-a, B-b and B-c mean independently respectively by any represented organic coordination base of following Formula B-1～Formula B-10 or are the salt person by the acidic groups that any represented organic coordination bases of Formula B-1～Formula B-10 has.
[changing 38]
Figure BDA00002803131000531
In Formula B-1～Formula B-10, R 11～R 22mean substituting group.
As substituting group, can enumerate: the aryl that is substituted or is unsubstituted that the aralkyl that is substituted or is unsubstituted that the thiazolinyl that is substituted or is unsubstituted that the alkyl that is substituted or is unsubstituted that halogen atom, carbonatoms are 1～12, alkoxyl group, carbonatoms are 2～20, carbonatoms are 7～12, alkoxy aryl, carbonatoms are 6～12 or described acidic groups (these acidic groups also can form salt).The moieties of alkyl and aralkyl can be the straight chain shape, can be also branch-like.In addition, the aryl moiety of aryl and aralkyl can be monocycle, can be also many rings (condensed ring, ring set).By R 11～R 22represented substituting group can further be substituted, and the substituting group further replaced is as R 11～R 22cited substituting group, preferably replaced by acidic groups.By R 11～R 22represented substituting group itself is preferably acidic groups or has acidic groups as substituent base.
E1～e12 means the integer more than 0.Particularly, e1 and e2 mean respectively 0～4 integer independently, e3 means 0～3 integer, e4 and e5 mean respectively 0～4 integer independently, e6 means 0～2 integer, e7 and e8 mean respectively 0～3 integer independently, and e9 means 0～4 integer, and e10～e12 means respectively 0～6 integer independently.When e1～e12 is 2 when above, R 11～R 22respectively can be identical, also can be different.Preferably e1～e12 is independently respectively 1 situation.
R 11with R 12can be identical, also can be different, but preferably identical.R 13～R 15can be identical, also can be different, but preferably identical.R 16～R 18can be identical, also can be different, but preferably identical.R 19with R 20can be identical, also can be different, but preferably identical.R 21with R 22can be identical, also can be different, but preferably identical.
B-a, B-b and B-c can be identical, also can be different.But, in the compound represented by general formula (10), there is at least 1 acidic groups.
The concrete example of the pigment with structure represented by general formula (2) below used in expression the present invention, but the present invention is not limited to these concrete examples.Moreover, when the pigment in following concrete example comprises the dentate with proton dissociation base, this dentate optionally can be dissociated and be discharged proton.
[changing 39]
Figure BDA00002803131000551
[changing 40]
Figure BDA00002803131000561
The pigment represented by general formula (2) of the present invention can synthesize with reference to the method for quoting in Japanese Patent Laid-Open 2001-291534 communique or this communique.
The scope of the maximum absorption wavelength preferred 300nm～700nm of pigment in solution with structure of general formula (2), the more preferably scope of 400nm～650nm, the particularly preferably scope of 500nm～600nm.
And then the photoabsorption wave band of represented pigment is preferably in the scope in 300nm～900nm, more preferably in the scope in 350nm～850nm by general formula (2).
In photo-electric conversion element of the present invention and photoelectrochemical cell, use by the represented metal complex dye of general formula (1), but also can be used together the pigment of the structure with described general formula (2).By in photo-electric conversion element and photoelectrochemical cell, also using these pigments, can utilize the light of the wavelength had a wide reach in photo-electric conversion element and photoelectrochemical cell, and can guarantee high conversion efficiency.And then, can reduce the rate of descent of efficiency of conversion.
About metal complex dye with structure represented by general formula (2) with there is the allotment ratio of the pigment of the structure represented by general formula (1), if the former is made as to R, the latter is made as to S, in % by mole ratio, R/S=90/10～10/90, preferably R/S=80/20～20/80, more preferably R/S=70/30～30/70, R/S=60/40～40/60 particularly preferably, R/S=55/45～45/55 most preferably, mole used both to wait usually.
(charge transfer body)
In the preferred example of photo-electric conversion element of the present invention as shown in Figure 1, the charge transfer body layer 3 used in photo-electric conversion element can be applied the layer that comprises the electrolyte ingredient thing.As its redox couple, such as enumerating: the combination of the iron complex (such as red prussiate of potash and yellow prussiate of potash) of the combination of the combination of the combination of iodine and iodide (such as lithium iodide, tetrabutylammonium iodide, iodate tetrapropyl ammonium etc.), alkyl viologen (such as methyl viologen muriate, hexyl purpurine bromide, benzyl viologen a tetrafluoro borate) and its Reduction Body, poly-Hydroxybenzenes (such as Resorcinol, naphthalene quinhydrones etc.) and its oxysome, the iron complex of divalence and trivalent etc.Among these combinations, the preferably combination of iodine and iodide.
The positively charged ion of salt compounded of iodine is 5 Yuans rings or the nitrogenous aromatic series positively charged ion of 6 Yuans rings preferably.Especially, when the compound represented by general formula (1) and by general formula (2) when any or one of represented compound Non-iodizedsalt, preferred also No. WO95/18456, use, No. 8-259543, Japanese patent laid-open, electrochemistry, the 65th volume, No. 11, the salt compounded of iodine such as the pyridinium salt of putting down in writing in 923 pages (1997) etc., imidazole salts, triazolium salt.
In the electrolyte ingredient thing used, preferably contain heterocycle level Four salt compound and iodine in photo-electric conversion element of the present invention.With respect to whole electrolyte ingredient thing, the content of iodine is 0.1 quality %～20 quality % preferably, more preferably 0.5 quality %～5 quality %.
The electrolyte ingredient thing used in photo-electric conversion element of the present invention also can contain solvent.Below 50 quality % of the preferred whole constituent of solvent in the electrolyte ingredient thing, more preferably below 30 quality % of whole constituent, particularly preferably below 10 quality % of whole constituent.
As solvent, preferred viscosities is low and ion mobility is high or specific inductivity is high and can improve efficient carrier concentration or can manifest the solvent of excellent ionic conductivity because of described two aspects.As this kind of solvent, can enumerate: carbonate products (NSC 11801, propylene carbonate etc.), heterogeneous ring compound (3-methyl-2-oxazolidone etc.), ether compound (dioxan, diethyl ether etc.), chain ethers (glycol dialkyl ether, the propylene glycol dialkyl ether, the polyoxyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether etc.), alcohols (methyl alcohol, ethanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, polyalkylene glycol monoalkyl ether, polypropylene glycol monoalky lether etc.), polyalcohols (ethylene glycol, propylene glycol, polyoxyethylene glycol, polypropylene glycol, glycerine etc.), nitrile compound (acetonitrile, trimethylene cyanide, methoxyacetonitrile, propionitrile, benzonitrile, dicyanogen methyl isophorone ether etc.), ester class (carboxylicesters, phosphoric acid ester, phosphonic acid ester etc.), non-proton property polar solvent (dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide, DMSO), tetramethylene sulfone etc.), water, the aqueous electrolyte of putting down in writing in Japanese Patent Laid-Open 2002-110262, Japanese Patent Laid-Open 2000-36332 communique, Japanese Patent Laid-Open 2000-243134 communique, and the electrolyte solvent of putting down in writing in Japanese public table WO/00-54361 communique again etc.These solvents also can be use mixing two or more.
In addition, as electrolyte solvent, also can use at room temperature as liquid state and/or have lower than the fusing point of room temperature and be the salt of inertia aspect electrochemistry.Such as enumerating: the imidazole salts of 1-ethyl-3-methylimidazole triflate, 1-butyl-3-Methylimidazole triflate etc., the nitrogen heterocyclic ring level Four salt compounds such as pyridinium salt, or tetraalkylammonium salt etc.
In can be used for the electrolyte ingredient thing of photo-electric conversion element of the present invention, also can add the method such as polymkeric substance or oleogel agent or the polymerization by the polyfunctional monomer class or the crosslinking reaction of polymkeric substance and gelation (solidification).
When by the interpolation polymkeric substance, making the gelation of electrolyte ingredient thing, can add the compound put down in writing in polymer dielectric comment (Polymer Electrolyte Reviews)-1 and polymer dielectric comment-2 (J.R. Mike lime (J.R.MacCallum) is compiled in collaboration with C.A. guest gloomy (C.A.Vincent), Ai Er Seville applied science (ELSEVIER APPLIED SCIENCE)) etc.In the case, preferably use polyacrylonitrile or poly(vinylidene fluoride).
When by interpolation oleogel agent, making the gelation of electrolyte ingredient thing, as the oleogel agent, can use Japanization association will, India chemistry meeting will (J.Chem.Soc.Japan, Ind.Chem.Soc.), 46779 (1943), american chemical magazine (J.Am.Chem.Soc.), 111, 5542 (1989), chemistry meeting will, chemical communication (J.Chem.Soc., Chem.Commun.), 390 (1993), the international version of applied chemistry (English) (Angew.Chem.Int.Ed.Engl.), 35, 1949 (1996), chemistry wall bulletin (Chem.Lett.), 885, (1996), chemistry meeting will, chemical communication (J.Chem.Soc., Chem.Commun.), 545, etc. (1997) compound of putting down in writing in, preferably use the compound with amide structure.
When the polymerization by the polyfunctional monomer class makes the gelation of electrolyte ingredient thing, the method be preferably as follows: by polyfunctional monomer class, polymerization initiator, ionogen and solvent, prepare solution, and utilize the methods such as teeming practice, coating method, pickling process, impregnation method carrying on the electrode of pigment the dielectric substrate that forms the colloidal sol shape, make its gelation by the radical polymerization of polyfunctional monomer is incompatible thereafter.The polyfunctional monomer class preferably has the compound of 2 above ethene unsaturated groups, preferably Vinylstyrene, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, Diethylene Glycol dimethacrylate, triethylene glycol diacrylate, TEGDMA, pentaerythritol triacrylate, Viscoat 295 etc.
Except described polyfunctional monomer class, the polymerization of the mixture that gel electrolyte also can be by containing monofunctional monomer forms.As monofunctional monomer, can use: vinylformic acid or alpha-alkyl vinylformic acid (vinylformic acid, methacrylic acid, methylene-succinic acid etc.) or their ester or acid amides (methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the vinylformic acid n-pentyl ester, vinylformic acid 3-pentyl ester, the vinylformic acid tert-pentyl ester, the just own ester of vinylformic acid, vinylformic acid 2,2-dimethyl butyl ester, the vinylformic acid n-octyl, 2-EHA, vinylformic acid 4-methyl-2-propyl pentyl ester, Process Conditions of Cetane Acrylate, n-stearyla crylate, cyclohexyl acrylate, vinylformic acid ring pentyl ester, benzyl acrylate, Hydroxyethyl Acrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 2-methoxyl group ethyl ester, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-methoxy ethoxy ethyl ester, the vinylformic acid phenoxy ethyl, vinylformic acid 3-methoxyl group butyl ester, the ethyl carbitol acrylate, vinylformic acid 2-methyl-2-nitro propyl ester, vinylformic acid 2,2, the 2-trifluoro ethyl ester, vinylformic acid octafluoro pentyl ester, vinylformic acid 17 fluorine esters in the last of the ten Heavenly stems, methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, the methacrylic acid tert-pentyl ester, the positive octadecyl ester of methacrylic acid, benzyl methacrylate, methacrylic acid hydroxyl ethyl ester, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 2-methoxyl group ethyl ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 2-methoxy ethoxy ethyl ester, dimethylaminoethyl methacrylate, methacrylic acid 2,2, the 2-trifluoro ethyl ester, the tetrafluoropropyl propyl ester, methacrylic acid hexafluoro propyl ester, methacrylic acid 17 fluorine esters in the last of the ten Heavenly stems, diglycol carbonate ethyl ester methacrylic ester, methacrylic acid 2-isobornyl thiocyanoacetate, methacrylic acid 2-norcamphyl methyl esters, methacrylic acid 5-norbornylene-2-base methyl esters, methacrylic acid 3-methyl-2-norcamphyl methyl esters, acrylamide, NIPA, N-normal-butyl acrylamide, N tert butyl acrylamide, N,N-DMAA, N hydroxymethyl acrylamide, diacetone acrylamide, the 2-acrylamide-2-methyl propane sulfonic, the acrylamide propyl trimethyl ammonium chloride, Methacrylamide, N-methyl acrylamide, N-methylol methacrylamide etc.), vinyl ester (vinyl acetate etc.), maleic acid or FUMARIC ACID TECH GRADE or the ester class (dimethyl maleate derived from these acid, dibutyl maleate, diethyl fumarate etc.), the sodium salt of p styrene sulfonic acid, vinyl cyanide, methacrylonitrile, dienes (divinyl, cyclopentadiene, isoprene etc.), aromatic ethenyl compound (vinylbenzene, to chloro-styrene, t-butyl styrene, alpha-methyl styrene, Sodium styrene sulfonate etc.), the N-vinyl formamide, N-vinyl-N-METHYLFORMAMIDE, the N-vinyl acetamide, N-vinyl-N-methylacetamide, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, the methacryloyl sodium sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers class (methylvinylether etc.), ethene, propylene, butylene, iso-butylene, N-phenyl maleimide etc.
With respect to whole monomer, the allotment amount of polyfunctional monomer preferably is made as 0.5 quality %～70 quality %, more preferably 1.0 quality %～50 quality %.Described monomer can be general by the conduct of putting down in writing in refined happy work " laboratory method of Polymer Synthesizing " (chemical same people) altogether or the large grand row in Tianjin " polyreaction opinion lecture 1 radical polymerization (I) " (chemical same people) under the grand row wood in large Tianjin the radical polymerization of Polymer Synthesizing method incompatiblely carry out polymerization.The gel electrolyte of using in the present invention can carry out radical polymerization by heating, light or electron beam with monomer, or carries out radical polymerization with electrochemical means, but particularly preferably by heating, carries out radical polymerization.In the case, the polymerization initiator that can preferably use is 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), dimethyl 2,2 '-azos such as the two isobutyrates of azo are initiator, the peroxidation system initiators such as lauryl peroxide, benzoyl peroxide, the peroxidation acid tert-butyl ester etc.With respect to the monomer total amount, the preferred addition of polymerization initiator is 0.01 quality %～20 quality %, more preferably 0.1 quality %～10 quality %.
Monomer is the preferred 0.5 quality %～70 quality % of shared weight compositing range in gel electrolyte.More preferably 1.0 quality %～50 quality %.When the crosslinking reaction by polymkeric substance makes the gelation of electrolyte ingredient thing, preferably to adding and there is polymkeric substance and the linking agent that can carry out crosslinked reactive base in constituent.Preferred reactive base is the nitrogen heterocyclic rings such as pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, preferred linking agent is that nitrogen-atoms has the compound (electrophilic reagent) that can carry out the functional group of nucleophillic attack more than 2, such as being halogenated alkyl more than two senses, halogenated aralkyl, sulphonate, acid anhydrides, acyl chlorides, isocyanic ester etc.
In can be used for electrolyte ingredient thing of the present invention, can add metal iodide (LiI, NaI, KI, CsI, CaI 2deng), metal bromide (LiBr, NaBr, KBr, CsBr, CaBr 2deng), level Four ammonium bromine salt (bromination tetra-allkylammonium, pyridinium bromide etc.), metal complex (Ferrocyanide salt-ferricyanide, ferrocene-ferricinium ion etc.), sulphur compound (poly-sodium sulphite, alkyl sulfhydryl-alkyl disulfide etc.), purpurine pigment, Resorcinol-quinone etc.These compounds also can mix use.
In addition, in can be used for electrolyte ingredient thing of the present invention, also can add U.S.'s ceramics meeting magazine (J.Am.Ceram.Soc.), 80, (12), the tert .-butylpyridine of putting down in writing in 3157-3171 (1997) or 2-picoline, 2, the basic cpds such as 6-lutidine.Preferred concentration range while adding basic cpd is 0.05M～2M.
In addition, the charge transfer body layer 3 as in photo-electric conversion element of the present invention, also can be used the charge transport layer that contains the hole conductor material.As the hole conductor material, can use 9,9 '-spirobifluorene derivative etc.
In addition, as the formation of electrochemical element, lamination electroconductibility supporter (electrode layer), photoelectric conversion layer photoreceptor layers and charge transfer body layer successively), hole transmission layer, conducting stratum, to electrode layer.
Can be using the hole mobile material as p-type semi-conductor performance function as hole transmission layer.As preferred hole transmission layer, for example can use the hole mobile material of inorganic system or organic system.As inorganic be hole mobile material, can enumerate CuI, CuO, NiO etc.In addition, as the organic system hole mobile material, can enumerate macromolecular and the low material that divides subsystem, as the material of macromolecular, such as enumerating: polyvinyl carbazole, polyamine, organopolysilane etc.In addition, as the material of low minute subsystem, such as enumerating: triphenylamine derivative, diphenyl ethylene derivatives, hydrazone derivative, phenamine (phenamine) derivative etc.Wherein, organopolysilane is that polymer is different from previous carbon, and it is the polymer with main chain Si chain.And, contribute to the light conduction along the σ-electron of main chain Si delocalization (delocalization), therefore there is high hole rate of flow (with reference to " physical comment B (Phys.Rev.B) ", 35,2818 (1987) etc.), so preferably.
Can be arranged on conducting stratum in photo-electric conversion element of the present invention so long as the good layer of electroconductibility is not particularly limited, such as enumerating: inorganic conductive material, organic conductive material, electric conductive polymer, Intermolecular charge transfer complex etc.Wherein, preferred Intermolecular charge transfer complex.Herein, Intermolecular charge transfer complex is formed by donor material and acceptor material.In addition, can preferably use organic donor and organic receptor.
The material that is rich in electronics in donor material preferred molecular structure.For example, as organic donor material, the π-electron that can enumerate molecule has the material of the amido, hydroxyl, ether, selenium or the sulphur atom that are substituted or are unsubstituted in being, particularly, can enumerate: phenyl amine system, triphenyl methane system, carbazole system, phenol system, tetrathiafulvalene (thiafulvalene) based material.As acceptor material, the material of electron deficiency in preferred molecular structure.For example, as the organic receptor material, can enumerate soccerballene, there is nitro in the π-electron system of molecule, cyano group, the substituent material such as carboxyl or halogen, particularly, can enumerate: [6, 6]-phenyl-C61-methyl-butyrate ([6, 6]-Phenyl-C61-Butyric Acid Methyl Ester, PCBM), benzoquinones system, the quinones such as naphthoquinones system system, Fluorenone (fluorenone) is, tetrachlorobenzoquinone (chloranil) is, tetrabromo-quinone (bromanil) is, four cyano quinone bismethane (tetracyanoquinodimethane) is, tetracyanoethylene (tetracyanoethylene) is etc.
Moreover the thickness of conducting stratum is not particularly limited, but preferably can bury the degree of Porous fully.
(electroconductibility supporter)
In the preferred example of photo-electric conversion element of the present invention as shown in Figure 1, be formed with the photoreceptor layers 2 on the semiconductor microactuator particle 22 that sensitizing coloring matter 21 is adsorbed on Porous on electroconductibility supporter 1.As described later, for example the dispersion liquid of semiconductor microactuator particle is coated on the electroconductibility supporter and in addition after drying, is immersed in pigment solution of the present invention, can manufacture photoreceptor layers 2 thus.
As the electroconductibility supporter, can use and there is glass or the macromolecular material that electroconductibility person or surface have conductive film layer as supporter itself as metal.The electroconductibility supporter is preferably transparent in fact.If transparent in fact, the transmitance that means light is more than 10%, preferably more than 50%, particularly preferably more than 80%.As the electroconductibility supporter, can use the metal oxide of electroconductibility is coated with and is located at glass or the macromolecular material person of forming.The glue spread of the metal oxide of electroconductibility now is at every 1m of the supporter of glass or macromolecular material 2upper, preferred 0.1g～100g.When using the transparent conductivity supporter, preferably make light inject from supporting side.An example as the macromolecular material of preferred use, can enumerate: tetrem acyl Mierocrystalline cellulose (Triacetyl Cellulose, TAC), polyethylene terephthalate (Polyethylene terephthalate, PET), PEN (Polyethylene naphthalate, PEN), syndiotactic polystyrene (Syndiotactic polystyrene, SPS), polyphenylene sulfide (Polyphenylene sulfide, PPS), polycarbonate (Polycarbonate, PC), polyarylester (Polyarylate, PAR), polysulfones (Polysulfone, PSF), polyester sulfone (Polyestersulfone, PES), polyetherimide (Polyetherimide, PEI), cyclic polyolefin, bromination phenoxy group etc.On the electroconductibility supporter, also can apply the light regime function by effects on surface, for example can enumerate the alternately lamination of putting down in writing in Japanese Patent Laid-Open 2003-123859 has the photoconduction function of putting down in writing in the anti-reflective film of the oxide film of high refraction film and low-refraction, Japanese Patent Laid-Open 2002-260746.
In addition, also can preferably use metal support.As the one example, can enumerate: titanium, aluminium, copper, nickel, iron, stainless steel.These metals can be also alloys.More preferably titanium, aluminium, copper, particularly preferably titanium or aluminium.
Preferably make on the electroconductibility supporter to have the function of blocking UV-light.The method that for example also can be listed below: make the fluorescent material that UV-light can be become to visible ray be present in transparent supporting body or the method for transparent support surface or the method for use UV light absorber.
On the electroconductibility supporter, also can further give the function of putting down in writing in Japanese patent laid-open 11-250944 communique etc.
As preferred conducting film, can enumerate: the metal oxide of metal (such as platinum, gold and silver, copper, aluminium, rhodium, indium etc.), carbon or electroconductibility (indium-Xi composite oxides, to doped with fluorine person of forming in stannic oxide etc.).
The thickness of conductive film layer is 0.01 μ m～30 μ m preferably, more preferably 0.03 μ m～25 μ m, particularly preferably 0.05 μ m～20 μ m.
The surface resistivity of electroconductibility supporter 1 is more low better.The scope of preferred surface resistivity is 50 Ω/cm 2below, more preferably 10 Ω/cm 2below.There is no particular restriction for its lower limit, but be generally 0.1 Ω/cm 2left and right.
If it is large that cellar area becomes, the resistance value of conducting film becomes large, therefore also can configure collecting electrodes.Also can configure gas barrier film and/or anti-ion diffusion barrier between electroconductibility supporter and nesa coating.As gas barrier layer, can use resin molding or mineral membrane.
In addition, transparency electrode also can be set and Porous semi-conducting electrode photocatalyst contains layer.Transparency conducting layer can be also the lamination structure, as preferred method, and for example can be at the upper lamination fluorine-doped tin oxide (Fluorine-doped Tin Oxide, FTO) of tin indium oxide (Indium Tin Oxide, ITO).
(semiconductor microactuator particle)
As shown in Figure 1, in the preferred example of photo-electric conversion element of the present invention, be formed with the photoreceptor layers 2 on the semiconductor microactuator particle 22 that pigment 21 is adsorbed on Porous on electroconductibility supporter 1.As described later, for example the dispersion liquid of semiconductor microactuator particle is coated on described electroconductibility supporter and in addition after drying, is immersed in pigment solution of the present invention, can manufacture photoreceptor layers 2 thus.
As the semiconductor microactuator particle, preferably use the chalkogenide (such as oxide compound, sulfide, selenide etc.) of metal or the micropartical of uhligite.As the chalkogenide of metal, can preferably enumerate the oxide compound of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum, Cadmium Sulfide, cadmium selenide etc.As uhligite, can preferably enumerate strontium titanate, calcium titanate etc.Among them, particularly preferably titanium oxide, zinc oxide, stannic oxide, Tungsten oxide 99.999.
Semi-conductor exists N-shaped that the current carrier relevant with conduction is electronics, and the current carrier p-type that is hole, with regard to the viewpoint of efficiency of conversion, and preferred use N-shaped in element of the present invention.In the N-shaped semi-conductor, except the proper semiconductor's (or proper semiconductor) that does not there is impurity level and utilize conduction band electron to equate with the concentration of the current carrier in valence band hole, because there is the N-shaped semi-conductor that electronic carrier concentration is high in the structure defect that is derived from impurity.The inorganic semiconductor of the N-shaped preferably used in the present invention is TiO 2, TiSrO 3, ZnO, Nb 2o 3, SnO 2, WO 3, Si, CdS, CdSe, V 2o 5, ZnS, ZnSe, SnSe, KTaO 3, FeS 2, PbS, InP, GaAs, CuInS 2, CuInSe 2deng.Among them, most preferred N-shaped semi-conductor is TiO 2, ZnO, SnO 2, WO 3, and Nb 2o 3.In addition, the semiconductor material that also preferably a plurality of described semi-conductors is composited.
For the viscosity by semiconductor microactuator particle dispersion liquid keeps highly, the median size of the preferred primary particle of particle diameter of semiconductor microactuator particle is more than 2nm, below 50nm, and in addition, more preferably the median size of primary particle is the ultramicron that 2nm is above, 30nm is following.Micropartical of more than two kinds that also can size distribution is different mixes, and in the case, preferably the mean sizes of small-particle is below 5nm.In addition, in order to make to inject scattering of light, promote the light capture rate, also can surpass the macroparticle of 50nm or other layers are coated with respect to described ultramicron median size to hang down the containing ratio interpolation.In the case, below 50% of quality that the preferred median size of the containing ratio of macroparticle is the following particle of 50nm, more preferably below 20%.Add the preferred 100nm of median size of macroparticle of mixing with described purpose more than, more preferably more than 250nm.
Preferably, by the macroparticle that uses scattering of light to use, the mist degree rate becomes more than 60%.The mist degree rate is to be meaned by (diffusional permeability) ÷ (total light transmittance).
As the making method of semiconductor microactuator particle, the sol-gel method of putting down in writing in preferred " science of sol-gel method " Ah lattice's a kind of apple (Agune) Cheng Fengshe (1998) that does flower Ji husband etc.In addition, by hydrogen-oxygen salt, the muriate of Degussa (Degussa) company exploitation being carried out to pyrohydrolysis, to make the method for oxide compound also preferred.When the semiconductor microactuator particle is titanium oxide, described sol-gel method, sol-gel method, the flame hydrolysis of muriate in hydrogen-oxygen salt is all preferred, and then " titanium oxide physical property and utilisation technology " skill newspaper hall that also can using leaves nothing usable to the invading enemy learns is published sulfuric acid process and the chlorine method of putting down in writing in (1997).And then, as sol-gel method, U.S.'s ceramics meeting magazine (Journal of American Ceramic Society) of BABEI (Barbe) etc., the 80th volume, No. 12, the Materials science (Chemistry ofMaterials) of the method for putting down in writing in 3157 pages～3171 pages (1997) or Ben Saide (Burnside) etc., the 10th volume, No. 9, the method for putting down in writing in 2419 pages～2425 pages is also preferred.
In addition, manufacture method as the semiconductor microactuator particle, for example, as the manufacture method of titanium dioxide nano-particle, can preferably enumerate the hydrolysis of the combustion method of method, the titanium tetrachloride of the flame hydrolysis that utilizes titanium tetrachloride, stable chalkogenide complex compound, adjacent metatitanic acid hydrolysis, form after the semiconductor microactuator particle Hydrothermal Synthesis that soluble portions is dissolved to the method removed, peroxide aqueous solution or utilize the manufacture method of titanium oxide microparticle of the core/shell structure of sol-gel method by soluble portions and insoluble.
As the crystalline texture of titanium dioxide, can enumerate Detitanium-ore-type, brookite type or rutile-type, preferably Detitanium-ore-type, brookite type.
Also titania nanotube, titanium dioxide nano thread, titanium dioxide nano-rod can be mixed in titanium dioxide particle.
Titanium dioxide also can be adulterated by non-metallic element etc.As the additive for titanium dioxide, except doping agent, also can use to improve the tackiness agent of necking down (necking) or the effects on surface use additive in order to prevent anti-electron from shifting.As the example of preferred additive, can enumerate: the charge transfer bond molecule such as fibrous material, metal, organosilicon, dodecyl Phenylsulfonic acid, the silane compounds such as ITO, SnO particle, whisker, fibrous Nano graphite carbon pipe, zinc oxide necking down bond base, Mierocrystalline cellulose and current potential apsacline branch-shape polymer etc.
In order to remove surface imperfection on titanium dioxide etc., also can before pigment absorption, to titanium dioxide, carry out that the soda acid reduction is processed or the redox processing.Also can be processed by etching, oxide treatment, hydrogen peroxide treatment, dehydrogenation processing, ultraviolet ray (Ultraviolet, UV)-ozone, oxygen plasma etc.
(semiconductor microactuator particle dispersion liquid)
In the present invention, semiconductor microactuator particle dispersion liquid below the 10 quality % that the content of the solids component beyond the semiconductor microactuator particle is comprised to semiconductor microactuator particle dispersion liquid integral body is coated on described electroconductibility supporter, and moderately heated, can obtain thus Porous semiconductor microactuator particle coating layer (photoreceptor layers).
As the method for making semiconductor microactuator particle dispersion liquid, except described sol-gel method, can be listed below method etc.: when synthesized semiconductor, in solvent, as micropartical, separate out and directly the method for use, micropartical irradiated to ultrasonic wave etc. be ground into the method for ultramicron or the method for using pulverizing mill or mortar etc. mechanically to pulverize and grind.As dispersion solvent, can make water and/or various organic solvent.As organic solvent, can enumerate: the alcohols such as methyl alcohol, ethanol, Virahol, geraniol, Terpineol 350, the ketones such as acetone, the ester classes such as vinyl acetic monomer, methylene dichloride, acetonitrile etc.
During dispersion, optionally for example can use a small amount of as the polymkeric substance as polyoxyethylene glycol, Natvosol, carboxymethyl cellulose, interfacial agent, acid, or sequestrant etc. is as dispersing auxiliary.But, preferably before the step of masking on the electroconductibility supporter, by filtration method or use the method for separatory membrane or centrifugal separation etc. is removed the major part of these dispersing auxiliaries.Semiconductor microactuator particle dispersion liquid can be made as the content of the solids component beyond the semiconductor microactuator particle below 10 quality % of dispersion liquid integral body.This concentration is preferably below 5%, more preferably below 3%, particularly preferably below 1%.More preferably below 0.5%, particularly preferably 0.2%.That is,, in semiconductor microactuator particle dispersion liquid, the solids component beyond solvent and semiconductor microactuator particle can be made as below 10 quality % of semiconductor microactuator particle dispersion liquid integral body.Preferably in fact only comprise semiconductor microactuator particle and dispersion solvent.
If the viscosity of semiconductor microactuator particle dispersion liquid is too high, dispersion liquid cohesion and can't being filmed, on the contrary, if the viscosity of semiconductor microactuator particle dispersion liquid is too low, exist dispersion liquid to flow and the situation that can't be filmed.Therefore, the viscosity of dispersion liquid preferred 10Ns/m under 25 ℃ 2～300Ns/m 2.Under 25 ℃, be more preferably 50Ns/m 2～200Ns/m 2.
As the coating process of semiconductor microactuator particle dispersion liquid, as the method for application system, can use roller method, pickling process etc.In addition, as the method for metering system, can use the air knife method, scrape the skill in using a kitchen knife in cookery etc.In addition, as can be by the method for the method of application system and metering system for a part of method, sliding hopper (slide hopper) method of putting down in writing in the line rod method preferably disclosed in No. 58-4589, Japanese Patent examined patent publication, No. 2681294 specification sheetss of United States Patent (USP) etc., extrusion process, heavy curtain method etc.In addition, with general-purpose machinery and be coated with also preferred by rotational method or spray method.As the wet printing method, headed by 3 large print processes of relief printing plate, lithographic plate and intaglio plate, preferred intaglio plate, flexographic, screen painting etc.Corresponding to liquid viscosity or wet thickness, select preferred film-forming method from these methods.In addition, described semiconductor microactuator particle dispersion liquid is because viscosity is high, and has toughness, and therefore cohesive force is strong sometimes, situation about can't successfully be combined with supporter while having coating.In such cases, carry out the clean and hydrophilization on surface by the UV ozonize, the semiconductor microactuator particle dispersion liquid that is coated with thus and the cohesive force of electroconductibility supporting body surface increase, and the coating of semiconductor microactuator particle dispersion liquid becomes and easily carries out.
The preferred thickness of semiconductor microactuator particle layer integral body is 0.1 μ m～100 μ m.The thickness of semiconductor microactuator particle layer is 1 μ m～30 μ m more preferably, and then more preferably 2 μ m～25 μ m.The semiconductor microactuator particle is at every 1m 2supporter on the preferred 0.5g～400g of bearing capacity, more preferably 5g～100g.
In order to strengthen the contact of electronics each other of semiconductor microactuator particle, and to promote the adhesion with supporter, in addition, in order to make be coated with semiconductor microactuator particle dispersion liquid drying, and the layer of be coated with semiconductor microactuator particle is implemented to heat treated.Can form Porous semiconductor microactuator particle layer by this heat treated.In addition, also can be corresponding to the characteristic of member or purposes and suitablely utilize known method to form the semiconductor microactuator particle layer.For example, can be with reference to the material of putting down in writing in Japanese Patent Laid-Open 2001-291534 communique or preparation method, making method, and be referenced in this specification sheets.
In addition, except heat treated, also can utilize luminous energy.For example, when using titanium oxide as the semiconductive particles period of the day from 11 p.m. to 1 a.m, can make surface active by giving the light that can absorb as the semiconductor microactuator particle as UV-light, and can utilize laser etc. only to make the activation of semiconductor microactuator particle surface.By the semi-conductor micropartical is irradiated to the light that this micropartical can absorb, the impurity that is adsorbed on particle surface decomposes because of the activation of particle surface, can become preferred state for described purpose.When heat treated and UV-light are combined, preferably one side irradiates to the semi-conductor micropartical light that this micropartical can absorb, and one side is with more than 100 ℃, below 250 ℃ or preferably with more than 100 ℃, heated below 150 ℃.So, the semi-conductor micropartical is carried out to optical excitation, can be cleaned sneaking into to the impurity in the particulate sublayer by photolysis thus, and strengthen the physical engagement between micropartical.
In addition, semiconductor microactuator particle dispersion liquid is coated on described electroconductibility supporter, except heating or irradiation light, also can carries out other processing.As preferred method, such as enumerating energising, chemical treatment etc.
Also can exert pressure after coating, as the method for exerting pressure, can enumerate the method put down in writing in the special table of Japanese Patent 2003-500857 communique etc.As the example that irradiates light, can enumerate the method put down in writing in Japanese Patent Laid-Open 2001-357896 communique etc.As the example of plasma microwave energising, can enumerate the method put down in writing in Japanese Patent Laid-Open 2002-353453 communique etc.As chemical treatment, for example can enumerate the method for putting down in writing in Japanese Patent Laid-Open 2001-357896 communique.
Described semiconductor microactuator particle is coated with to method on the electroconductibility supporter except described semiconductor microactuator particle dispersion liquid being coated on to the method on the electroconductibility supporter, can make to wait with the following method method: the precursor of the semiconductor microactuator particle put down in writing in No. 2664194 communique of Japanese Patent is coated on the electroconductibility supporter, by airborne moisture, is hydrolyzed and obtains semiconductor microactuator particle film.
As precursor, for example can enumerate: (NH 4) 2tiF 6, titanium peroxide, metal alkoxide, metal complex, metal organic acid salt etc.
In addition, can enumerate: the slurry that coating coexists metal organic oxygen compound (alkoxide etc.) the method that forms semiconductor film by heat treated, optical processing etc.; To making inorganic, it is the method for the proterties special stipulation of the pH of the slurry that coexists of precursor, slurry and the TiO 2 particles that disperses.Also can in these slurries, add a small amount of tackiness agent, as tackiness agent, can enumerate: Mierocrystalline cellulose, fluoropolymer, cross-linked rubber, poly(tributoxy titanium), carboxymethyl cellulose etc.
The relevant technology as the formation to semiconductor microactuator particle or its precursor layer, can enumerate: by physical methods such as corona discharge, plasma, UV, carry out the method for hydrophilization in addition, utilize the chemical treatment of alkali or polyethylene dioxythiophene and polystyrolsulfon acid etc., the formation of intermediate coat etc. such as the joint of polyaniline etc.
As the semiconductor microactuator particle is coated with to the method on the electroconductibility supporter, also can be by described (1) damp process and (2) drying process, (3) additive method use.
As (2) drying process, can preferably enumerate Japanese Patent Laid-Open 2000-231943 communique etc.
As (3) additive method, can preferably enumerate Japanese Patent Laid-Open 2002-134435 communique etc.
As drying process, can enumerate evaporation or sputter, gas glue sedimentation etc.In addition, also can use electrophoretic method, electrolysis method.
In addition, also can use on heat resistant substrate temporary transient make film after, be transferred to the method on the film of plastics etc.Can preferably be listed below method etc.: the method for transfer printing via ethylene-vinyl acetate (Ethylene Vinyl Acetate, EVA) of putting down in writing in Japanese Patent Laid-Open 2002-184475 communique; That in Japanese Patent Laid-Open 2003-98977 communique, puts down in writing after formation semiconductor layer conductive layer, is transferred on organic substrate on the sacrificial substrate that contains the inorganic salt that can utilize ultraviolet ray, water solvent to remove, and then removes the method for sacrificial substrate.
For adsorbable a large amount of pigment, semiconductor microactuator particle preferred surface is amassed large semiconductor microactuator particle.For example, the semiconductor microactuator particle is coated with under the state on supporter, with respect to shadow area, its surface-area is preferably more than 10 times, more preferably more than 100 times.There is no particular restriction for its upper limit, but be generally 5000 times of left and right.As the structure of preferred semiconductor microactuator particle, can enumerate Japanese Patent Laid-Open 2001-93591 communique etc.
Usually, the thickness of semiconductor microactuator particle layer is thicker, and the amount of the pigment that can carry on per unit area more increases, so the assimilated efficiency of light uprises, but the diffusion length of the electronics produced increases, and therefore by electric charge, in conjunction with the loss produced, is also increased again.The preferred thickness of semiconductor microactuator particle layer is according to the purposes of element and difference, but typical thickness is 0.1 μ m～100 μ m.When the photoelectrochemical cell, preferably 1 μ m～50 μ m, more preferably 3 μ m～30 μ m.The semiconductor microactuator particle, in order after coating on supporter, particle to be connected airtight each other, also can heat 10 minutes～10 hours at the temperature of 100 ℃～800 ℃.When using glass as supporter, preferably 400 ℃～600 ℃ of masking temperature.
When using macromolecular material as supporter, preferably below 250 ℃, be filmed post-heating.Film-forming method as in the case, can be any of (1) damp process, (2) drying process, (3) electrophoretic method (comprising the electrolysis method), preferably (1) damp process or (2) drying process, more preferably (1) damp process.
Moreover the semiconductor microactuator particle is at every 1m 2supporter on glue spread be 0.5g～500g, more preferably 5g～100g.
For pigment is adsorbed on the semiconductor microactuator particle, preferably make to be immersed in for a long time in the pigment absorption use pigment solution that comprises solution and pigment of the present invention through the semiconductor microactuator particle of abundant drying.Pigment adsorbs with the solution used in pigment solution so long as the soluble solution of pigment of the present invention can be used with no particular limitation.Such as using: ethanol, methyl alcohol, Virahol, toluene, the trimethyl carbinol, acetonitrile, acetone, propyl carbinol etc.Wherein, can preferably use ethanol, toluene.
The pigment absorption that comprises solution and pigment of the present invention optionally can be heated to 50 ℃ to 100 ℃ with pigment solution.The absorption of pigment can be carried out before the coating of semiconductor microactuator particle, also can after the coating of semiconductor microactuator particle, carry out.In addition, also simultaneously coating semiconductor micropartical and pigment pigment is adsorbed.The pigment of absorption does not remove by cleaning.When carrying out the calcining of coated film, the absorption of pigment is preferably carried out after calcining.After calcining, be adsorbed in the coated film surface particularly preferably in water and before pigment promptly adsorbed.The pigment of absorption can be a kind, also several mixing can be used.When being mixed, pigment of the present invention of more than two kinds can be mixed, also can in the scope of harmless purport of the present invention, the complex compound pigment be mixed with pigment of the present invention.Select the pigment mixed in the mode of the wave band that enlarges as far as possible opto-electronic conversion.When pigment is mixed, the mode that must dissolve with all pigments is made pigment absorption pigment solution.
The usage quantity of pigment is in integral body, at every 1m 2supporter on preferably 0.01 mmole～100 mmoles, more preferably 0.1 mmole～50 mmoles, particularly preferably 0.1 mmole～10 mmoles.In the case, preferably by general formula (1), the usage quantity of represented metal complex dye is made as more than 5 % by mole by of the present invention.And then, when and while using the pigment represented by general formula (2), the usage quantity of pigment that preferably will be represented by general formula (2) is made as more than 80 % by mole.
In addition, the adsorptive capacity about pigment for the semiconductor microactuator particle, with respect to semiconductor microactuator particle 1g, preferably 0.001 mmole～1 mmole, more preferably 0.1 mmole～0.5 mmole.
By being made as this kind of amount of pigment, can obtain fully the sensitizing effect in semi-conductor.With respect to this, if amount of pigment is few, the sensitizing effect becomes insufficient, if amount of pigment is too much, the pigment be not attached on semi-conductor suspends and becomes the reason that the sensitizing effect is descended.
In addition, in order to reduce association, wait pigment interaction each other, also can make colourless compound co-adsorption.As carrying out co-adsorption hydrophobic compound, can enumerate sterid (such as cholic acid, trimethylacetic acid (pivalic acid)) with carboxyl etc.
After making pigment absorption, also can utilize amine to be processed the atomic surface of semi-conductor.As preferred amine, can enumerate 4-tert .-butylpyridine, polyvinylpyridine etc.These amines, in the situation that liquid can directly be used, also can be dissolved in organic solvent and use.
(to electrode)
Positive pole to electrode (counter electrode) as photoelectrochemical cell plays a role.The implication of electrode is usually identical with described electroconductibility supporter, but in obtain the formation fully kept as intensity, may not be to electrode.But, with regard to the viewpoint of stopping property, have electrode support more favourable.
As the material to electrode, can enumerate platinum, carbon, electric conductive polymer etc.As preferred example, can enumerate platinum, carbon, electric conductive polymer.
As the structure to electrode, the preferred high structure of current collection effect.As preferred example, can enumerate Japanese patent laid-open 10-505192 communique etc.
Be subject to optoelectronic pole can use titanium oxide and stannic oxide (TiO 2/ SnO 2) etc. combined electrode.As the mixed electrods of titanium dioxide, such as the mixed electrods that can enumerate Japanese Patent Laid-Open 2000-113913 communique record etc.As the mixed electrods beyond titanium dioxide, such as the mixed electrods that can enumerate Japanese Patent Laid-Open 2001-185243 communique, the record of Japanese Patent Laid-Open 2003-282164 communique etc.
(being subject to optoelectronic pole)
In order to improve utilization ratio of injecting light etc., can will be subject to optoelectronic pole to be made as tandem type.As the configuration example of preferred tandem type, can enumerate the example of putting down in writing in Japanese Patent Laid-Open 2000-90989, Japanese Patent Laid-Open 2002-90989 communique etc.
Also the inner light regime function of carrying out efficiently scattering of light, reflection that arranges of optoelectronic pole layer can be subject to.Can preferably enumerate and put down in writing in Japanese Patent Laid-Open 2002-93476 communique.
As the formation of element, also can there is the structure that lamination successively has the 1st electrode layer, the 1st photoelectric conversion layer, conductive layer, the 2nd photoelectric conversion layer, the 2nd electrode layer.In the case, the 1st photoelectric conversion layer can be identical or different from the pigment used in the 2nd photoelectric conversion layer, when pigment is different, and preferred absorption spectrum difference.In addition, applied structure or member in can this kind of electrochemical element of suitable application.
Between electroconductibility supporter and Porous semiconductor microactuator particle layer, in order to prevent directly contacting produced reverse current by electrolytic solution with electrode, be preferably formed anti-short circuit layer.As preferred example, can enumerate Japanese patent laid-open 06-507999 communique etc.
For prevent from being subject to optoelectronic pole with to the contacting of electrode, preferably use pad or dividing plate.As preferred example, can enumerate Japanese Patent Laid-Open 2001-283941 communique.
Sealing Method as unit, module, by aluminum alkoxide, for polyisobutene, be preferably the method for thermosetting resin, novolac resin, photo-hardening (methyl) acrylate resin, epoxy resin, ionomer resin, glass powder, aluminum oxide, the low melting glass slurry carried out to the method for lf etc.When using glass powder, can be also that glass powder is mixed in to the method in the acrylic resin that becomes tackiness agent.
[example]
Below, illustrate in greater detail the present invention according to example, but the present invention is not limited to these examples.
(synthesis example 1) exemplary compounds A-2b's is synthetic
Synthesize illustration compd A-2b by the synthesis path shown in following.
[changing 41]
Figure BDA00002803131000711
(1) compound-1 is synthetic
Add dimethyl formamide 10mL, 6-bromo-2 in the there-necked flask with cooling tube, 3-dicyano naphthalene 0.13g, 4-(methoxycarbonyl) phenyl-boron dihydroxide 0.18g, 1,4-diaza-bicyclo [2,2,2] octane 0.5mL, cesium carbonate 0.54g, and palladium (II) 0.03g, till being heated to 110 ℃ and stir 4 hours under stream of nitrogen gas.After being cooled to till room temperature, to adding diethyl ether in reaction solution and water is extracted.To adding water in the diethyl ether layer, after again being extracted, utilize sal epsom to carry out the diethyl ether layer predrying, and concentrated.Utilize alumina column chromatography to be made with extra care concentrated residue, obtain thus the compound-1 of 0.08g.
(2) compound-2 is synthetic
To adding amylalcohol 6mL, compound-10.16g, 4-tert-Butyl Phthalonitrile 0.38g, zinc chloride 0.14g, and 1 in the there-necked flask with cooling tube, 8-diaza-bicyclo [5,4,0]-7-hendecene 0.5mL, till being heated to 140 ℃ and stir 25 hours under stream of nitrogen gas.After being cooled to till room temperature, solvent is concentrated, utilize methyl alcohol to suspend and clean rear leaching solid residue., utilize alumina column chromatography to the solid of institute leaching made with extra care, and then utilize HPLC to divide to get refining, obtain thus the compound-2 of 0.17g thereafter.
(3) exemplary compounds A-2b's is synthetic
To adding tetrahydrofuran (THF) 5mL, compound-20.1g, and 1.0M aqueous sodium hydroxide solution 1mL in the there-necked flask with cooling tube, till being heated to 70 ℃ and stir 25 hours.After being cooled to till room temperature, solvent is concentrated, add water 10mL in residue, and carry out suspending in 1 hour under 100 ℃ and clean.After being cooled to till room temperature, by the insolubles filtering, and add acetic acid in filtrate.By separated out crystallization filtering, obtain thus the A-2b of 0.08g after making pH become below 7.
Mensuration by milli quality (milli mass) is identified.
Mass measured value (m/z); (M+H) +: 915.3111
Mass calculated value (m/z); (M+H) +: 915.3113 (C 55h 47n 8o 2zn)
(synthesis example 2) exemplary compounds C-2b's is synthetic
Synthesize illustration Compound C-2b by the synthesis path shown in following.
[changing 42]
Figure BDA00002803131000721
(1) compound-3 is synthetic
To adding 2-butanone 40mL, 2 in the there-necked flask with cooling tube, 6-dimethyl benzene mercaptan 4.0g, 4,5-dichloro phthalonitrile 1.9g, and salt of wormwood 6.03g, till being heated to 80 ℃ and stir 4 hours under stream of nitrogen gas.After being cooled to till room temperature, adding water 150mL, and directly stir 1 hour.Add toluene 50mL in obtained crystallization, be heated to till 60 ℃, and stir 30 minutes.Add methyl alcohol 100mL, and slowly cool to 5 ℃ till thereafter.By separated out crystallization filtering, obtain thus the compound-3 of 3.0g.
(2) compound-4 is synthetic
Obtain the compound-4 of 0.3g by the method identical with described compound-2.
(3) exemplary compounds C-2b's is synthetic
Obtain the exemplary compounds C-2b of 0.09g by the method identical with described exemplary compounds A-2b.Mensuration by the milli quality is identified.
Mass measured value (m/z); (M+H) +: 1563.3311
Mass calculated value (m/z); (M+H) +: 1563.3315 (C 91h 71n 8o 2s 6zn)
(synthesis example 3) exemplary compounds D-12j's is synthetic
Synthesize illustration Compound D-12j by the synthesis path shown in following.
[changing 43]
(1) compound-5 is synthetic
To adding dimethyl formamide 12.5mL, 2,6-diphenylphenol 4.7g, 4 in the there-necked flask with cooling tube, 5-dichloro phthalonitrile 1.25g, and salt of wormwood 8.75g, till being heated to 100 ℃ and stir 30 hours under stream of nitrogen gas.After being cooled to till room temperature, adding water 150mL, and utilize methylene dichloride to be extracted.Utilize anhydrous sodium sulphate to dichloromethane layer carry out predrying, and concentrated thereafter.Utilize silica gel column chromatography to be made with extra care obtained residue, then utilize methyl alcohol to carry out recrystallize to obtained coarse crystallization, obtain thus the compound-5 of 1.6g.
(2) compound-6 is synthetic
To adding tetrahydrofuran (THF) 8mL, 4 in the there-necked flask with cooling tube, 5-diamino phthalonitrile 1.58g, dioxo dimethyl succinate 1.91g, acetic acid 1.0mL, till being heated to 80 ℃ and stir 4 hours under stream of nitrogen gas.After being cooled to till room temperature, in reaction solution, add water, and by separated out crystallization filtering.Utilize alumina chromatography to be made with extra care obtained crystallization, obtain thus the compound-6 of 1.15g.
(3) compound-7 is synthetic
To adding propyl carbinol 7mL, compound-60.49g, compound-70.06g, lithium chloride 0.16g, and adjacent ethyl formate 0.13mL in the there-necked flask with cooling tube, under stream of nitrogen gas, be heated to till 110 ℃.Further heated after adding wherein 1,8-diaza-bicyclo [5,4,0]-7-hendecene 0.3mL, and stirred 8 hours.After being cooled to till room temperature, that solvent is concentrated, utilize methyl alcohol to suspend and clean leaching solid afterwards residue., utilize alumina column chromatography to the solid of institute leaching made with extra care, obtain thus compound-7 runic of 0.20g thereafter.
(4) compound-8 is synthetic
Add quinoline 5mL, compound-7 runic 0.62g vanadium (III) 0.2g in the there-necked flask with cooling tube, under 110 ℃, heating is 4 hours.After being cooled to till room temperature, adding water 20mL and acetic acid 30mL and stirred the solid that then leaching is separated out., utilize alumina column chromatography to the solid of institute leaching make with extra care after, and then utilize HPLC divide get refining, obtain thus the compound-8 of 0.06g thereafter.
(5) exemplary compounds D-12j's is synthetic
To adding tetrahydrofuran (THF) 5mL, compound-80.23g, 1.0M aqueous sodium hydroxide solution 1mL in the there-necked flask with cooling tube, till being heated to 70 ℃ and stir 33 hours.After being cooled to till room temperature, solvent is concentrated, add water 10mL in residue, and carry out suspending in 1.2 hours under 100 ℃ and clean.After being cooled to till room temperature, by the insolubles filtering, and add acetic acid in filtrate.By separated out crystallization filtering, obtain thus the exemplary compounds D-12j of 0.12g after making pH become below 7.Mensuration by the milli quality is identified.
Mass measured value (m/z); (M+H) +: 2183.5992
Mass calculated value (m/z); (M+H) +: 2183.6074 (C 144h 88n 10o 11v)
(synthesis example 4) exemplary compounds B-2b's is synthetic
Described compound-3 are become by the compound-9 of following synthesis path synthesized, in addition, obtain the exemplary compounds B-2b of 0.07g in the mode identical with synthesis example 2.
Mensuration by the milli quality is identified.
Mass measured value (m/z); (M+H) +: 1730.5103
Mass calculated value (m/z); (M+H) +: 1730.5115 (C 103h 94n 8o 2s 6zn)
[changing 44]
Figure BDA00002803131000761
(synthesis example 5) exemplary compounds E-2b's is synthetic
By described compound-3, become by the compound-10 of following synthesis path synthesized, in addition, obtain the exemplary compounds E-2b of 0.05g in the mode identical with synthesis example 2.
Mensuration by the milli quality is identified.
Mass measured value (m/z); (M+H) +: 1583.7072
Mass calculated value (m/z); (M+H) +: 1583.7118 (C 103h 97n 11o 2zn)
[changing 45]
Figure BDA00002803131000762
(synthesis example 6) comparative compound S-2's is synthetic
Synthesize comparative compound S-2 by the synthesis path shown in following.
[changing 46]
(1) compound-11 is synthetic
Add dimethyl formamide 10mL, the iodo-phthalonitrile 0.13g of 4-, 4-(methoxycarbonyl) phenyl-boron dihydroxide 0.18g, 1 in the there-necked flask with cooling tube, 4-diaza-bicyclo [2,2,2] octane 0.5mL, cesium carbonate 0.54g, and palladium (II) 0.03g, till being heated to 110 ℃ and stir 4 hours under stream of nitrogen gas.After being cooled to till room temperature, to adding diethyl ether in reaction solution and water is extracted.To adding water in the diethyl ether layer, after again being extracted, utilize sal epsom to carry out the diethyl ether layer predrying, and concentrated.Utilize alumina column chromatography to be made with extra care concentrated residue, obtain thus the compound-11 of 0.08g.
(2) compound-12 is synthetic
Obtain the compound-12 of 0.3g by the method identical with described compound-2.
(3) comparative compound S-2's is synthetic
Obtain the comparative compound S-2 of 0.08g by the method identical with described exemplary compounds A-2b.
Mensuration by the milli quality is identified.
Mass measured value (m/z); (M+H) +: 1513.3155
Mass calculated value (m/z); (M+H) +: 1513.3159 (C 87h 69n 8o 2s 6zn)
(synthesis example 7) comparative compound S-1's is synthetic
According to the international version of applied chemistry (Angew.Chem.Int.Ed.), 46,8358 (2007), synthetic following comparative compound S-1.
[changing 47]
Figure BDA00002803131000781
The mensuration of the maximum absorption wavelength of (test example) pigment
For the metal complex dye of synthesized in described synthesis example 1～synthesis example 7, measure maximum absorption wavelength.The results are shown in table 1.Mensuration is to utilize spectrophotometer (U-4100 (trade(brand)name), Hitachi's new and high technology (Hitachi High-Technologies) company manufactures) carry out, solution is used THF: ethanol=1: 1, and adjusted in the mode that concentration becomes 2 μ M.
[table 1]
Table 1
The pigment numbering Maximum absorption wavelength (nm) Remarks
A-2b 697 The present invention
A-3b 719 The present invention
B-2b 796 The present invention
C-li 720 The present invention
C-2b 718 The present invention
C-9f 735 The present invention
D-2b 708 The present invention
D-12j 753 The present invention
E-2b 746 The present invention
E-9h 764 The present invention
S-1 680 Comparative example
S-2 672 Comparative example
And then, in the absorption spectrum of described metal complex dye, measure and to be arranged in poor less than the maximum absorption wavelength of the maximum absorption wavelength at the longest wavelength place of the wavelength of 500nm and the wavelength more than 500nm.The results are shown in table 2.The maximum absorption wavelength be arranged in less than the longest wavelength place of the wavelength of 500nm is derived from the Q band, and the maximum absorption wavelength in the above wavelength of 500nm is derived from the special band of Soret, and this is poor less, means that absorption band is narrowlesser and small.
[table 2]
Table 2
The pigment numbering Wavelength difference (nm) Remarks
A-2b 332 The present invention
A-3b 300 The present invention
B-2b 326 The present invention
C-li 311 The present invention
C-2b 324 The present invention
C-9f 287 The present invention
D-2b 335 The present invention
D-12j 297 The present invention
E-2b 322 The present invention
E-9h 276 The present invention
S-1 361 Comparative example
S-2 356 Comparative example
Known according to the result of table 2, with the pigment of comparative example, to compare, the not absorption band of metal complex dye of the present invention is narrow and small, the special band of the Soret in ultraviolet region long wavelengthization, the photoabsorption wave band is wide.
[testing 1]
(making of photo-electric conversion element)
Photo-electric conversion element shown in construction drawing 1 10 as follows.
On glass substrate, form stannic oxide doped with fluorine as nesa coating by sputter, utilize laser to be rule to it, and nesa coating is divided into to 2 parts.
Then, allocate anatase-type titanium oxide (P-25 (trade(brand)name) that Japanese Ai Luoxier (Aerosil) company manufactures) 32g in the mixed solvent 100ml that comprises water that volume ratio is 4: 1 and acetonitrile, then use rotation/revolve round the sun and use the hybrid regulator of formula to disperse equably, mix, and obtaining semiconductor microactuator particle dispersion liquid.This dispersion liquid is coated on nesa coating, and is heated under 500 ℃ and make and be subject to optoelectronic pole.
, similarly make the dispersion liquid that with 40: 60 (mass ratio) contain silicon dioxide granule and Titanium Dioxide (Rutile) Top grade, this dispersion liquid is coated on to described being subject on optoelectronic pole, and heated under 500 ℃ and form the insulativity porous insert thereafter.Then, form carbon dioxide process carbon electrode as to electrode.
Then, make to be formed with the ethanolic soln (3 * 10 of the sensitizing coloring matter that the glass substrate of described insulativity porous insert puts down in writing in following table 3 -4mol/L) in, dipping is 48 hours.The glass that is stained with sensitizing coloring matter is flooded after 30 minutes in 10% ethanolic soln of 4-tert .-butylpyridine, utilize ethanol to be cleaned and make its seasoning.The thickness of the photoreceptor layers obtained in this way is 10 μ m, and the glue spread of semiconductor microactuator particle is 20g/m 2.Electrolytic solution is used the methoxypropionitrile solution of iodate dimethyl propyl imidazoles (0.5mol/L), iodine (0.1mol/L).
(mensuration of efficiency of conversion)
Make the light of the xenon lamp (oxtail trade (Ushio) manufacture) of 500W pass AM1.5G spectral filter (trade(brand)name, the manufacture of Ao Lier (Oriel) company), reach sharp wave spectral filter (sharp cut filter) (Ken Keer-42 (KenkoL-42), trade(brand)name), produce thus not containing ultraviolet simulated solar irradiation.This light intensity is 89mW/cm 2.Photo-electric conversion element to made irradiates this light, and utilizes current/voltage determinator (Keithley (Keithley) 238 types, trade(brand)name) to be measured produced electricity.In addition, the photoelectric transformation efficiency of photo-electric conversion element under 400nm～800nm of photoelectric transformation efficiency (Incident Photon to Current Efficiency, IPCE) the determinator mensuration made that utilizes peck Xie Er (Peccell) company to manufacture.The result that to be measured the efficiency of conversion of the photoelectrochemical cell obtained by these modes, and 450nm under photoelectric transformation efficiency (IPCE) be shown in following table 3.By the result of efficiency of conversion, be that efficiency of conversion is that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, less than 3.5%, is evaluated as zero, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 3]
Table 3
Specimen coding Sensitizing coloring matter Efficiency of conversion IPCE is (under 450nm, %) Remarks
1-1 A-1a ○ 19 The present invention
1-2 A-2b ○ 21 The present invention
1-3 A-3c ◎ 27 The present invention
1-4 A-5f ○ 24 The present invention
1-5 A-11e ○ 26 The present invention
1-6 A-11i ○ 28 The present invention
1-7 A-12b ◎ 32 The present invention
1-8 A-12h ◎ 35 The present invention
1-9 A-13b ◎ 29 The present invention
1-10 B-14b ◎ 28 The present invention
1-11 C-2b ○ 25 The present invention
1-12 C-13b ○ 34 The present invention
1-13 C-14j ○ 42 The present invention
1-14 D-2b ◎ 40 The present invention
1-15 D-14b ◎ 46 The present invention
1-16 E-14b ◎ 53 The present invention
1-17 S-1 × 5 Comparative example
1-18 S-2 × 11 Comparative example
As shown in table 3, use the electrochemical cell of metal complex dye made of the present invention, especially in the situation that use A-3c, A-12b, A-12h, A-13b, B-14b, D-2b, D-14b, E-14b as pigment, IPCE is high, as its result, efficiency of conversion shows the high value more than 3.5%.Even if, in the situation that use other pigments of the present invention, efficiency of conversion is also the higher level more than 2.5%, less than 3.5%.
With respect to this, the efficiency of conversion of the comparative example of specimen coding 1-17 and specimen coding 1-18 is insufficient less than 2.0%.
[testing 2]
Make ITO (tin indium oxide) film on glass substrate, and on the ITO film lamination FTO (fluorine-doped tin oxide) film, make thus nesa coating., on nesa coating form oxide semiconductor porous film, obtain thus transparent electrode plate thereafter.Then, use this transparent electrode plate to make photoelectrochemical cell, and measure efficiency of conversion.Its method is as shown in following (1)～(5).
(1) preparation of starting compound solution for the ITO film
Indium chloride (III) tetrahydrate 5.58g and tin chloride (II) dihydrate 0.23g are dissolved in ethanol 100ml, and make ITO film starting compound solution.
(2) preparation of starting compound solution for the FTO film
Tin chloride (IV) pentahydrate 0.701g is dissolved in ethanol 10ml, and add wherein the saturated aqueous solution of Neutral ammonium fluoride 0.592g, last in Ultrasonic Cleaners and approximately within 20 minutes, make this mixture dissolve fully, and make FTO film starting compound solution.
(3) making of ITO/FTO nesa coating
Matting is carried out on the surface of the heat resistant glass plate that is 2mm to thickness, after drying, this sheet glass is placed in reactor, and utilizes well heater to be heated in addition.When the Heating temperature of well heater becomes 450 ℃, under the pressure of 0.06MPa, the nozzle that will be 0.3mm with starting compound solution from bore apart from the ITO film that makes to obtain in (1) apart from being made as 400mm of sheet glass carries out spraying in 25 minutes.
After the spraying of this ITO film with starting compound solution, (during this period, glass baseplate surface was continued to the ethanol spraying through 2 minutes, and the rising of inhibition substrate surface temperature), when the Heating temperature of well heater becomes 530 ℃, under identical condition, make the FTO film obtained in (2) carry out spraying in 2 minutes 30 seconds with starting compound solution.Thus, obtain the transparent electrode plate be formed with successively ITO film that thickness is 530nm, FTO film that thickness is 170nm on heat resistant glass plate.
In order to compare, make in the same manner the transparent electrode plate only make film forming on heat resistant glass plate that ITO film that thickness is 530nm is 2mm at thickness, and make in the same manner the transparent electrode plate that only makes film forming on heat resistant glass plate that FTO film that thickness is 180nm is 2mm at thickness.
Utilize process furnace, under 450 ℃, described 3 kinds of transparent electrode plates are carried out to heating in 2 hours.
(4) making of photoelectrochemical cell
Then, use described 3 kinds of transparent electrode plates, make the photoelectrochemical cell of the structure shown in the Fig. 2 in No. 4260494 specification sheets of Japanese Patent.The formation of oxide semiconductor porous film 15 is that the titanium oxide microparticle that makes median size be about 230nm is dispersed in acetonitrile 100ml and makes slurry, on transparency electrode 11, utilizing excellent painting method that it is coated with into to thickness is 15 μ m, carry out calcining in 1 hour after drying under 450 ℃, the pigment of then putting down in writing in carrying table 4 on this oxide semiconductor porous film 15.Immersion condition in pigment solution is made as identical with described experiment 1.
And then, will be on sheet glass lamination conductive board that ITO film and FTO film arranged for to electrode 16, will comprise the used for electrolyte of non-aqueous solution of iodine/iodide in dielectric substrate 17.The planar dimension of photoelectrochemical cell is made as to 25mm * 25mm.
(5) evaluation of photoelectrochemical cell
This photoelectrochemical cell is irradiated to simulated sunlight (AM1.5), and obtain its efficiency of conversion.The results are shown in table 4.Be that 3.5% above person is evaluated as ◎ by efficiency of conversion, efficiency of conversion be more than 2.5%, be evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 4]
Table 4
Specimen coding TCO Sensitizing coloring matter Efficiency of conversion Remarks
2-1 ITO only C-3b ○ The present invention
2-2 FTO only C-3b ○ The present invention
2-3 ITO+FTO C-3b ◎ The present invention
2-4 ITO only D-2b ○ The present invention
2-5 FTO only D-2b ○ The present invention
2-6 ITO+FTO D-2b ◎ The present invention
2-7 ITO only E-14b ○ The present invention
2-8 FTO only E-14b ○ The present invention
2-9 ITO+FTO E-14b ◎ The present invention
2-10 ITO only S-1 × Comparative example
2-11 FTO only S-1 × Comparative example
2-12 ITO+FTO S-1 × Comparative example
Known use S-1 is low as the efficiency of conversion of the specimen coding 2-10 of sensitizing coloring matter～specimen coding 2-12, with respect to this, uses the specimen coding 2-1 of metal complex dye of the present invention～specimen coding 2-9 to show good result.Knownly only make the transparent electrode plate of ITO film or FTO film film forming compare as the situation of transparent electrode plate with using, use lamination to have the transparent electrode plate of ITO film and FTO film high especially as the efficiency of conversion of the photoelectrochemical cell of transparent electrode plate, its effect is high because of metal complex dye of the present invention.
[testing 3]
On the FTO film, the configuration collecting electrodes is made photoelectrochemical cell, and estimates efficiency of conversion.Estimate as described below, use-testing unit (i) and 2 kinds of test units of test unit (iv).
(test unit (i))
Matting is carried out on surface to the heat resistant glass plate of length 100mm * width 100mm * thickness 2mm, in addition after drying, this sheet glass is placed in reactor, after utilizing well heater to be heated, under the pressure of 0.06MPa, to carry out spraying in 25 minutes apart from the nozzle that FTO prepared in 2 (fluorine-doped tin oxide) film is 0.3mm with starting compound solution from bore that makes to test apart from being made as 400mm of sheet glass, and prepare the glass substrate with the FTO film.On its surface, the flute profile that is 5 μ m by the degree of depth by etching method becomes grid circuit pattern shape.After forming pattern by photoetching, use hydrofluoric acid to carry out etching.In order to form coating, utilize sputtering method to form metal conducting layer (Seed Layer) thereon, and then electroplate (additive plating) by additivity and form metallic wiring layer.Metallic wiring layer be formed to 3 μ m height from the transparency carrier surface with being lens-shaped till.Circuit width is made as to 60 μ m.This metallic wiring layer, utilize large plastometric set (Severe Plastic Deformation, SPD) method to using the thickness of 400nm and form the FTO film as shielding layer, and make electrode base board (i).Moreover the section shape of electrode base board (i) becomes the section shape shown in the Fig. 2 in Japanese Patent Laid-Open 2004-146425.
The dispersion liquid that titanium oxide that median size is 25nm is obtained in being dispersed in acetonitrile 100ml in the upper coating of electrode base board (i) is also in addition dry, then under 450 ℃, carries out heat-agglomerating in 1 hour.Make in its ethanolic soln that is immersed in the pigment shown in table 5 to make pigment absorption.Immersion condition is made as with to test 1 identical.Thick thermoplastic polyolefin resin's sheet via 50 μ m and, by the configuration of itself and platinum sputter FTO substrate subtend, then make resin sheet section heat fusing that two pole plates are fixed.
Moreover, from the spout of the electrolytic solution that is opened in advance platinum sputter utmost point side, inject the methoxyacetonitrile solution of the iodine of iodized salt that principal constituent comprises 0.5M and 0.05M, and make between electrode to be full of this solution.And then using epoxy is that sealing resin formally seals periphery and injecting electrolytic solution mouth, and make test unit (i) at current-collecting terminals section silver coating slurry.
Utilize the simulated solar irradiation of AM1.5, the efficiency of conversion of test unit (i) is estimated.The results are shown in table 5.
(test unit (iv))
Prepare the glass substrate with the FTO film of length 100mm * width 100mm with the method identical with test unit (i).Form metallic wiring layer (golden circuit) on this FTO glass substrate by the additivity electrochemical plating.Metallic wiring layer (golden circuit) is to be formed on substrate surface with being reticulation, and circuit width is made as to 50 μ m, and circuit thickness is made as to 5 μ m.Utilize the SPD method to form FTO film that thickness is 300nm on its surface as shielding layer, and make test unit (iv).Utilization is with scanning electron microscope (the Scanning Electron Microscopy with Energy Dispersive X-ray of power spectrum, SEM-EDX) section of electrode base board (iv) is confirmed, result exists the end be considered to by resistance plating agent to roll caused piercing in the distribution bottom, and is not coated with FTO in part backlight.
Use electrode base board (iv), with test unit (i), similarly make test unit (iv).Utilize the simulated solar irradiation of AM1.5, the efficiency of conversion of test unit (iv) is estimated, and shown the result in table 5.
Moreover, by efficiency of conversion, be that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, is evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 5]
Table 5
Specimen coding Test unit Sensitizing coloring matter Efficiency of conversion Remarks
3-1 (i) A-3b ◎ The present invention
3-2 (iv) A-3b ○ The present invention
3-3 (i) C-2b ◎ The present invention
3-4 (iv) C-2b ○ The present invention
3-5 (i) C-13b ◎ The present invention
3-6 (iv) C-13b ○ The present invention
3-7 (i) D-11b ◎ The present invention
3-8 (iv) D-11b ○ The present invention
3-9 (i) E-12b ◎ The present invention
3-10 (iv) E-12b ○ The present invention
3-11 (i) S-1 × Comparative example
3-12 (iv) S-1 × Comparative example
According to table 5, when using metal complex dye of the present invention, the efficiency of conversion in the situation of test unit (i) shows the high value more than 3.5%.On the other hand, if the situation of use-testing unit (iv) is observed, with the situation of the pigment that uses comparative example, compare, in the situation that use metal complex dye of the present invention, efficiency of conversion uprises.Therefore, the metal complex dye of known the application of the invention, the degree of freedom rising (comparison of specimen coding 3-2, specimen coding 3-4, specimen coding 3-6, specimen coding 3-8 and specimen coding 3-10 and specimen coding 3-12) that test unit is selected.
[testing 4]
Make (A)～photoelectrochemical cell of photoelectrochemical cell (photocell unit) (photocell unit) (D) as shown in following, and the efficiency of conversion of the photocell unit of made is estimated.
(photocell unit (A))
(1) oxide semiconductor film forms the preparation with coating fluid (A)
The titanium hydride of 5g is suspended in the pure water of 1L, lasts the hydrogen peroxide liquid 400g that adds 5 quality % in 30 minutes, then be heated to 80 ℃ of solution that dissolved and make pertitanic acid.Minute get 90 volume % from the total amount of this solution, and add strong aqua pH is adjusted to 9, then be added in autoclave, at saturated vapo(u)r, depress with 250 ℃ and carry out 5 hours hydrothermal treatment consists and make colloidal tio 2 particle (A).According to X ray diffraction, the colloidal tio 2 particle (A) obtained is the high anatase-type titanium oxide of crystallinity.
Then, till the colloidal tio 2 particle (A) that will obtain by described mode is concentrated into 10 quality %, and mix described pertitanic acid solution, then the titanium in this mixed solution is carried out to TiO 2convert, to become TiO 2the mode of 30 quality % of quality is added the hydroxypropylcellulose that forms auxiliary agent as film, and make semiconductor film, forms with coating fluid (A).
(2) making of oxide semiconductor film (A)
Secondly, be formed with fluorine-doped tin oxide as the transparent glass substrate of electrode layer on coating described coating fluid (A), and make its seasoning, then use low-pressure mercury light irradiation 6000mJ/cm 2ultraviolet ray peroxy acid is decomposed, and the sclerosis that makes to film.Decomposition and the annealing of hydroxypropylcellulose are carried out in the heating of filming under 300 ℃ in 30 minutes, thereby form oxide semiconductor film (A) on glass substrate.
(3) pigment is towards the absorption on oxide semiconductor film (A)
Then, preparation is 3 * 10 as the concentration of the pigment shown in the table 6 of light splitting sensitizing coloring matter -4the ethanolic soln of mol/L.Utilize the 100rpm turner that this pigment solution is coated on to oxide semiconductor film (A) upper and in addition dry.This coating and drying step are carried out 5 times.
(4) preparation of electrolyte solution
In the mixed solvent that the volume ratio of acetonitrile and NSC 11801 is 1: 5, so that the tetrapropyl ammonium iodide becomes the concentration of 0.46mol/L, the mode that makes iodine become the concentration of 0.07mol/L dissolves both and makes electrolyte solution.
(5) making of photovoltaic element (A)
The glass substrate of the oxide semiconductor film (A) that pigment is adsorbed being formed with of made in described (3) is as the electrode of a side, electrode using following transparent glass substrate as opposite side and with the configuration of its subtend, this transparent glass substrate is to form and carry the transparent glass substrate of platinum thereon using fluorine-doped tin oxide as electrode, utilize resin by side seal, and prepared electrolyte solution in described (4) is enclosed between electrode, and then utilize wire to be connected between electrode and make photovoltaic element (A).
(6) evaluation of photovoltaic element (A)
Utilizing solar simulator is 100W/m to photovoltaic element (A) exposure intensity 2light, and measure η (efficiency of conversion).The results are shown in table 6.
(photocell unit (B))
Irradiation ultraviolet radiation decomposes peroxy acid, make to film the sclerosis after, carry out ion exposure (day new Electric Manufacture: ion implantation apparatus of Ar gas, under 200eV, irradiate 10 hours), in addition, form oxide semiconductor film (B) in the mode identical with oxide semiconductor film (A).
With oxide semiconductor film (A) similarly, the absorption of the pigment shown in oxide semiconductor film (B) carry out table 6.
, with photocell unit (A) identical method make photovoltaic element (B), and measure efficiency of conversion thereafter.The results are shown in table 6.
(photocell unit (C))
Utilize pure water to be diluted the titanium tetrachloride of 18.3g, with TiO 2the meter that converts obtains the aqueous solution of the titanium tetrachloride that contains 1.0 quality %.One in the face of this aqueous solution is stirred, and one side is added the ammoniacal liquor of 15 quality %, and obtains the white slurry that pH is 9.5.This slurry is filtered to cleaning, with TiO 2convert and count, obtain the block of the hydrous titanium oxide gel of 10.2 quality %.This block is mixed with 5 quality % hydrogen peroxide liquid 400g, then be heated to 80 ℃ of solution that dissolved and make pertitanic acid.Minute get 90 volume % from the total amount of this solution, and add wherein strong aqua pH is adjusted to 9, then be added in autoclave, at saturated vapo(u)r, depress with 250 ℃ and carry out 5 hours hydrothermal treatment consists and make colloidal tio 2 particle (C).
Then, use the pertitanic acid solution and the colloidal tio 2 particle (C) that obtain by described mode, in the mode identical with oxide semiconductor film (A), form oxide semiconductor film (C).And then, in the mode identical with metal-oxide semiconductor (MOS) film (A), carry out the absorption as the pigment shown in the table 6 of light splitting sensitizing coloring matter.
, with photovoltaic element (A) identical method make photovoltaic element (C), and measure efficiency of conversion thereafter.The results are shown in table 6.
(photocell unit (D))
Utilize pure water to be diluted the titanium tetrachloride of 18.3g, with TiO 2the meter that converts obtains the aqueous solution of the titanium tetrachloride that contains 1.0 quality %.One in the face of this aqueous solution is stirred, and one side is added the ammoniacal liquor of 15 quality %, and obtains the white slurry that pH is 9.5.After this slurry is filtered and cleans, it is suspended in pure water and is made as TiO 2the slurry of hydrous titanium oxide gel of 0.6 quality %, after adding wherein hydrochloric acid and making pH become 2, be added in autoclave, depress with 180 ℃ and carry out 5 hours hydrothermal treatment consists and make colloidal tio 2 particle (D) at saturated vapo(u)r.
Then, till colloidal tio 2 particle (D) is concentrated into to 10 quality %, to be converted into TiO 2after become 30 quality % mode add wherein the hydroxypropylcellulose that forms auxiliary agent as film, form and use coating fluid and make semiconductor film.Then, be formed with fluorine-doped tin oxide as the transparent glass substrate of electrode layer on the described coating fluid of coating, and make its seasoning, then use low-pressure mercury light irradiation 6000mJ/cm 2ultraviolet ray make film sclerosis.And then decomposition and the annealing of hydroxypropylcellulose is carried out in heating in 30 minutes under 300 ℃, thereby form oxide semiconductor film (D).
Then, the absorption of the pigment shown in carry out table 6 in the mode identical with oxide semiconductor film (A).
, with photovoltaic element (A) identical method make photovoltaic element (D), and measure efficiency of conversion thereafter.Show the result in table 6.
Moreover, by efficiency of conversion, be that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, is evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 6]
Table 6
Specimen coding The photocell unit Sensitizing coloring matter Efficiency of conversion (η) Remarks
4-1 (A) A-2b ◎ The present invention
4-2 (B) A-2b ◎ The present invention
4-3 (C) A-2b ◎ The present invention
4-4 (D) A-2b ○ The present invention
4-5 (A) A-12b ◎ The present invention
4-6 (B) A-12b ◎ The present invention
4-7 (C) A-12b ◎ The present invention
4-8 (D) A-12b ○ The present invention
4-9 (A) S-1 × Comparative example
4-10 (B) S-1 × Comparative example
4-11 (C) S-1 × Comparative example
4-12 (D) S-1 × Comparative example
Known according to table 6, with the photocell unit of comparative example, compare, use the efficiency of conversion of photocell unit of metal complex dye of the present invention high.Especially, known when by metal complex dye of the present invention during for test unit (A)～test unit (C), efficiency of conversion is high especially.
[testing 5]
As shown in following, carry out the preparation of titanium oxide or synthesize, make oxide semiconductor film by obtained titanium oxide, and make photoelectrochemical cell, and it is estimated.
(1) utilize the preparation of the titanium oxide 1 of heat treating process
Use commercially available anatase-type titanium oxide (the former industry of stone (share) manufacture, trade(brand)name ST-01), be heated to approximately 900 ℃ and convert the titanium oxide 1 of brookite type to.
(2) utilize the titanium oxide 2 (brookite type) of damp process and synthesizing of titanium oxide 3 (brookite type)
(titanium oxide 2 (brookite type))
Distilled water 954mL is loaded in the reactive tank with reflux cooler, and heats to 95 ℃.One side remains about 200rpm by stirring velocity, and one side drops to titanium tetrachloride (Ti content: 16.3 quality %, proportion is 1.59, purity is 99.9%) aqueous solution 46mL in reactive tank in distilled water with the speed of about 5.0mL/min.Now, note not making the temperature of reaction solution to descend.Its result, titanium tetrachloride concentration is 0.25mol/L (titanium oxide is scaled 2 quality %).In reactive tank, immediately start to produce white Turbid after dropwise reaction liquid, but continue to keep with the temperature under this state, drip finish after so that heat up and be heated near boiling point till (104 ℃), the maintenance end that makes to react completely after 60 minutes under this state.
Obtained colloidal sol is filtered, then with the vacuum drier of 60 ℃, made powder.Utilize the X ray diffraction method to carry out quantitative analysis to this powder, result (peak strengths that brookite type is 121)/(peak strengths of three overlapping positions) are than being 0.38, and (the main peak intensity of rutile-type)/(peak strengths of three overlapping positions) are than being 0.05.If the crystallinity of obtaining obtained titanium oxide according to these, the crystallinity of the titanium oxide that obtained is that brookite type is about 70.0 quality %, rutile-type and is about the crystallinity that 1.2 quality %, Detitanium-ore-type are about 28.8 quality %.In addition, utilize transmission electron microscope to be observed this micropartical, the median size of 1 particle is 0.015 μ m as a result.
(titanium oxide 3 (brookite type))
Utilize distilled water to be diluted titanium trichloride aqueous solution (Ti content: 28 quality %, proportion is 1.5, purity is 99.9%), make the solution of 0.25mol/L in the titanium concentration conversion.Now, it is cooling that the mode do not risen with liquid temperature is carried out ice bath, and remain below 50 ℃.Then, this solution 500mL is fed in the reactive tank with reflux cooler, one side heats to 85 ℃ of one sides from the ozone gas generation device ozone gas that purity is 80% is bubbled with 1L/min, and carries out oxidizing reaction.Keep after 2 hours making to react completely end under this state.
To obtained colloidal sol filtered, vacuum-drying and make powder.Utilize the X ray diffraction method to carry out quantitative analysis to this powder, result (peak strengths that brookite type is 121)/(peak strengths of three overlapping positions) are than being 0.85, and (the main peak intensity of rutile-type)/(peak strengths of three overlapping positions) are than being 0.If the crystallinity of obtaining obtained titanium oxide according to these, the crystallinity of the titanium oxide that obtained be brookite type be about 98 quality %, rutile-type be 0 quality %, Detitanium-ore-type be 0 quality %, approximately 2% for amorphous.In addition, utilize transmission electron microscope to be observed this micropartical, the median size of 1 particle is 0.05 μ m as a result.
(making of dye-sensitized photoelectric conversion device and evaluation)
Using described titanium oxide 1～titanium oxide 3 as semi-conductor, as made the photo-electric conversion element of the formation as shown in the Fig. 1 with Japanese Patent Laid-Open 2000-340269 as following.
Be coated with fluorine-doped tin oxide on glass substrate, and make the conductive clear electrode.Make the slurry using each Titanium particles as raw material on electrode surface, after utilizing excellent painting method to be coated with into thickness to be 50 μ m, calcined under 500 ℃ and form the thin layer that thickness is about 20 μ m.Then, the pigment shown in preparation table 7 is 3 * 10 -4the ethanolic soln of volumetric molar concentration, the glass substrate that makes to be formed with the thin layer of described titanium oxide is immersed in this ethanolic soln, and at room temperature keeps 12 hours.
The salt compounded of iodine of use tetrapropyl ammonium and the acetonitrile solution of lithium iodide are as electrolytic solution, using platinum as electrode being made to the photo-electric conversion element of the formation shown in the Fig. 1 with Japanese Patent Laid-Open 2000-340269.Opto-electronic conversion is described element to be irradiated to the light (utilizing spectral filter to end infrared rays section) of the high pressure mercury vapour lamp of 160w, and measures efficiency of conversion now.Show the result in table 7.
Moreover, by efficiency of conversion, be that 3.5% above person is expressed as ◎, efficiency of conversion is more than 2.5%, is expressed as zero less than 3.5%, efficiency of conversion is more than 2.0%, is expressed as △ less than 2.5%, by efficiency of conversion less than 2.0% being expressed as *.
[table 7]
Table 7
Specimen coding Titanium oxide Sensitizing coloring matter Efficiency of conversion Remarks
1 Titanium oxide 1 A-8j ○ The present invention
2 Titanium oxide 2 A-8j ○ The present invention
3 Titanium oxide 3 A-8j ○ The present invention
4 Titanium oxide 1 C-12i ○ The present invention
5 Titanium oxide 2 C-12i ○ The present invention
6 Titanium oxide 3 C-12i ◎ The present invention
7 Titanium oxide 1 S-1 × Comparative example
8 Titanium oxide 2 S-1 × Comparative example
9 Titanium oxide 3 S-1 × Comparative example
Known according to table 7, use the efficiency of conversion of photo-electric conversion element of metal complex dye of the present invention high.
[testing 6]
As shown in following, use the semi-conducting electrode that contains the different titanium oxide of particle diameter to make photoelectrochemical cell, and estimate its characteristic.
[preparation of slurry]
At first, prepare the semiconductor layer of the semi-conducting electrode in order to form the formation photoelectrochemical cell or the slurry of light scattering layer by following program.
(starch 1 preparation)
By spherical TiO 2particle (Detitanium-ore-type, median size; 25nm, hereinafter referred to as spherical TiO 2particle 1) be added in salpeter solution and stirred, making thus titania slurry.Then, to adding the cellulose-based tackiness agent as tackifier in titania slurry, and mixed and made slurry 1.
(starch 2 preparation)
By spherical TiO 2particle 1 and other spherical TiO 2particle (Detitanium-ore-type, median size; 200nm, below, spherical TiO be called 2particle 2) be added in salpeter solution and stirred, making thus titania slurry.Then, to adding the cellulose-based tackiness agent as tackifier in titania slurry, and mixed and made slurry 2 (TiO 2the quality of particle 1: TiO 2the quality of particle 2=30: 70).
(starch 3 preparation)
By described slurry 1 and bar-shaped TiO 2particle (Detitanium-ore-type, diameter; 100nm, aspect ratio; 5, hereinafter referred to as bar-shaped TiO 2particle 1) mix, make bar-shaped TiO 2the quality of particle 1: the slurry 3 of starching 1 quality=10: 90.
(starch 4 preparation)
By described slurry 1 and bar-shaped TiO 2particle 1 mixes, and makes bar-shaped TiO 2the quality of particle 1: the slurry 4 of starching 1 quality=30: 70.
(starch 5 preparation)
By described slurry 1 and bar-shaped TiO 2particle 1 mixes, and makes bar-shaped TiO 2the quality of particle 1: the slurry 5 of starching 1 quality=50: 50.
(starch 6 preparation)
By described slurry 1 and tabular mica particle (diameter; 100nm, aspect ratio; 6, hereinafter referred to as sheet mica particle 1) mix, make the quality of tabular mica particle 1: the slurry 6 of starching 1 quality=20: 80.
(starch 7 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 30nm, aspect ratio; 6.3, hereinafter referred to as bar-shaped TiO 2particle 2) mix, make the quality of bar-shaped TiO2 particle 2: the slurry 7 of starching 1 quality=30: 70.
(starch 8 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 50nm, aspect ratio; 6.1, hereinafter referred to as bar-shaped TiO 2particle 3) mix, make bar-shaped TiO 2the quality of particle 3: the slurry 8 of starching 1 quality=30: 70.
(starch 9 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 75nm, aspect ratio; 5.8, hereinafter referred to as bar-shaped TiO 2particle 4) mix, make bar-shaped TiO 2the quality of particle 4: the slurry 9 of starching 1 quality=30: 70.
(starch 10 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 130nm, aspect ratio; 5.2, hereinafter referred to as bar-shaped TiO 2particle 5) mix, make bar-shaped TiO 2the quality of particle 5: the slurry 10 of starching 1 quality=30: 70.
(starching 11)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 180nm, aspect ratio; 5, hereinafter referred to as bar-shaped TiO 2particle 6) mix, make bar-shaped TiO 2the quality of particle 6: the slurry 11 of starching 1 quality=30: 70.
(starch 12 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 240nm, aspect ratio; 5, hereinafter referred to as bar-shaped TiO 2particle 7) mix, make bar-shaped TiO 2the quality of particle 7: the slurry 12 of starching 1 quality=30: 70.
(starch 13 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 110nm, aspect ratio; 4.1, hereinafter referred to as bar-shaped TiO 2particle 8) mix, make bar-shaped TiO 2the quality of particle 8: the slurry 13 of starching 1 quality=30: 70.
(starch 14 preparation)
By described slurry 1 and bar-shaped TiO 2particle (anatase octahedrite, diameter; 105nm, aspect ratio; 3.4, hereinafter referred to as bar-shaped TiO 2particle 9) mix, make bar-shaped TiO 2the quality of particle 9: the slurry 14 of starching 1 quality=30: 70.
[making of photoelectrochemical cell]
(photoelectrochemical cell 1)
By program shown below, making has the optoelectronic pole of the formation identical with the optoelectronic pole 12 shown in the Fig. 5 put down in writing in Japanese Patent Laid-Open 2002-289274, and then the use optoelectronic pole, make the photoelectrochemical cell 1 of the scale of the 10mm * 10mm that there is the formation identical with dye-sensitized solar cell 20 except this optoelectronic pole.
Preparation will be doped with the SnO of fluorine 2conducting film (thickness; 500nm) be formed on the transparency electrode formed on glass substrate.Then, by described slurry 2 screen paintings at this SnO 2on conducting film, then in addition dry.Thereafter, with in air, the condition of 450 ℃ calcined.And then, use described slurry 4 to repeat this screen painting and calcining, thus at SnO 2form the semi-conducting electrode (area of sensitive surface of the formation identical with the semi-conducting electrode 2 shown in Fig. 5 on conducting film; 10mm * 10mm, bed thickness; 10 μ m, the bed thickness of semiconductor layer; 6 μ m, the bed thickness of light scattering layer; 4 μ m, contained bar-shaped TiO in light scattering layer 2the containing ratio of particle 1; 30 quality %), make the optoelectronic pole that does not contain sensitizing coloring matter.
Then, the pigment shown in table 8 is adsorbed on semi-conducting electrode as follows.
At first, the dehydrated alcohol that will dewater by magnesium ethylate (magnesium ethoxide), as solvent, makes the pigment shown in table 8 become 3 * 10 with its concentration -4the mode of mol/L is dissolved in this solvent, and makes pigment solution.Then, semi-conducting electrode is immersed in this solution, thus, makes approximately 1.5 mmoles/m 2pigment be adsorbed on semi-conducting electrode, and complete optoelectronic pole.
Then, preparation has the platinum electrode (thickness of Pt film of the shape identical with described optoelectronic pole and size; 100nm) as to electrode,, and the iodine that preparation contains iodine and lithium iodide is that redox solution is as ionogen E.And then, preparation has the pad S (trade(brand)name: " house beautiful jade (Surlyn) ") of E.I.Du Pont Company's manufacture of the shape identical with the size of semi-conducting electrode, as as shown in the Fig. 3 put down in writing in Japanese Patent Laid-Open 2002-289274, make optoelectronic pole 10 with to electrode CE via pad S subtend, and fill described ionogen towards inside and complete photoelectrochemical cell 1.
(photoelectrochemical cell 2)
Carry out as follows the manufacture of semi-conducting electrode, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 1 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 2 of the identical formation of the dye-sensitized solar cell 20 shown in Fig. 3 of putting down in writing.
Described slurry 2 is formed with slurry as semiconductor layer.Then, by described slurry 2 screen paintings at SnO 2on conducting film, then in addition dry.Thereafter, with in air, the condition of 450 ℃ calcined, and forms semiconductor layer.
Inner most layer by described slurry 3 as light scattering layer forms with slurry.In addition, by described slurry 5, the outermost layer as light scattering layer forms with slurry.Then, form light scattering layer in the mode identical with dye-sensitized solar cell 1 on semiconductor layer.
Then, at SnO 2form the semi-conducting electrode (area of sensitive surface of the formation identical with the semi-conducting electrode 2 shown in the Fig. 1 put down in writing in Japanese Patent Laid-Open 2002-289274 on conducting film; 10mm * 10mm, bed thickness; 10 μ m, the bed thickness of semiconductor layer; 3 μ m, the bed thickness of inner most layer; 4 μ m, contained bar-shaped TiO in inner most layer 2the containing ratio of particle 1; 10 quality %, the bed thickness of outermost layer; 3 μ m, contained bar-shaped TiO in inner most layer 2the containing ratio of particle 1; 50 quality %), make the optoelectronic pole that does not contain sensitizing coloring matter.With photoelectrochemical cell 1 similarly, make optoelectronic pole with to electrode CE via pad S subtend, and fill described ionogen towards inside and complete photoelectrochemical cell 2.
(photoelectrochemical cell 3)
When manufacturing semi-conducting electrode, described slurry 1 is formed with slurry as semiconductor layer, described slurry 4 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 3 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, the area of the sensitive surface of semi-conducting electrode; 10mm * 10mm, bed thickness; 10 μ m, the bed thickness of semiconductor layer; 5 μ m, the bed thickness of light scattering layer; 5 μ m, contained bar-shaped TiO in light scattering layer 2the containing ratio of particle 1; 30 quality %.
(photoelectrochemical cell 4)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 6 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 4 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, the area of the sensitive surface of semi-conducting electrode; 10mm * 10mm, bed thickness; 10 μ m, the bed thickness of semiconductor layer; 6.5 μ m, the bed thickness of light scattering layer; 3.5 μ m, the containing ratio of contained sheet mica particle 1 in light scattering layer; 20 quality %.
(photoelectrochemical cell 5)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 8 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 5 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 3; 30 quality %.
(photoelectrochemical cell 6)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 9 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 6 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 4; 30 quality %.
(photoelectrochemical cell 7)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 10 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 7 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 5; 30 quality %.
(photoelectrochemical cell 8)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 11 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 8 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 6; 30 quality %.
(photoelectrochemical cell 9)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 13 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 9 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 8; 30 quality %.
(photoelectrochemical cell 10)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 14 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 10 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 9; 30 quality %.
(photoelectrochemical cell 11)
When manufacturing semi-conducting electrode, only use described slurry 2 to make the semi-conducting electrode (area of sensitive surface that only comprises semiconductor layer; 10mm * 10mm, bed thickness; 10 μ m), in addition, with the program making optoelectronic pole identical with photoelectrochemical cell 1 and photoelectrochemical cell 11.
(electrochemical cell 12)
When manufacturing semi-conducting electrode, described slurry 2 is formed with slurry as semiconductor layer, described slurry 7 is formed with slurry as light scattering layer, in addition, with the program making identical with photoelectrochemical cell 1 have with Japanese Patent Laid-Open 2002-289274 in the optoelectronic pole 10 shown in Fig. 5 of putting down in writing, and Japanese Patent Laid-Open 2002-289274 in optoelectronic pole, and the photoelectrochemical cell 12 of the identical formation of the photoelectrochemical cell 20 shown in Fig. 3 of putting down in writing.Moreover, contained bar-shaped TiO in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 2; 30 quality %.
[battery behavior test]
Carry out the battery behavior test, photoelectrochemical cell 1～photoelectrochemical cell 12 is measured to efficiency eta.Battery behavior test is by using Tai Yang Mo Be device (and hat (WACOM) manufacture, trade(brand)name WXS-85H), irradiate through the AM1.5 spectral filter from xenon lamp 1000W/m 2simulated solar irradiation carry out.Use the I-V tester to measure I-E characteristic, and obtain effciency of energy transfer (η/%).The results are shown in table 8.
Moreover, by efficiency of conversion, be that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, is evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 8]
Table 8
Specimen coding Photoelectrochemical cell Sensitizing coloring matter Efficiency of conversion Remarks
6-1 1 A-2b ○ The present invention
6-2 2 A-2b ○ The present invention
6-3 3 A-2b ◎ The present invention
6-4 4 A-2b ◎ The present invention
6-5 5 A-2b ○ The present invention
6-6 6 A-2b ○ The present invention
6-7 1 A-14b ◎ The present invention
6-8 2 A-14b ◎ The present invention
6-9 3 A-14b ◎ The present invention
6-10 4 A-14b ◎ The present invention
6-11 5 A-14b ○ The present invention
6-12 6 A-14b ◎ The present invention
6-13 7 A-14b ◎ The present invention
6-14 8 A-14b ◎ The present invention
6-15 9 A-14b ◎ The present invention
6-16 10 A-14b ◎ The present invention
6-17 1 S-1 × Comparative example
6-18 2 S-1 × Comparative example
6-19 3 S-1 × Comparative example
6-20 4 S-1 × Comparative example
6-21 5 S-1 × Comparative example
6-22 6 S-1 × Comparative example
6-23 7 S-1 × Comparative example
6-24 8 S-1 × Comparative example
6-25 9 S-1 × Comparative example
6-26 10 S-1 × Comparative example
6-27 11 S-1 × Comparative example
6-28 12 S-1 × Comparative example
As shown in table 8, use the efficiency of conversion of electrochemical cell of metal complex dye of the present invention high.
[testing 7]
Will be in metal oxide microparticle add metal alkoxide and become pulp-like person and be coated on conductive board, thereafter, carry out the irradiation of UV ozone, UV irradiates or dry, and make electrode., make photoelectrochemical cell, and measure efficiency of conversion thereafter.
(metal oxide microparticle)
As metal oxide microparticle, use titanium oxide.Titanium oxide is used 30% to be that rutile-type, 70% is the P25 powder (Degussa (Degussa) company manufactures, trade(brand)name) that Detitanium-ore-type and median size are 25nm by quality ratio.
(pre-treatment of the sub-powder of metal oxide microparticle)
In advance metal oxide microparticle is heat-treated, thus by surperficial organism and moisture removal.In the situation that titanium oxide microparticle utilizes the baking oven of 450 ℃ to heat 30 minutes under atmosphere.
(mensuration of contained amount of moisture in metal oxide microparticle)
By Ka Er Fischer (Kcal Fisher) titration of heavily measuring the few and amount of moisture that break away from while being heated to 300 ℃ of Minus in the thermogravimetric flow measurement, contained amount of moisture in titanium oxide in the environment that is kept at 26 ℃ of temperature, humidity 72%, P25 powder (Degussa (Degussa) company manufactures, trade(brand)name) is carried out quantitatively.
By the Ka Er Karl Fischer titration, the amount of moisture broken away from when 300 ℃ of lower heated oxide titaniums, P25 powder (Degussa (Degussa) company manufactures, trade(brand)name) is carried out quantitatively the water that contains 0.253mg in the titanium oxide fine powder end of 0.1033g as a result.That is, titanium oxide fine powder end is containing the moisture of 2.5wt% (% by weight) of having an appointment, so the sub-powder of metal oxide microparticle utilizes the baking oven of 450 ℃ to carry out thermal treatment in 30 minutes with before the mixing of metal alkoxide, and is kept in moisture eliminator after cooling and uses.
(preparation of metal alkoxide slurry)
Metal alkoxide as the effect of bringing into play bond metal oxide microparticle, use tetraisopropoxy titanium (IV) (Titanium tetraisopropoxide, TTIP) as titanium material, use four n-propoxyzirconium (IV) as the zirconium raw material, use five oxyethyl group niobiums (V) as niobium raw material (being aldrich (Aldrich) company manufactures).
Metal oxide microparticle is with the mode that excessively the combination each other of thickening and particle can not carried out fully of the amorphous layer that hydrolysis was produced by metal alkoxide, the suitable adjusting corresponding to the sub-diameter of metal oxide microparticle with the molar concentration rate of metal alkoxide.Moreover, metal alkoxide is all made to the ethanolic soln of 0.1M.When titanium oxide microparticle while (TTIP) mixing, with respect to titanium oxide microparticle 1g, is mixed to the TTIP solution of the 0.1M of 3.55g with tetraisopropoxy titanium (IV).Now, the titanium oxide concentration in the slurry obtained becomes approximately 22 quality %, and becomes the viscosity that is suitable for coating.In addition, titanium oxide now and TTIP and ethanol are 1: 0.127: 3.42 by quality ratio, take molar ratio computing as 1: 0.036: 5.92.
Similarly, about the mixed pulp of the alkoxide beyond titanium oxide microparticle and TTIP, prepared by the mode that also with micropartical concentration, becomes 22 quality %.Be made as 16 quality % in using zinc oxide and the atomic slurry of stannic oxide.In the situation that zinc oxide and stannic oxide, with respect to the sub-1g of metal oxide microparticle, the ratio that metal alkoxide solution is 5.25g is mixed.
In encloses container, utilize magnetic stirring apparatus that metal oxide microparticle is obtained to slurry uniformly with metal alkoxide solution stirring 2 hours.
Coating process towards coating slurry on conductive board can be used doctor method, screen painting method, spraying method etc., and suitable slurry viscosity is according to coating process and suitable selection.Use easily the method (being similar to the doctor method) be coated with by glass stick herein.The concentration of in the case, giving metal oxide microparticle of suitable slurry viscosity becomes the scope of general 5 quality %～30 quality %.
In the scope of the layer thickness of the amorphous metal oxide generated by the decomposition of metal alkoxide in this example, in 0.1nm～0.6nm left and right.General 0.05nm～1.3nm left and right becomes the scope of the room temperature masking that is suitable for utilizing present method.
(towards coating and the air-dry processing of the slurry on conductive board)
At polyethylene terephthalate (PET) film substrate (20 Ω/cm with tin-doped indium oxide (ITO) conducting film 2) or with the glass substrate (10 Ω/cm of fluorine-doped tin oxide (FTO) conducting film 2) upper, 2 adhesion zones are attached abreast to each slurry that then uses glass stick to be coated with equably to prepare according to described method as pad and with fixed intervals.
After the coating slurry, before pigment absorption, for having or not UV ozonize, UV radiation treatment or drying treatment, the change condition is made porous film.
(drying treatment)
To in atmosphere, with room temperature, carry out about 2 minutes air-dry towards the film after coating on conductive board.In this process, the metal alkoxide in slurry is hydrolyzed because of the moisture in atmosphere, forms respectively titanium oxide, zirconium white, the niobium oxides of amorphous from Ti alkoxide, Zr alkoxide, Nb alkoxide.
The amorphous metal oxide performance generated reaches metal oxide microparticle the effect of film and conductive board bonding each other, therefore only by the air-dry porous film that just can obtain physical strength and tack excellence.
(UV ozonize)
Use Japanese electronic laser (Nippon Laser&amp in the UV ozonize; Electronics) the NL-UV253UV ozone clean machine that company manufactures.The UV light source possesses 3 4.5W mercuryvapour lamps that have open-wire line at 185nm and 254nm place, and sample flatly is configured in from light source to the approximately distance of 6.5 centimetres.Produce ozone by import oxygen flow in reaction chamber.In this example, carry out 2 hours these UV ozonize.Moreover, do not see the decline by the electroconductibility of the caused ITO film of this UV ozonize and FTO film fully.
(UV processing)
Processed after nitrogen replacement carrying out in reaction chamber, in addition, similarly carry out processing in 2 hours in the mode identical with described UV ozonize.Do not see the decline of being processed the electroconductibility of caused ITO film and FTO film by this UV fully.
(pigment absorption)
Use the pigment shown in table 9 as sensitizing coloring matter, make the ethanolic soln of 0.5mM.In this example, the porous film of made in described processing procedure is immersed in the solution of sensitizing coloring matter after dry 1 hour in the baking oven of 100 ℃, and directly at room temperature places and make sensitizing coloring matter be adsorbed on titania surface in 50 minutes.Utilize ethanol to be cleaned the sample after sensitizing coloring matter absorption, and in addition air-dry.
(making of photoelectrochemical cell and battery behavior evaluation)
To be formed with the conductive board of the porous film after pigment absorption as optoelectronic pole, make its with by sputter to the platinum micropartical carried out the ITO/PET film modified or FTO/ glass to electrode pair to, and trial-production photoelectrochemical cell.The useful area of described optoelectronic pole is made as to about 0.2cm 2.Electrolyte solution is used LiI, the I of 0.05M that contains 0.5M 2, 0.5M the 3-methoxypropionitrile of tert .-butylpyridine, and it is directed in two interelectrode gaps by capillary phenomenon.
The evaluation of battery performance (efficiency of conversion) is by fixed light subnumber (10 16cm -2) irradiate lower photoelectric current action spectrum and measure, reach AM1.5 simulated solar irradiation (100mW/cm 2) I-V under irradiating measures to carry out.The CEP-2000 type light splitting sensitometry device that these use light splitting gauge (Bunkoukeiki) company to manufacture in measuring.Show the result in table 9.
Moreover, by efficiency of conversion, be that 2.5% above person is evaluated as ◎, efficiency of conversion is more than 2.0%, is evaluated as zero less than 2.5%, efficiency of conversion is more than 1.5%, is evaluated as △ less than 2.0%, by efficiency of conversion less than 1.5% being evaluated as *.
[table 9]
Table 9
Figure BDA00002803131001021
Figure BDA00002803131001031
" pre-treatment of titanium oxide " hurdle of table 9 means to have or not the pre-treatment (carrying out thermal treatment in 30 minutes in the baking oven of 450 ℃) of titanium oxide microparticle.Moreover sample 7-6, sample 7-14 and sample 7-22 are the samples that uses the slurry made of high TTIP concentration (mol ratio of titanium oxide: TTIP is 1: 0.356).Other samples (sample 7-1～sample 7-5, sample 7-7～sample 7-13, sample 7-23 and sample 7-24) are use titanium oxide: TTIP=1: the sample of 0.0356 slurry made.
In table 9, after the hurdle of " UV ozone ", " UV ", " drying " means respectively to have or not the formation of porous film, UV ozonize, UV radiation treatment, drying treatment before sensitizing coloring matter absorption.Mean treated person with " zero ", with " * ", mean untreated person.
Known according to the result shown in table 9, no matter UV ozonize, UV radiation treatment, drying treatment after using the photoelectrochemical cell of metal complex dye of the present invention to have or not the formation of porous film, before sensitizing coloring matter absorption, efficiency of conversion is all high.
[testing 8]
Use acetonitrile as solvent, preparation is dissolved with the electrolyte solution of lithium iodide 0.1mol/l, iodine 0.05mol/L, iodate dimethyl propyl imidazoles 0.62mol/l.The mode that the benzoglyoxaline based compound of No.1～No.8 shown in following is become respectively to 0.5mol/L with concentration is added respectively, is dissolved in this electrolyte solution.
[changing 48]
Figure BDA00002803131001041
On glass substrate, by the stannic oxide to doped with fluorine, undertaken that sputter forms conducting film and as nesa coating.On this conducting film, coating contains anatase-type titanium oxide dispersion of particles liquid and (allocates anatase-type titanium oxide (P-25 (trade(brand)name) of Japanese Ai Luoxier company manufacture) 32g in the water that to comprise volume ratio be 4: 1 and the mixed solvent 100ml of acetonitrile, and use rotation/revolve round the sun and use the hybrid regulator of formula to disperse equably, mix and the semiconductor microactuator particle dispersion liquid that obtains, carry out sintering thereafter under 500 ℃ and form the photoreceptor layers that thickness is 15 μ m.The benzoglyoxaline based compound electrolytic solution of No.1～No.8 is dropped on this photoreceptor layers.
The frame-type pad of polyethylene film system (thickness is 25 μ m) is positioned on this photoreceptor layers, and utilizes platinum to cover this pad to electrode, and make photo-electric conversion element.
Using the Xe lamp as light source, to obtained photo-electric conversion element exposure intensity, be 100mW/cm 2light.Measure open circuit voltage and photoelectric transformation efficiency.The results are shown in table 10.
Be that the above person of 6.3V is evaluated as ◎ by open circuit voltage, open circuit voltage be more than 6.0V, less than 6.3V person, be evaluated as zero, open circuit voltage is more than 5.7V, less than 6.0V person, is evaluated as △, by open circuit voltage less than 5.7V person be evaluated as *.
Be that 3.5% above person is evaluated as ◎ by efficiency of conversion, efficiency of conversion be more than 2.5%, be evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
Moreover, also mean to use the result of the photo-electric conversion element of the electrolytic solution that does not add the benzoglyoxaline based compound in table 10.
[table 10]
Table 10
Known according to the result of table 10, use open circuit voltage and the efficiency of conversion of photo-electric conversion element of metal complex dye of the present invention all high.
[testing 9]
(photoelectrochemical cell 21)
By program shown below, the optoelectronic pole that making has a formation identical with the optoelectronic pole 10 shown in the Fig. 1 put down in writing in Japanese Patent Laid-Open 2004-152613 (still, semi-conducting electrode 2 is made as to double-layer structural), and then use this optoelectronic pole, in addition, make the photoelectrochemical cell 21 (area of the sensitive surface F2 of semi-conducting electrode 2: 1cm with formation identical with the dye-sensitized solar cell 20 shown in the Fig. 1 put down in writing in Japanese Patent Laid-Open 2004-152613 2).Moreover, about each layer of semi-conducting electrode 2 with double-layer structural, the layer be configured near the side of transparency electrode 1 is called to " the 1st layer ", the layer be configured near the side to electrode CE is called to " the 2nd layer ".
At first, (Degussa (Degussa) company manufactures to use the P25 powder that median size is 25nm, trade(brand)name), reach particle diameter Titanium particles, the P200 powder (median size: 200nm different from it, Degussa (Degussa) company manufactures, trade(brand)name), the mass ratio that the content of total of P25 and P200 of take is 15 quality % and P25 and P200 becomes P25: P200=30: 70 mode, to adding methyl ethyl diketone, ion exchanged water in them, (Shu Jing changes into company and manufactures interfacial agent, trade(brand)name; " Te Lidun-X (Triton-X) "), and mixed and make the slurry (below, be called " slurry 1 ") of the 2nd layer of formation use.
And then, do not use P200, and only use P25, in addition, make the slurry (content of P1 of the 1st layer of formation use by the preparation procedure identical with described slurry 1; 15 quality %, below, be called " slurry 2 ").
On the other hand, preparation will be doped with the SnO of fluorine 2conducting film (thickness: 700nm) be formed on the transparency electrode (thickness: 1.1mm) formed on glass substrate (transparent conductivity glass).Then, utilize rod coater that described slurry 2 is coated on to this SnO 2on conducting film, then in addition dry.In air with 450 ℃ carry out 30 minute calcining thereafter.So, form the 1st layer of semi-conducting electrode 2 on transparency electrode.
And then, use slurry 1 to repeat and described identical coating and calcining, form the 2nd layer thus on the 1st layer.So, at SnO 2form the semi-conducting electrode 2 (area of sensitive surface on conducting film; 1.0cm 2, the 1st layer with the aggregate thickness of the 2nd layer: 10 μ m (thickness of the 1st layer: 3 μ m, the thickness of the 2nd layer: 7 μ m)), and make not the optoelectronic pole containing the state of sensitizing coloring matter.
Then, preparation is as the ethanolic soln (concentration of sensitizing coloring matter of the sensitizing coloring matter shown in the table 11 of sensitizing coloring matter; 3 * 10 -4mol/L).Described optoelectronic pole is immersed in this solution, and places 20 hours with the temperature condition of 80 ℃, and make sensitizing coloring matter absorption.In order to promote open circuit voltage Voc, semi-conducting electrode pigment absorption after in the acetonitrile solution of 4-tert .-butylpyridine flooded to 15 minute after, during remaining the stream of nitrogen gas of 25 ℃ make its drying, and complete described optoelectronic pole 10 thereafter.
Then, make have the shape identical with described optoelectronic pole and size to electrode CE.At first, the hexahydrated aqueous isopropanol of Platinic chloride is dropped to transparent conductivity on glass, carry out carrying out 30 minutes calcination processing with 450 ℃ after drying in atmosphere, obtain thus the platinum sintering to electrode CE.Moreover, be provided with in advance the hole (diameter is 1mm) of the injection use of ionogen E in to electrode CE at this.
Then, make zinc iodide, iodate-1,2-dimethyl-3-propyl imidazole, iodine, and the 4-tert .-butylpyridine be dissolved in the methoxyacetonitrile that becomes solvent, and make aqueous ionogen (iodate zinc concentration: 10mmol/L, the concentration of iodate dimethyl propyl imidazoles: 0.6mol/L, the concentration of iodine: 0.05mol/L, 4-tert .-butylpyridine concentration: 1mol/L).
Then, preparation has the pad S (trade(brand)name: " coughing Milan (Himilan) " of Mitsui Du Pont polymeric chemical (Du Pont-Mitsui Polychemicals) the company manufacture of the shape identical with the size of semi-conducting electrode, ethylene/methacrylic acid random copolymers ionomeric membrane), as as shown in the Fig. 1 put down in writing in Japanese Patent Laid-Open 2004-152613, make optoelectronic pole with to electrode via pad subtend, and by thermo-welding, both laminatings are obtained to the framework (not filling ionogen) of battery.
Then, injecting aqueous ionogen in from the hole to electrode to framework, utilize the member plugging hole with the pad same story, so by this member thermo-welding in the sealing of the Zhong Laijiang hole, hole to electrode, and complete photoelectrochemical cell 21.
(photoelectrochemical cell 22)
Iodate zinc concentration in aqueous ionogen is made as to 50mmol/L, in addition, with the program identical with photoelectrochemical cell 21 and condition, makes photoelectrochemical cell 22.
(photoelectrochemical cell 23)
Add lithium iodide and replace the zinc iodide in aqueous ionogen, and the concentration of the lithium iodide in aqueous ionogen is made as to 20mmol/L, in addition, with the program identical with photoelectrochemical cell 21 and condition, make photoelectrochemical cell 23.
(electrochemical cell 24)
Add lithium iodide and replace the zinc iodide in aqueous ionogen, and the concentration of the lithium iodide in aqueous ionogen is made as to 100mmol/L, in addition, with the program identical with photoelectrochemical cell 21 and condition, make photoelectrochemical cell 24.
(battery behavior evaluation test)
By following program, photoelectrochemical cell 21～photoelectrochemical cell 24 is measured to photoelectric transformation efficiency (η (%)).
The battery behavior evaluation test is to use Tai Yang Mo Be device (and to be preced with (WACOM) and to manufacture, trade(brand)name; " WXS-85-H type "), be made as 100mW/cm at the illuminate condition of the simulated solar irradiation from xenon source that will pass AM spectral filter (AM1.5) 2(illuminate condition of so-called " 1Sun ") condition determination under carry out.
For each photoelectrochemical cell, use the I-V tester at room temperature to measure I-E characteristic, and obtain photoelectric transformation efficiency η [%] according to these I-E characteristics.Using obtained result as table 11, " fresh " of (illuminate condition of 1Sun) means.In addition, to irradiate at 60 ℃, 1Sun, under the operation condition under 10 Ω loads, the result that the durability evaluation that the photoelectric transformation efficiency η of photoelectrochemical cell 21～photoelectrochemical cell 24 [%] was investigated out under 80 ℃ after 300 hours is tested also is shown in table 11.
Moreover, by the efficiency of conversion of Fresh, be that 3.5% above person is evaluated as ◎, the efficiency of conversion of Fresh is more than 2.5%, less than 3.5%, is evaluated as zero, the efficiency of conversion of Fresh is more than 2.0%, is evaluated as △ less than 2.5%, by the efficiency of conversion of Fresh less than 2.0% being evaluated as *.
[table 11]
Table 11
As the result according to as shown in table 11 and as clear and definite, even if the photoelectrochemical cell of known use metal complex dye of the present invention is in the situation that, during zinc iodide is added into to ionogen, efficiency of conversion and weather resistance are also excellent.
[testing 10]
1. the preparation of titanium oxide dispersion
(Japanese Ai Luoxier (share) manufactures to add titanium dioxide particle in the stainless steel container made that is 200ml to the internal capacity that inboard has been coated with to fluoro-resin, trade(brand)name: Degussa P-25) (aldrich company manufactures for 15g, water 45g, dispersion agent, trade(brand)name: zirconium oxide bead (manufacture of Ni Kaduo (Nikkato) company) 30g that special power dragon X-100 (Triron X-100)) 1g, diameter are 0.5mm, used sand mill (sand grinder mill) (manufacture of Ai Maikesi (Aimex) company) to carry out 2 hours dispersion treatment with 1500rpm.Filtering zirconium oxide bead from obtained dispersion liquid.The median size of the titanium dioxide particle in the dispersion liquid obtained is 2.5 μ m.Moreover particle diameter is that the Ma Shitesaizhe (Mastersizer) (trade(brand)name) manufactured by Ma Erwen (MALVERN) company measures.
2. absorption has the making of the titanium oxide microparticle sublayer (electrode A) of pigment
Preparation is coated with the conductive glass plate of the 20mm * 20mm of fluorine-doped tin oxide, and (Asahi Glass (Asahi Glass) (share) is manufactured, trade(brand)name: TCO Glass-U, surface resistivity: about 30 Ω/m 2), pad is attached to the two ends (part of the width of 3mm from end) of its conductive layer side with adhesion zone, use glass stick that described dispersion liquid is coated on conductive layer.The coating dispersion liquid after, adhesion zone is peeled off, and at room temperature carry out 1 day air-dry.Then, this semi-conductor coated glass plate is fed in electric furnace (large and retort furnace FP-32 type that science (Yamato Scientific) (share) is manufactured), and carries out calcining in 30 minutes under 450 ℃.Take out semi-conductor coated glass plate and in addition cooling after, in the ethanolic soln (concentration: 3 * 10 of the sensitizing coloring matter shown in table 12 -4mol/L) in, dipping is 3 hours.Make absorption have the semi-conductor coated glass plate of sensitizing coloring matter to flood after 15 minutes in the 4-tert .-butylpyridine, utilize ethanol to be cleaned, and make its seasoning, and obtain the titanium oxide microparticle sublayer (electrode A) that absorption has sensitizing coloring matter.The thickness of the dye-sensitized titanium oxide microparticle sublayer of electrode A is 10 μ m, and the glue spread of titanium oxide microparticle is 20g/m 2.In addition, the adsorptive capacity of pigment is 0.1mmol/m corresponding to its kind 2～10mmol/m 2scope in.
3. the making of dye-sensitized solar cell
Make 3 kinds of dye-sensitized solar cells of dye-sensitized solar cell a～dye-sensitized solar cell c by following method.In these dye-sensitized solar cells, use sensitizing coloring matter, following nitrogen containing polymer α and the following electrophilic reagent β shown in table 12, and obtain specimen coding 10-1～specimen coding 10-15.
(a) making of dye-sensitized solar cell a
As solvent, the mixture that the volume ratio of using acetonitrile and 3-methyl-2-oxazolidone is 90/10.To adding the salt compounded of iodine of iodine with 1-methyl as electrolytic salt-3-hexyl imidazoles in this solvent, and make the solution of the iodine of the electrolytic salt that contains 0.5mol/L and 0.05mol/L.With respect to (solvent+nitrogen containing polymer compound+salt) 100 mass parts, to adding the following nitrogen containing polymer compound α of 10 mass parts in this solution.And then, mix the following electrophilic reagent β of the reactive nitrogen atom for following nitrogen containing polymer compound α of 0.1 mole, and make uniform reaction soln.
[changing 49]
[changing 50]
Figure BDA00002803131001102
On the other hand, will comprise evaporation has the side of the platinum film to electrode of the sheet glass of platinum to be positioned in via pad on the dye-sensitized titanium oxide microparticle sublayer of described electrode A, and conductive glass plate and platinum evaporation sheet glass are fixed.The open end of obtained assembly is immersed in described electrolyte solution, and by capillary phenomenon, reaction soln is infiltrated in dye-sensitized titanium oxide microparticle sublayer.
Then heat 30 minutes under 80 ℃, and carry out crosslinking reaction.So, as as shown in Fig. 2 of Japanese Patent Laid-Open 2000-323190 communique, obtaining on the conductive layer 12 of conductive glass plate 10 lamination successively has dye-sensitized titanium oxide microparticle sublayer 20, dielectric substrate 30 and comprises platinum film 42 and the of the present invention dye-sensitized solar cell a-1 to electrode 40 of sheet glass 41 (specimen coding 10-1).
In addition, except change pigment as shown in table 12, by repeating said steps, obtain dye-sensitized solar cell a-2～dye-sensitized solar cell a-5.
(b) making of dye-sensitized solar cell b
The electrode A (20mm * 20mm) that will comprise the titanium oxide microparticle sublayer that makes in this way sensitizing coloring matter absorption is superimposed upon via pad on the platinum evaporation sheet glass of formed objects.Then, utilize capillary phenomenon that electrolytic solution (mixture that is 90/10 using the volume ratio of acetonitrile and 3-methyl-2-oxazolidone is as the iodine 0.05mol/L of solvent, the solution of lithium iodide 0.5mol/L) is infiltrated in the gap of two sheet glass, and make dye-sensitized solar cell b-1 (specimen coding 10-2).In addition, except change pigment as shown in table 12, by repeating said steps, obtain dye-sensitized solar cell b-2～dye-sensitized solar cell b-5.
(c) making of dye-sensitized solar cell c (ionogen of putting down in writing in Japanese patent laid-open 9-27352 communique)
Electrolytic solution is coated on to the electrode A (20mm * 20mm) that comprises the titanium oxide microparticle sublayer that makes in this way sensitizing coloring matter absorption upper, and makes its impregnation.Moreover, electrolytic solution is to contain (Japanese oil chemistry (share) manufacture of six glycolmethacrylates by lithium iodide 500mg is dissolved in, BlemmerPE-350) 1g, ethylene glycol 1g, and (Japanese vapour Ba-Jia Ji (Ciba-Geigy) (share) manufactures as the 2-hydroxy-2-methyl of polymerization initiator-1-phenyl-propane-1-ketone, Da Luoke 1173 (Darocur1173)) in the mixed solution of 20mg, and carry out vacuum stripping in 10 minutes and obtain.Then, to the porousness titanium oxide layer of described mixing solutions impregnation be placed under decompression, remove thus the bubble in the porousness titanium oxide layer, after promoting the infiltration of monomer, by UV-irradiation, carry out after polymerization uniform gel-filled to the fine emptying aperture of porousness titanium oxide layer by macromolecular compound.Make winner in this way expose 30 minutes in the iodine environment, after making iodine diffuse in macromolecular compound, stack platinum evaporation sheet glass, and obtain dye-sensitized solar cell c-1 (specimen coding 10-3).In addition, except change pigment as shown in table 12, by repeating said steps, obtain photoelectrochemical cell c-2～photoelectrochemical cell c-5.
4. the mensuration of photoelectric transformation efficiency
Make the light of the xenon lamp (oxtail motor (share) manufacture) of 500W pass AM1.5 spectral filter (manufacture of Ao Lier (Oriel) company) and sharp wave spectral filter (trade(brand)name: Ken Keer-42 (KenkoL-42)), form thus containing ultraviolet simulated solar irradiation.Light intensity is made as to 89mW/cm 2.
Conductive glass plate 10 at described photoelectrochemical cell is connected respectively crocodile clip with on platinum evaporation sheet glass 40, and each crocodile clip is connected on current/voltage determinator (Keithley SMU238 type).From conductive glass plate 10 sides, it is irradiated to simulated solar irradiation, and utilize the current/voltage determinator to measure the electricity produced.By the initial value (fresh) of the efficiency of conversion (η) of the photoelectrochemical cell obtained therefrom, and the rate of descent of efficiency of conversion during 300 hours Continuous irradiation gather and be shown in table 12.
Moreover, by the efficiency of conversion of Fresh, be that 3.5% above person is evaluated as ◎, the efficiency of conversion of Fresh is more than 2.5%, less than 3.5%, is evaluated as zero, the efficiency of conversion of Fresh is more than 2.0%, is evaluated as △ less than 2.5%, by the efficiency of conversion of Fresh less than 2.0% being evaluated as *.
[table 12]
Table 12
Figure BDA00002803131001121
As the result according to as shown in table 12 and as clear and definite, using the initial value of efficiency of conversion of the photoelectrochemical cell of metal complex dye of the present invention is qualified level, and then the rate of descent of the efficiency of conversion after 300 hours is also low, and shows excellent weather resistance
[testing 11]
Use by the prepared suspension of sol-gel method, and it is on glass to utilize screen painting to be coated on FTO, and calcines TiO under 450 ℃ 2porous layer.Be immersed in metal complex dye A-2b of the present invention or compare 10 of pigment S-1 in it -4in the mol/L ethanolic soln, make thus pigment absorption.
Make 2,2 of 100mg ', 7,7 '-tetra-(diphenylamino)-9,9 '-spiral shell two fluorenes are dissolved in the chloroform of 5ml.Solution is coated in to the dyestuff surface lightly, makes thus this solution infiltrate to the pore of layer.Then, one of solution directly is placed in to surface and at room temperature carries out drying.Then, the coating supporter is arranged in evaporation coating device, by the hot evaporation under the vacuum of about 10-5 millibar so that applied thickness be 100nm 2,2 ', 7,7 '-tetra-(diphenylamino)-9,9 '-layer of spiral shell two fluorenes.And then the gold layer that is 200nm using thickness in evaporation coating device is as electrode is overlayed on this coating supporter.
The sample of so preparation is arranged in the Optical devices that comprise high-voltage lamp, spectral filter, lens and mounting paper (mounting).Can change intensity by the use of spectral filter and the movement of lens.At gold layer and SnO 2contact is installed on layer, and is arranged in during sample is irradiated on the device shown in current-flow test set.In order to be measured, use the light of suitable spectral filter blocking wavelength less than 430nm.And then, so that the intensity of radioactive rays and about 1000W/m 2consistent mode setting device roughly.
At gold layer and SnO 2contact is installed on layer, in addition, two contacts is connected on potentiostat in during sample is irradiated.Use the electric current that produces about 90nA in the sample of S-1 not applying external voltage, but produce the electric current of about 190nA in the sample that uses metal complex dye A-2b of the present invention.
Known according to this result, use the efficiency of conversion excellence of the photoelectrochemical cell of metal complex dye of the present invention.
Moreover, in the situation that any sample, if do not irradiated, electric current all disappears.
[testing 12]
In the series unit of similarly making at the example 1 with Japanese Patent Laid-Open 2000-90989, also can confirm to compare with using the relatively photoelectrochemical cell of pigment S-1, use the efficiency of conversion of photoelectrochemical cell of metal complex dye A-2b of the present invention high.
[testing 13]
Titanium isopropoxide 125ml is dropped in 0.1M-aqueous nitric acid (bank field chemistry (Kishida Chemical) limited-liability company manufacture) 750ml, and heating 8 hours under 80 ℃ and hydrolysis reaction is carried out, make sol solutions thus.Obtained sol solutions is kept 15 hours with 250 ℃ in titanium autoclave processed, make grain growth, thereafter, carry out 30 minutes ultrasonic wave and disperse, obtain thus the colloidal solution that contains the Titanium particles that average primary particle diameter is 20nm.
Utilize vaporizer, after being concentrated into lentamente till the concentration that titanium oxide becomes 10wt% by the obtained colloidal solution that contains Titanium particles, add 40% polyethylene glycol (bank field chemistry limited-liability company manufacture in the weight ratio with respect to titanium oxide, weight average molecular weight: 200000), and stirred, obtain thus the suspension that is dispersed with Titanium particles.
Utilize the doctor method that prepared titanium oxide suspension is coated on and is formed with SnO 2film, as the nesa coating side of the glass substrate of nesa coating, is filming of 10mm * 10mm left and right and obtain area.Under 120 ℃ to this film carry out 30 minutes predrying, and then under oxygen atmosphere, carry out calcining in 30 minutes with 500 ℃, and form the oxidation titanium film that the thickness of the 1st layer of Porous semiconductor layer that becomes the 1st layer of Porous photoelectric conversion layer is 10 μ m left and right.
Then, by commercially available titanium oxide microparticle, (Supreme Beingization (Tayca) company manufactures, goods name: safe tower Knicks JA-1 (TITANIX JA-1), particle diameter is about 180nm) 4.0g, and magnesium oxide powder (bank field chemistry limited-liability company manufacture) 0.4g be added in distilled water 20ml, and utilize hydrochloric acid to be adjusted to pH=1.And then, add zirconium oxide bead, utilize the coating oscillator to carry out 8 hours dispersion treatment to this mixing solutions.Thereafter, (bank field chemistry limited-liability company manufactures, weight average molecular weight: 200000), and stirred, obtain thus the suspension that is dispersed with Titanium particles to add 40% polyethylene glycol in the weight ratio with respect to titanium oxide.
On the 1st layer of Porous semiconductor layer of the glass substrate of the oxidation titanium film that is formed with the 1st layer of Porous semiconductor layer, utilize the doctor method to be coated with prepared titanium oxide suspension, and obtain, film.Under 80 ℃ to this film carry out 20 minutes predrying, and then under oxygen atmosphere, with approximately 500 ℃ carry out calcining in 60 minutes, and form the oxidation titanium film 1 that the thickness of the 2nd layer of Porous semiconductor layer that becomes the 2nd layer of Porous photoelectric conversion layer is 22 μ m left and right.Mist degree rate to the Porous semiconductor layer is measured, and result is 84%.
Making the merocyanine represented by following formula is that pigment S-3 in being dissolved in ethanol, is 3 * 10 and make concentration as the pigment that has the sensitivity maximum absorbing wavelength zone in absorption spectrum at short wavelength side (the 1st pigment) -4the absorption pigment solution of the 1st pigment of mol/L.
[changing 51]
Figure BDA00002803131001151
The glass substrate that makes to possess nesa coating and Porous semiconductor layer is heating to the about dipping in pigment solution 10 minutes for absorption of the 1st pigment of 50 ℃, and the 1st pigment is adsorbed on the Porous semiconductor layer., utilize dehydrated alcohol by cleaning glass substrate several times, then approximately carrying out approximately 20 minutes dryings under 60 ℃ thereafter.Then, glass substrate is flooded approximately 10 minutes in 0.5N-hydrochloric acid, utilize thereafter ethanol to be cleaned, and the 1st pigment that makes to be adsorbed on the 2nd layer of Porous semiconductor layer breaks away from.And then, approximately glass substrate is being carried out to approximately 20 minutes dryings under 60 ℃.
Then, making described relatively pigment S-1 or metal complex dye A-12b of the present invention in being dissolved in ethanol, is 3 * 10 and make concentration as the pigment that has the sensitivity maximum absorbing wavelength zone in absorption spectrum at long wavelength side (the 2nd pigment) -4the absorption pigment solution of the 2nd pigment of mol/L.
Under room temperature, normal pressure, the glass substrate that possesses nesa coating and Porous semiconductor layer is flooded 15 minutes in pigment solution is used in the absorption of the 2nd pigment, and the 2nd pigment is adsorbed on the Porous semiconductor layer., utilize dehydrated alcohol by cleaning glass substrate several times, then approximately carrying out approximately 20 minutes dryings under 60 ℃ thereafter., the mist degree rate of Porous semiconductor layer is measured, result is 84% (using the relatively situation of pigment S-1), 85% (using the situation of metal complex dye A-12b of the present invention) herein.
Then, so that the concentration of iodate dimethyl propyl imidazoles becomes 0.5mol/L, make the concentration of lithium iodide become 0.1mol/L, make the concentration of iodine become the mode of 0.05mol/L, they are dissolved in 3-methoxypropionitrile solvent, and make oxidation-reduction quality electrolytic solution.With the Porous semiconductor layer side of glass substrate, arranged with the mode of platinum side subtend to electrode side supporter, prepared oxidation-reduction quality electrolytic solution is injected between the two, and utilize epoxy be resin the sealing material will around the sealing, and complete the coloring matter sensitization type photoelectrochemical cell, described glass substrate possesses the Porous semiconductor layer that makes the absorption of the 1st pigment and the 2nd pigment, described electrode side supporter is comprised and possesses platinum as the ito glass to electrode layer.
In addition, the 2nd layer of Porous semiconductor layer is made as to the layer identical with the 1st Porous semiconductor layer, utilize the titanium oxide suspension that forms the 1st Porous semiconductor layer to form the 2nd layer of Porous semiconductor layer, in addition, similarly make oxidation titanium film 2 with oxidation titanium film 1, use this oxidation titanium film 2 similarly to make photoelectrochemical cell, and measure the mist degree rate.Its result, the mist degree rate of Porous photoelectric conversion layer is 15% (using the relatively situation of pigment S-1), 16% (using the situation of metal complex dye A-12b of the present invention).
Will be at condition determination: AM-1.5 (100mW/cm 2) under obtained photoelectrochemical cell is estimated the results are shown in table 13.
Moreover, by efficiency of conversion, be that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, is evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 13]
Table 13
Specimen coding Oxidation titanium film The 1st pigment The 2nd pigment Efficiency of conversion Remarks
11-1 1 S-3 A-12b ◎ The present invention
11-2 1 S-3 S-1 △ Comparative example
11-3 2 S-3 A-12b ◎ The present invention
11-4 2 S-3 S-1 × Comparative example
As the result according to as shown in table 13 and as clear and definite, the photoelectric transformation efficiency excellence of the photoelectrochemical cell of known use metal complex dye of the present invention.
[testing 14]
Use the hard glass pearl, and make commercially available Titanium particles (Supreme Beingization company manufactures, and median size is 20nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make in 6 hours titanium oxide suspension by the coating oscillator.Then, use doctor, this titanium oxide suspension is coated on the sheet glass (electrode layer) that makes in advance the fin oxide condutire layer adhere to, under 100 ℃, carry out 30 minutes predrying after, carry out calcining in 40 minutes with 500 ℃ in electric furnace, and form oxidation titanium film (semiconductor material) on sheet glass.
In addition, the sensitizing coloring matter shown in table 14 be dissolved in ethanol and obtain light sensitizing coloring matter solution.The concentration of this light sensitizing coloring matter solution is 5 * 10 -4mol/L.
Then, the described sheet glass that will be formed with membranaceous titanium oxide is fed in this solution, carry out the absorption of 60 minutes pigments under 60 ℃ after, in addition dry, forms thus the photoelectric conversion layer that comprises semiconductor material and sensitizing coloring matter on sheet glass.And then coating, as the toluene solution (1%) of the polyvinyl carbazole (weight average molecular weight is 3,000) of hole mobile material, and is carried out drying under reduced pressure and is formed hole transmission layer on photoelectric conversion layer.And then, make to be dissolved in 100mL acetone as ethyl carbazole 1.95g and the 5-nitro naphthoquinones 2.03g of Intermolecular charge transfer complex, obtained solution is coated on hole transmission layer repeatedly and forms conducting stratum.Then, gold evaporation electrode (to electrode) and obtain photo-electric conversion element on conducting stratum.
Utilizing Tai Yang Mo Be device is 100W/m to obtained photo-electric conversion element exposure intensity 2light.Show the result in table 14.
Moreover, by efficiency of conversion, be that 1.5% above person is evaluated as ◎, efficiency of conversion is more than 1.0%, is evaluated as zero less than 1.5%, efficiency of conversion is more than 0.5%, is evaluated as △ less than 1.0%, by efficiency of conversion less than 0.5% being evaluated as *.
[table 14]
Table 14
Specimen coding Sensitizing coloring matter Efficiency of conversion Remarks
12-1 A-2b ◎ The present invention
12-2 A-3c ○ The present invention
12-3 C-12b ◎ The present invention
12-4 S-1 × Comparative example
As the result according to as shown in table 14 and as clear and definite, the efficiency of conversion excellence of the photoelectrochemical cell of known use metal complex dye of the present invention.
[testing 15]
The formation of (1) the 1st photoelectric conversion layer
Use the hard glass pearl, and make commercially available Titanium particles (Supreme Beingization company manufactures, and median size is 30nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make in 6 hours titanium oxide suspension by the coating oscillator.Then, use doctor, this titanium oxide suspension be coated on the sheet glass that is attached with in advance the fin oxide condutire layer, under 100 ℃, carry out 30 minutes predrying after, carry out calcining in 40 minutes with 500 ℃ in electric furnace, and obtain oxidation titanium film.
In addition, [cis-dithio cyanine-N-two (2 to make the pigment represented by following S-4,2 '-bipyridyl-4,4 '-dicarboxylic acid) (cis-dithiocyanine-N-bis (2 for ruthenium, 2 '-bipyridyl-4,4 '-dicarboxylic acid) ruthenium)] be dissolved in ethanol.
[changing 52]
The concentration of this pigment is 3 * 10 -4mole.
Then, the described sheet glass that will be formed with membranaceous titanium oxide is fed in this solution, under 60 ℃, carries out after the absorption of 720 minutes pigments in addition dryly, and forms the 1st photoelectric conversion layer, thereby obtains Sample A.
The formation of (2) the 2nd photoelectric conversion layers
Use granulated glass sphere, and make commercially available nickel oxide particle (bank field chemical company manufactures, and median size is 100nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make in 8 hours nickel oxide suspension by the coating oscillator.Then, use doctor, this nickel oxide suspension be coated on the sheet glass that is attached with in advance the fin oxide condutire layer, under 100 ℃, carry out 30 minutes predrying after, carry out calcining in 30 minutes with 300 ℃ in electric furnace, and obtain nickel oxide film.
In addition, the sensitizing coloring matter shown in table 15 is dissolved in dimethyl sulfoxide (DMSO).The concentration of this pigment is 1 * 10 -4mole.
Then, the described sheet glass that will be formed with membranaceous nickel oxide is fed in this solution, under 70 ℃, carries out after the absorption of 60 minutes pigments in addition dryly, and forms the 2nd photoelectric conversion layer, thereby obtains sample B.
(3) making of photo-electric conversion element
Sample B is positioned on described Sample A.Add liquid electrolyte between described 2 electrodes, utilize resin by after its side seal, conducting wire, and make photo-electric conversion element (element forms C).Moreover the mode that liquid electrolyte makes concentration that tetrapropyl ammonium iodide and iodine be take separately become 0.46mol/L, 0.06mol/L is dissolved in the person of forming in the mixed solvent (volume ratio is 1: 4) of acetonitrile/NSC 11801.
In addition, towards and possess described Sample A as the electrode of a side and carry platinum as between the transparent conductivity sheet glass to electrode, adding liquid electrolyte, utilize resin by after its side seal, conducting wire, and make photo-electric conversion element (element forms D).
Utilizing Tai Yang Mo Be device is 1000W/m to obtained photo-electric conversion element exposure intensity 2light, and measure efficiency of conversion.The results are shown in table 15.
Moreover, by efficiency of conversion, be that 6.5% above person is evaluated as ◎, efficiency of conversion is more than 6.0%, is evaluated as zero less than 6.5%, efficiency of conversion is more than 5.0%, is evaluated as △ less than 6.0%, by efficiency of conversion less than 5.0% being evaluated as *.
[table 15]
Table 15
Specimen coding Element forms The 1st sensitizing coloring matter The 2nd sensitizing coloring matter Efficiency of conversion Remarks
13-1 C S-4 C-1b ◎ The present invention
13-2 C S-4 D-13b ◎ The present invention
13-3 C S-4 S-1 × Comparative example
13-4 D S-4 - × Reference example
As the result according to as shown in table 15 and as clear and definite, the efficiency of conversion excellence of the photoelectrochemical cell of known use metal complex dye of the present invention.And then, known except metal complex dye of the present invention, and use other sensitizing coloring matters, efficiency of conversion further promotes thus.
[testing 16]
Production example to the coloring matter sensitization type photoelectrochemical cell that uses polymer electrolyte describes.
About making the masking liquid of oxidation titanium film, use granulated glass sphere, and by the coating oscillator make commercially available Titanium particles (Supreme Beingization company manufactures, trade(brand)name AMT-600, the Detitanium-ore-type crystallization, median size is 30nm, specific surface area is 50m 2/ g) 4.0g and diethylene glycol monomethyl ether 20mL disperse 7 hours, and make titanium oxide suspension.By SnO 2as nesa coating, be produced on the substrate formed on glass substrate, use doctor, with the thickness of 11 μ m left and right, the area of 10mm * 10mm left and right, this titanium oxide suspension is coated on to the nesa coating side, under 100 ℃, carry out 30 minutes predrying after, carry out calcining in 40 minutes with 460 ℃ under oxygen, its result, making thickness is the oxidation titanium film of 8 μ m left and right.
Then, make the sensitizing coloring matter shown in table 16 with concentration 3 * 10 -4mol/L is dissolved in dehydrated alcohol and makes the absorption pigment solution.With pigment solution and possess in this way the oxidation titanium film obtained and be fed in container respectively with the transparency carrier of nesa coating, and this absorption is permeated approximately 4 hours with pigment solution this absorption, make thus pigment adsorb., utilize dehydrated alcohol clean several times, and approximately carrying out approximately 20 minutes dryings under 60 ℃ thereafter.
Then, using among the monomeric unit represented by following general formula (105), is methyl, the A monomer that is 8 polyethylene oxide bases and 2 poly(propylene oxide) bases as centronucleus the monomeric unit that comprises butane four bases using R, makes monomer solution.
[changing 53]
General formula (105)
Figure BDA00002803131001201
(in formula, R means hydrogen atom or methyl, and A is for carrying out the residue of bond by carbon atom and ester group, and n means 2～4 integer)
Make this monomeric unit with the concentration of 20wt% be dissolved in propylene carbonate (below, be recited as PC (Propylene Carbonate)) in, in addition, make to dissolve make monomer solution with respect to monomeric unit with the concentration of 1wt% as the azobis isobutyronitrile (Azobisisobutyronitrile, AIBN) of thermopolymerization initiator.According to program shown below, make this monomer solution containing being immersed in described oxidation titanium film.
The containers such as beaker are set in vacuum vessel, and the oxidation titanium film A that will possess on the transparency carrier of nesa coating packs wherein into, then utilize rotor pump to carry out approximately within 10 minutes, vacuumizing.
One side is injected into monomer solution in beaker remaining vacuum state one side in vacuum vessel, makes this monomer solution impregnation approximately 15 minutes and monomer solution is infiltrated to titanium oxide fully.Polyethylene dividing plate processed, PET film and pressing plate are set and utilize fixture to fix., approximately 85 ℃ under carrying out 30 minute heating, carrying out thermopolymerization thus and make macromolecular compound thereafter.
Then, make containing being immersed in the oxidation-reduction quality electrolytic solution in macromolecular compound.Oxidation-reduction quality electrolytic solution is using PC as solvent, makes the iodine that lithium iodide that concentration is 0.5mol/L and concentration are 0.05mol/L dissolve to make.The macromolecular compound that is made into described oxidation titanium film is flooded approximately 2 hours in this solution, make thus oxidation-reduction quality electrolytic solution infiltrate to macromolecular compound and make polymer electrolyte.
, the conductive board that possess platinum film be set, utilize the sealing agent of epoxy system that sealing is on every side made to element A thereafter.
In addition, after oxidation titanium film is carried out to pigment absorption, do not carry out the monomer processing, directly towards and to injecting redox electrolytes liquid between electrode and being sealed, and make element B, described redox electrolytes liquid is using PC as solvent, makes the iodine that lithium iodide that concentration is 0.5mol/L and concentration are 0.05mol/L dissolve made redox electrolytes liquid.
Use element A, element B, utilizing Tai Yang Mo Be device exposure intensity is 1000W/m 2light, and measure efficiency of conversion.Show the result in table 16.
Moreover, by efficiency of conversion, be that 3.5% above person is evaluated as ◎, efficiency of conversion is more than 2.5%, is evaluated as zero less than 3.5%, efficiency of conversion is more than 2.0%, is evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as *.
[table 16]
Table 16
Specimen coding Element Sensitizing coloring matter Efficiency of conversion Remarks
14-1 A D-2b ◎ The present invention
14-2 B D-2b ◎ The present invention
14-3 A S-1 × Comparative example
14-4 B S-1 △ Comparative example
As the result according to as shown in table 16 and as clear and definite, the efficiency of conversion excellence of the photo-electric conversion element of known use metal complex dye of the present invention.
[testing 17]
(making of photo-electric conversion element)
Photo-electric conversion element shown in construction drawing 1 10 as follows.
The mode identical with example 1 of usining make be formed with the insulativity porous insert be subject to optoelectronic pole, and as the carbon dioxide process carbon electrode to electrode.
Then, make in the ethanolic soln of the sensitizing coloring matter (mixing multiple or independent) that the described glass substrate that is formed with the insulativity porous insert puts down in writing in following table 17 dipping 5 hours.The glass that is stained with sensitizing coloring matter is flooded after 30 minutes in 10% ethanolic soln of 4-tert .-butylpyridine, utilize ethanol to be cleaned and make its seasoning.The thickness of the photoreceptor layers obtained in this way is 10 μ m, and the glue spread of semiconductor microactuator particle is 20g/m 2.Electrolytic solution is used the methoxypropionitrile solution of iodate dimethyl propyl imidazoles (0.5mol/L), iodine (0.1mol/L).
(mensuration of efficiency of conversion)
Similarly measure the efficiency of conversion of the photoelectrochemical cell obtained with experiment 1.The results are shown in table 17.
Moreover, by efficiency of conversion, be that 7.5% above person is evaluated as ◎, efficiency of conversion is more than 7.3%, is evaluated as zero less than 7.5%, efficiency of conversion is more than 7.1%, is evaluated as △ less than 7.3%, by efficiency of conversion less than 7.1% being evaluated as *.
[table 17]
Table 17
Figure BDA00002803131001221
Below mean the structure of sensitizing coloring matter S-5, sensitizing coloring matter S-6.
[changing 54]
Figure BDA00002803131001231
[changing 55]
Figure BDA00002803131001232
As the result according to as shown in table 17 and as clear and definite, the efficiency of conversion excellence of the photoelectrochemical cell of known use metal complex dye of the present invention.And then, known except metal complex dye of the present invention, and use other sensitizing coloring matters, efficiency of conversion further promotes thus.
[testing 18]
1. the making of electrode 1A
The sensitizing coloring matter be adsorbed on the titanium oxide microparticle sublayer is become to the sensitizing coloring matter shown in table 18, in addition, in the mode identical with experiment 10, make electrode 1A.
2. the making of dye-sensitized solar cell
To comprise the platinum evaporation glass stack of electrode 1A (20mm * 20mm) with the formed objects of the titanium oxide microparticle sublayer that makes in this way sensitizing coloring matter absorption.Then, utilize capillary phenomenon, the following electrolyte ingredient thing that contains heterocycle level Four salt compound 98 quality % and iodine 2 quality % is infiltrated in the gap of two glass, and ionogen is directed in Titanium oxide electrode.Thus, as shown in Figure 1, the electroconductibility supporter 1 that lamination comprises conductive glass successively (on the transparency carrier of glass, be provided with the conductive layer person), photoreceptor layers 2, charge transfer body layer 3, the transparency carrier to electrode 4 and glass (not shown) that comprises platinum, and make by the dye-sensitized solar cell that roughly is dispersed with equably the sealing agent sealing that glass spheres that diameter is 25 μ m forms in the resin combination comprising according to a Ke Tai 828 (Epikote828) (trade(brand)name, japan epoxy resin (Japan Epoxy Resins) company manufacture), stiffening agent and plastics slurry.But, when the viscosity of electrolyte ingredient thing high and while being difficult to utilize capillary phenomenon to make the infiltration of electrolyte ingredient thing, the electrolyte ingredient thing is heated to 50 ℃, after on its coating Titanium oxide electrode, this electrode is placed under decompression, the electrolyte ingredient thing fully permeate and electrode in air spill after, stack platinum evaporation glass (to electrode) and similarly make dye-sensitized solar cell.
[changing 56]
Figure BDA00002803131001241
3. the mensuration of photoelectric transformation efficiency
Make the light of the xenon lamp (oxtail motor (share) manufacture) of 500W pass AM1.5 spectral filter (manufacture of Ao Lier (Oriel) company) and sharp wave spectral filter (trade(brand)name: Ken Keer-37 (KenkoL-37)), produce thus containing ultraviolet simulated solar irradiation.This light intensity is 70mW/cm 2.Under 50 ℃, the dye-sensitized solar cell 16-1 that makes in this way～dye-sensitized solar cell 16-10 is irradiated this simulated solar irradiation, and utilizes current/voltage determinator (Keithley SMU238 type) to measure the electricity produced.In addition, also be determined at the rate of descent that is kept at the efficiency of conversion of dark place after 1000 hours under 85 ℃, and the Continuous irradiation light of 500 hours after the rate of descent of efficiency of conversion.By their table 18 that the results are shown in.
[table 18]
Table 18
Figure BDA00002803131001242
Figure BDA00002803131001251
According to table 18, compare with dye-sensitized solar cell 16-8～dye-sensitized solar cell 16-9, use the initial value of the efficiency of conversion of the dye-sensitized solar cell 16-1 of metal complex dye made of the present invention～dye-sensitized solar cell 16-7 all to show high value.And then known and dye-sensitized solar cell 16-8～dye-sensitized solar cell 16-10 compares, be kept at behind dark place and Continuous irradiation light after the rate of descent of efficiency of conversion low, excellent in te pins of durability.
The present invention and its example together are illustrated, but as long as the contriver does not specify, do not want contriver's invention is limited in any details of explanation, and think the spirit of the invention shown in the scope that should not violate the claim of enclosing and scope and make an explanation widely.
The present invention advocates to have carried out in Japan based on August 3rd, 2010 right of priority of the Japanese Patent Patent 2010-174315 of patent application, herein in addition with reference to and quote its content as a part of putting down in writing in this specification sheets.
[explanation of symbol]
1: the electroconductibility supporter
2: photoreceptor layers
21: pigment
22: the semiconductor microactuator particle
3: charge transfer body layer
4: to electrode
5: be subject to optoelectronic pole
6: circuit
10: photo-electric conversion element
100: photoelectrochemical cell

Claims (15)

1. a metal complex dye is characterized in that: by following general formula (1), meaned,
[changing 1]
General formula (1)
(in general formula (1), R 11～R 14mean substituting group, wherein at least 1 means acidic groups; A11～a14 means the positive integer more than 1; M means metal, metal oxide or metal chloride; A～D means aromatic nucleus; Among the aromatic nucleus of described A～D, aromatic nucleus with acidic groups means phenylbenzene phenyl ring, naphthalene nucleus, phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, pentacene ring, thiazolyl phenyl ring, imidazolyl phenyl ring, 1,3,4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, benzothiazole ring, the assorted aromatic nucleus of the not enough system of π-electron or bond have phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of the not enough system of π-electron).
2. metal complex dye according to claim 1, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the aromatic nucleus with acidic groups is phenyl ring or the naphthalene nucleus that the assorted aromatic nucleus of the not enough system of π-electron or bond have the assorted aromatic nucleus of the not enough system of π-electron.
3. metal complex dye according to claim 1 and 2, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the quantity with aromatic nucleus of acidic groups is 1 or 2.
4. according to the described metal complex dye of any one in claims 1 to 3, it is characterized in that: in general formula (1), among the aromatic nucleus of described A～D, the aromatic nucleus that does not have acidic groups is independently respectively phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, thiphene ring or thionaphthene ring.
5. according to the described metal complex dye of any one in claim 1 to 4, it is characterized in that: in general formula (1), described acidic groups is carboxyl.
6. according to the described metal complex dye of any one in claim 1 to 5, it is characterized in that: in general formula (1), beyond described acidic groups by R 11～R 14represented substituting group is independent respectively is alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, alkyl silyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio or aryl silyl, heteroaryl silyl.
7. according to the described metal complex dye of any one in claim 1 to 6, it is characterized in that: in general formula (1), a11～a14 is independently respectively 1～4 integer.
8. according to the described metal complex dye of any one in claim 1 to 7, it is characterized in that: in general formula (1), M is copper, zinc, tin, nickel, iron, cobalt, silicon, palladium, chloro-aluminium, magnesium, gallium, titanyl oxygen or vanadium oxygen oxygen.
9. according to the described metal complex dye of any one in claim 1 to 8, it is characterized in that: by general formula (1), represented metal complex dye is by following general formula (8) or the represented metal complex dye of general formula (9),
[changing 2]
Figure FDA00002803130900021
General formula (8) general formula (9)
(in general formula (8) and general formula (9), A～D means aromatic nucleus; A 1and A 2mean independently respectively acidic groups; D 1～D 3mean independently respectively alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, alkyl silyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio or aryl silyl, heteroaryl silyl; A21～a22 means the integer more than 1; D21～d23 means the positive integer more than 1; M means metal, metal oxide or metal chloride).
10. a pigment for use with photoelectric conversion element, is characterized in that: comprise according to the described metal complex dye of any one in claim 1 to 9.
11. a photo-electric conversion element is characterized in that: comprise photoreceptor layers, this photoreceptor layers has according to the described metal complex dye of any one in claim 1 to 9 and semiconductor microactuator particle.
12. photo-electric conversion element according to claim 11 is characterized in that: described photoreceptor layers and then contain by the represented metal complex dye of following general formula (2),
Mz (LL 1) m1(LL 2) m2(X) m3cI general formula (2)
[in general formula (2), Mz means atoms metal, LL 1two teeth that expression is represented by following general formula (3) or the dentate of three teeth, LL 2two teeth that expression is represented by following general formula (4) or the dentate of three teeth, X means by selecting free acyloxy, the acyl sulfenyl, the sulfo-acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, the thiocarbamate base, dithiocarbamate groups, the thiocarbonic acid SOH ester group, the dithiocarbonic acid ester group, the trithiocarbonic acid ester group, acyl group, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form carrys out the dentate of single tooth or two teeth of coordination, or select free halogen atom, carbonyl, dialkyl ketone, 1, the 3-diketone, benzamide, single tooth in the cohort that thiobenzamide and thiocarbamide form or the dentate of two teeth, m1 means 0～3 integer, when m1 is 2 when above, and LL 1can be identical, also can be different, m2 means 1～3 integer, when m2 is 2 when above, and LL 2can be identical, also can be different, m3 means 0～3 integer, and when m3 is 2 when above, X can be identical, also can be different, and X also can be linked each other, CI is illustrated in general formula (2), in and electric charge and counter ion while needing counter ion,
[changing 3]
Figure FDA00002803130900031
general formula (3)
In general formula (3), R 21and R 22mean independently respectively acidic groups; R 23and R 24mean independently respectively substituting group, R 25and R 26mean independently respectively alkyl, aryl or heterocyclic radical; D1 and d2 mean respectively 0～5 integer; L 1and L 2mean independently respectively to comprise the conjugated chain of at least 1 in the cohort that the heterocyclic radical that selects free vinylidene, ethynylene and divalence forms; A1 and a2 mean respectively 0～3 integer independently, and when a1 is 2 when above, R21 can be identical, also can be different, and when a2 is 2 when above, R 22can be identical, also can be different; B1 and b2 mean respectively 0～3 integer independently, when b1 is 2 when above, and R 23can be identical, also can be different, and R 23can mutually link and form ring; When b2 is 2 when above, R 24can be identical, also can be different, and R 24can mutually link and form ring; When b1 and b2 are 1 when above, R 23with R 24can link and form ring; D3 means 0 or 1;
[changing 4]
Figure FDA00002803130900041
general formula (4)
In general formula (4), Za, Zb and Zc mean to form respectively the non-metallic atom group of 5 Yuans rings or 6 Yuans rings independently, and c means 0 or 1; Wherein, at least 1 in the formed ring of Za, Zb and Zc has acidic groups].
13., according to the described photo-electric conversion element of claim 11 or 12, it is characterized in that: have by described photoreceptor layers, charge transfer body and to electrode with this sequential lamination the structure on the electroconductibility supporter.
14., according to claim 11 to the described photo-electric conversion element of any one in 13, it is characterized in that: described metal complex dye is adsorbed on described semiconductor microactuator particle.
15. a photoelectrochemical cell is characterized in that: comprise according to claim 11 to the described photo-electric conversion element of any one in 14.
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