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CN103124774B - Metal complex dye, photo-electric conversion element and photoelectrochemical cell - Google Patents

Metal complex dye, photo-electric conversion element and photoelectrochemical cell Download PDF

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Publication number
CN103124774B
CN103124774B CN201180037813.2A CN201180037813A CN103124774B CN 103124774 B CN103124774 B CN 103124774B CN 201180037813 A CN201180037813 A CN 201180037813A CN 103124774 B CN103124774 B CN 103124774B
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Prior art keywords
ring
general formula
pigment
metal complex
slurry
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CN201180037813.2A
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CN103124774A (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

The present invention relates to a kind of metal complex dye, photo-electric conversion element and photoelectrochemical cell, metal complex dye is represented by following general formula (1). general formula (1) (in general formula (1), R 11~ R 14represent substituting group, wherein at least 1 represents acidic groups.A11 ~ a14 represents the positive integer of more than 1.M represents metal, metal oxide or metal chloride.A ~ D represents aromatic nucleus.Among the aromatic nucleus of described A ~ D, the aromatic nucleus with acidic groups represents phenylbenzene phenyl ring, naphthalene nucleus, phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, pentacene ring, thiazolyl phenyl ring, imidazolyl phenyl ring, 1, the assorted aromatic nucleus of 3,4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, benzothiazole ring, π-electron deficiency system or bond have phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of π-electron deficiency system.)。

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 used for various optical sensor, duplicating machine, solar cell etc.In this photo-electric conversion element, use the photo-electric conversion element of metal, use the photo-electric conversion element of semi-conductor, the various mode such as the photo-electric conversion element using pigment dyestuff or pigment or the photo-electric conversion element that they combined is practical.Wherein, utilize the solar cell of the sun power of non-exhaustion as not needing fuel, and utilize inexhaustible clean energy person, its real practical making us extremely is expected.Wherein, from the research and development having carried out silicon system solar cell since previously always.The treatment of the policy of Ye You various countries and popularizing.But silicon is inorganic materials, in turnout and molecular modification, naturally there is the limit.
Therefore, the research of dye-sensitized solar cell is carried out just energetically.Especially, the lattice Rachel (Graetzel) etc. of the Lausanne Polytechnics of Switzerland is developed and will be comprised the dye-sensitized solar cell of chromatopexis on the surface of porous titania thin films of ruthenium complex, and achieves the efficiency of conversion identical with non-crystalline silicon.Thus, dye-sensitized solar cell is subject to attracting attention of the investigator in the world quickly.
In patent documentation 1, record a kind of this technology of application, use the dye-sensitized photo-electric conversion element being obtained the semiconductor microactuator particle of sensitizing by ruthenium complex pigment.But when ruthenium complex pigment is used alone as sensitizing agent, price is high, and there is the problems such as supply is troubling in ruthenium.
The metal complex dye of a kind of porphyrin or tetraazatetradecane porphyrin (porphyrazine) skeleton is recorded 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.
The metal complex dye that a kind of aromatic nucleus with carboxyl is the porphyrin skeleton of pyrazine ring or quinoxaline ring is recorded in patent documentation 3.But Soret spy's band (Soret band) absorption of porphyrin skeleton pigment is originally in visibility region, and therefore pass through Soret spy band long wavelengthization, the effect for its performance boost is also little.
And then, photo-electric conversion element must initial efficiency of conversion high, after life-time service, the decline of efficiency of conversion is less and excellent in te pins of durability.But in weather resistance this point, the photo-electric conversion element recorded in patent documentation 2 and patent documentation 3 does not claim fully.
Prior art document
Patent documentation
Patent documentation 1: United States Patent (USP) No. 5463057 specification sheets
Patent documentation 2: Japanese Patent Laid-Open 2000-357543 publication
Patent documentation 3: Japanese Patent Laid-Open 2009-132657 publication
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 light absorption 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 the photo-electric conversion element and the photoelectrochemical cell that provide a kind of efficiency of conversion and excellent in te pins of durability.
Solve the technique means of problem
The present inventor etc. have carried out in view of described problem making great efforts research.Its result, finds to possess by the metal complex dye of phthalocyanine frame the aromatic nucleus that at least 1 has acidic groups, and be in the Soret spy band long wavelengthization in ultraviolet region, the light absorption wave band can carrying out opto-electronic conversion expands.And then the volume ratio of the aromatic nucleus finding to have acidic groups and the aromatic nucleus without acidic groups is comparatively large, uses the photo-electric conversion element of this metal complex dye and the weather resistance of photoelectrochemical cell to promote thus.The present invention is the invention finding according to these and complete.
In phthalocyanine compound, if with lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) be positioned at any one mode with the aromatic nucleus position of acidic groups and carry out molecular designing, then electron injection efficiency promotes, and efficiency of conversion uprises.Infer in the phthalocyanine compound of so design, by making the prolongation of the conjugation at the aromatic nucleus position with LUMO or aromatic nucleus position have electrophilic heterocycle, the energy level of LUMO declines, and light absorption wave band expands.
According to the present invention, provide following means.
<1> metal complex dye, is characterized in that: represented by following general formula (1).
[changing 1]
(in general formula (1), R 11~ R 14represent substituting group, wherein at least 1 represents acidic groups.A11 ~ a14 represents the positive integer of more than 1.M represents metal, metal oxide or metal chloride.A ~ D represents aromatic nucleus.Among the aromatic nucleus of described A ~ D, the aromatic nucleus with acidic groups represents phenylbenzene phenyl ring, naphthalene nucleus, phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, pentacene ring, thiazolyl phenyl ring, imidazolyl phenyl ring, 1, the assorted aromatic nucleus of 3,4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, benzothiazole ring, π-electron deficiency system or bond have phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of π-electron deficiency system)
The metal complex dye of <2> according to described <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 π-electron deficiency system or bond have the assorted aromatic nucleus of π-electron deficiency system.
The metal complex dye of <3> according to described <1> or <2>, it is characterized in that: in general formula (1), among the aromatic nucleus of described A ~ D, the quantity with the aromatic nucleus of acidic groups is 1 or 2.
The metal complex dye of <4> according to any one of described <1> to <3>, it is characterized in that: in general formula (1), among the aromatic nucleus of described A ~ D, the aromatic nucleus without acidic groups is independently phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, thiphene ring or thionaphthene ring.
The metal complex dye of <5> according to any one of described <1> to <4>, it is characterized in that: in general formula (1), described acidic groups is carboxyl.
The metal complex dye of <6> according to any one of described <1> to <5>, it is characterized in that: in general formula (1), beyond described acidic groups by R 11~ R 14represented substituting group is independently alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, aIkylsilyl groups, aryloxy, heteroaryloxy, arylthio, heteroarylthio or arylsilyl groups, heteroaryl silyl.
The metal complex dye of <7> according to any one of described <1> to <6>, it is characterized in that: in general formula (1), a11 ~ a14 is independently the integer of 1 ~ 4.
The metal complex dye of <8> according to any one of described <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.
The metal complex dye of <9> according to any one of described <1> to <8>, is characterized in that: the metal complex dye represented by general formula (1) is the metal complex dye represented by following general formula (8) or general formula (9).
[changing 2]
(in general formula (8) and general formula (9), A ~ D represents aromatic nucleus.A 1and A 2separately represent acidic groups.D 1~ D 3separately represent alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, aIkylsilyl groups, aryloxy, heteroaryloxy, arylthio, heteroarylthio or arylsilyl groups, heteroaryl silyl.A21 ~ a22 represents the integer of more than 1.D21 ~ d23 represents the positive integer of more than 1.M represents metal, metal oxide or metal chloride)
<10> pigment for use with photoelectric conversion element, is characterized in that: comprise the metal complex dye according to any one of described <1> to <9>.
<11> photo-electric conversion element, it is characterized in that: comprise photoreceptor layers, this photoreceptor layers has metal complex dye according to any one of described <1> to <9> and semiconductor microactuator particle.
The photo-electric conversion element of <12> according to described <11>, is characterized in that: described photoreceptor layers and then the metal complex dye contained represented by following general formula (2).
Mz (LL 1) m1(LL 2) m2(X) m3cI general formula (2)
[in general formula (2), Mz represents atoms metal, LL 1two teeth of expression represented by following general formula (3) or the dentate of three teeth, LL 2two teeth of expression represented by following general formula (4) or the dentate of three teeth.X represents by being selected from by 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, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form comes single tooth of coordination or the dentate of two teeth, or be selected from by halogen atom, carbonyl, dialkyl ketone, 1, 3-diketone, benzamide, single tooth in the cohort that thiobenzamide and thiocarbamide form or the dentate of two teeth.M1 represents the integer of 0 ~ 3, when m1 is more than 2, and LL 1can be identical, also can be different.M2 represents the integer of 1 ~ 3, when m2 is more than 2, and LL 2can be identical, also can be different.M3 represents the integer of 0 ~ 3, and when m3 is more than 2, X can be identical, also can be different, and X also can link each other.CI represents in general formula (2), in order in and electric charge and need counter ion time counter ion.
[changing 3]
In general formula (3), R 21and R 22separately represent acidic groups.R 23and R 24separately represent substituting group, R 25and R 26separately represent alkyl, aryl or heterocyclic radical.D1 and d2 represents the integer of 0 ~ 5 respectively.L 1and L 2separately represent the conjugated chain of at least 1 comprised in the cohort being selected from and being made up of the heterocyclic radical of vinylidene, ethynylene and divalence.A1 and a2 separately represents the integer of 0 ~ 3, when a1 is more than 2, and R 21can be identical, also can be different, when a2 is more than 2, R 22can be identical, also can be different.B1 and b2 separately represents the integer of 0 ~ 3, when b1 is more than 2, and R 23can be identical, also can be different, and R 23can be interconnected and form ring.When b2 is more than 2, R 24can be identical, also can be different, and R 24can be interconnected and form ring.When b1 and b2 is more than 1, R 23with R 24can link and form ring.D3 represents 0 or 1.
[changing 4]
In general formula (4), Za, Zb and Zc separately represent the non-metallic atom group that can form 5 Yuans rings or 6 Yuans rings, and c represents 0 or 1.Wherein, at least 1 in the ring that formed of Za, Zb and Zc has acidic groups]
The photo-electric conversion element of <13> according to described <11> or <12>, is characterized in that: have by described photoreceptor layers, Charger transfer body and to electrode with the structure of this sequential lamination in conductive support body.
The photo-electric conversion element of <14> according to any one of described <11> to <13>, is characterized in that: described metal complex dye is adsorbed on described semiconductor microactuator particle.
<15> photoelectrochemical cell, is characterized in that: comprise the photo-electric conversion element according to any one of described <11> to <14>.
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.
Accompanying drawing explanation
Fig. 1 is the sectional view of the preferred example schematically showing photo-electric conversion element of the present invention.
[explanation of symbol]
1: conductive support body
2: photoreceptor layers
21: pigment
22: semiconductor microactuator particle
3: Charger transfer body layer
4: to electrode
5: by optoelectronic pole
6: circuit
10: photo-electric conversion element
100: photoelectrochemical cell
Embodiment
Be described with reference to the graphic preferred example to photo-electric conversion element of the present invention.
As shown in Figure 1, photo-electric conversion element 10 comprises conductive support body 1, and the photoreceptor layers 2 sequentially configured in conductive support body 1, Charger transfer body layer 3 and to electrode 4.Be made up of by optoelectronic pole 5 with photoreceptor layers 2 described conductive support body 1.This photoreceptor layers 2 has semiconductor microactuator particle 22 and sensitizing coloring matter 21, pigment 21 be adsorbed on (pigment also can become adsorption equilibrium state, and a part is present on Charger transfer body layer) on semiconductor microactuator particle 22 at least partially.The conductive support body 1 being formed with photoreceptor layers 2 plays function as active electrode in photo-electric conversion element 10.Make this photo-electric conversion element 10 can be used for the battery use worked by external circuit 6, thus can be used as photoelectrochemical cell 100 and operate.
The electrodes being adsorbed with the photoreceptor layers (semiconductor layer) 2 of the semiconductor microactuator particle 22 of pigment 21 comprising conductive support body 1 and be configured in conductive support body 1 by optoelectronic pole 5.The light be incident upon in photoreceptor layers 2 excites pigment.Pigment is excited to have the high electronics of energy.Therefore, this electronics is sent to the conduction band of semiconductor microactuator particle 22 from pigment 21, and then arrives conductive support body 1 by spreading.Now, the molecule of pigment 21 becomes oxysome.Electronics one side on electrode is carried out work one side by external circuit 6 and is reverted to pigment oxidation body, plays a role thus as photoelectrochemical cell.Now, work is carried out by optoelectronic pole 5 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, then will become the direction side of electrode 4 being set to top (top) of sensitive side, the side of conductive support body 1 will be set to the direction of bottom (bottom).
Photo-electric conversion element of the present invention has photoreceptor layers in conductive support body, and this photoreceptor has the Porous semiconductor microactuator particle layer being adsorbed with pigment described later.Photoreceptor layers designs according to object, can be that individual layer is formed, and also can be that multilayer is formed.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 being used as photoelectrochemical cell, can obtain high conversion efficiency.
Below, the metal complex dye represented by following general formula (1) used in photo-electric conversion element of the present invention is described.
[changing 5]
In general formula (1), R 11~ R 14represent substituting group, wherein at least 1 represents acidic groups.A11 ~ a14 represents the positive integer of more than 1.M represents metal, metal oxide or metal chloride.A ~ D represents aromatic nucleus.Herein, so-called " M represents metal chloride ", refer to that chloride ion coordination is on central metal.In addition, so-called acidic groups, except the acidic groups such as carboxyl itself, also can be carry out the replacement person of forming via concatenating group in the scope obtaining desired effect, comprise this concatenating group and be called acidic groups.
In general formula (1), A ~ D represents aromatic nucleus.Described aromatic nucleus can be aromatic hydrocarbons ring, also can be heteroaromatic.
As the aromatic hydrocarbons ring of A, B, C and D of general formula (1), preferred carbon number is the monocycle of 6 ~ 30 or the aromatic hydrocarbons ring of two rings, more preferably carbon number is the monocycle of 6 ~ 20 or the aromatic hydrocarbons ring of two rings, and then more preferably carbon number is the monocycle of 6 ~ 12 or the aromatic hydrocarbons ring of two rings.As the concrete example of 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, phenanthrene ring, tetracene ring, Qu Huan, 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 D of general formula (1), particularly preferably phenyl ring and naphthalene nucleus.Described aromatic hydrocarbons ring can have substituting group, alternatively base, can enumerate substituting group T described later.
As heterocycle structure, preferably contain Sauerstoffatom, nitrogen-atoms, sulphur atom and/or selenium atom as heteroatomic heteroaromatic.As the concrete example of heteroaromatic, can enumerate: furan nucleus, pyrrole ring, thiphene ring, imidazole ring, pyrazole ring, triazole ring, triazine ring, indole ring, indazole ring, purine skeleton, thiazoline ring, thiazole ring, Thiadiazole, thionaphthene ring, thienothiophene ring, bithiophene ring, oxazoline ring, oxazole ring, oxadiazoles ring, phthalazines ring, naphthyridines ring, cinnolines ring, to talk endlessly pyridine ring, coffee quinoline ring, tetrazole ring, benzoglyoxaline ring, benzoxazoles ring, benzothiazole ring, benzotriazole ring, four benzazole rings, π-electron deficiency is heteroaromatic, bond has π-electron deficiency to be the phenyl ring or naphthalene nucleus etc. of heteroaromatic.So-called π-electron deficiency is heteroaromatic, refers to containing heteroatoms and there is the complete unsaturated heterocycle at the position of π-electron deficiency, as heteroatoms, and preferred nitrogen atom.Specifically, as its mother nucleus structure, the pyridine containing 1 nitrogen-atoms, quinoline, isoquinoline 99.9, acridine, indolizine, coffee pyridine can be enumerated, pyridazine containing 2 nitrogen-atoms, pyrimidine, pyrazine, quinazoline, quinoxaline, 1,5-naphthyridines, azophenlyene, symmetrical triazine containing 3 nitrogen-atoms, asymmetric triazine, the pterin etc. containing 4 nitrogen-atoms.In the present invention, the preferably heteroaromatic of 5 Yuans rings or 6 Yuans rings, also and then can carry out contracting ring with other rings.As heteroaromatic, more preferably quinoxaline ring, thiphene ring, pyridine ring, pyrazine ring, thiazole ring, thienothiophene ring, benzothiazole ring.
Alternatively base T, include, for example: (preferred carbonatoms is the alkyl of 1 ~ 20 to alkyl, and more preferably carbonatoms is the alkyl of 1 ~ 12, and particularly preferably carbonatoms is the alkyl of 1 ~ 8, include, for example methyl, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, positive hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), (preferred carbonatoms is 2 ~ 20 to thiazolinyl, and more preferably carbonatoms is 2 ~ 12, and particularly preferably carbonatoms is 2 ~ 8, include, for example vinyl, allyl group, crotyl, 3-pentenyl etc.), (preferred carbonatoms is 2 ~ 20 to alkynyl, and more preferably carbonatoms is 2 ~ 12, and particularly preferably carbonatoms is 2 ~ 8, include, for example propargyl, 3-pentynyl etc.), (preferred carbonatoms is 6 ~ 30 to aryl, and more preferably carbonatoms is 6 ~ 20, and particularly preferably carbonatoms is 6 ~ 12, include, for example phenyl, xenyl, naphthyl etc.), (preferred carbonatoms is 0 ~ 20 to the amino being substituted or being unsubstituted, and more preferably carbonatoms is 0 ~ 10, and particularly preferably carbonatoms is 0 ~ 6, include, for example amino, methylamino-, dimethylamino, diethylin, dibenzyl is amino),
(preferred carbonatoms is 1 ~ 20 to alkoxyl group, and more preferably carbonatoms is 1 ~ 12, and particularly preferably carbonatoms is 1 ~ 8, include, for example methoxyl group, oxyethyl group, butoxy etc.), (preferred carbonatoms is 6 ~ 20 to aryloxy, and more preferably carbonatoms is 6 ~ 16, and particularly preferably carbonatoms is 6 ~ 12, include, for example phenoxy group, 2-naphthyloxy etc.), (preferred carbonatoms is 1 ~ 20 to acyl group, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example ethanoyl, benzoyl, formyl radical, pivaloyl etc.), (preferred carbonatoms is 2 ~ 20 to alkoxy carbonyl, and more preferably carbonatoms is 2 ~ 16, and particularly preferably carbonatoms is 2 ~ 12, include, for example methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferred carbonatoms is 7 ~ 20, and more preferably carbonatoms is 7 ~ 16, and particularly preferably carbonatoms is 7 ~ 10, include, for example phenyloxycarbonyl etc.), (preferred carbonatoms is 2 ~ 20 to acyloxy, and more preferably carbonatoms is 2 ~ 16, and particularly preferably carbonatoms is 2 ~ 10, include, for example acetoxyl group, benzoyloxy etc.),
(preferred carbonatoms is 2 ~ 20 to acyl amino, and more preferably carbonatoms is 2 ~ 16, and particularly preferably carbonatoms is 2 ~ 10, include, for example acetylamino, benzoyl-amido etc.), alkoxycarbonyl amino (preferred carbonatoms is 2 ~ 20, and more preferably carbonatoms is 2 ~ 16, and particularly preferably carbonatoms is 2 ~ 12, include, for example methyloxycarbonylamino etc.), aryloxycarbonylamino (preferred carbonatoms is 7 ~ 20, and more preferably carbonatoms is 7 ~ 16, and particularly preferably carbonatoms is 7 ~ 12, include, for example phenoxycarbonylamino etc.), (preferred carbonatoms is 1 ~ 20 to sulfuryl amino, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example methane sulfonylamino, BENZENESUFONYLAMINO etc.), (preferred carbonatoms is 0 ~ 20 to sulfamyl, and more preferably carbonatoms is 0 ~ 16, and particularly preferably carbonatoms is 0 ~ 12, include, for example sulfamyl, Methylsulfamoyl, DimethylsuIfamoyl, phenyl sulfamoyl base etc.), (preferred carbonatoms is 1 ~ 20 to carbamyl, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example carbamyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl etc.),
(preferred carbonatoms is 1 ~ 20 to alkylthio, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example methylthio group, ethylmercapto group etc.), arylthio (preferred carbonatoms is 6 ~ 20, and more preferably carbonatoms is 6 ~ 16, and particularly preferably carbonatoms is 6 ~ 12, include, for example thiophenyl etc.), (preferred carbonatoms is 1 ~ 20 to alkylsulfonyl, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example methylsulfonyl, tosyl group etc.), (preferred carbonatoms is 1 ~ 20 to sulfinyl, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example methanesulfinyl, benzenesulfinyl etc.), (preferred carbonatoms is 1 ~ 20 to urea groups, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example urea groups, methyl urea groups, phenyl urea groups etc.), (preferred carbonatoms is 1 ~ 20 to phosphinylidyne amido, and more preferably carbonatoms is 1 ~ 16, and particularly preferably carbonatoms is 1 ~ 12, include, for example diethylphosphoryl amido, diphenylphosphoryl amido etc.), hydroxyl, sulfydryl, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), cyano group, sulfo group, carboxyl, nitro, hydroximic acid base, sulfino, diazanyl, imino-, (preferred carbonatoms is 1 ~ 30 to heterocyclic radical, and more preferably carbonatoms is 1 ~ 12, as heteroatoms, include, for example nitrogen-atoms, Sauerstoffatom, sulphur atom, specifically, include, for example imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl-, benzothiazolyl etc.), (preferred carbonatoms is 3 ~ 40 to silyl, and more preferably carbonatoms is 3 ~ 30, and particularly preferably carbonatoms is 3 ~ 24, include, for example trimethyl silyl, triphenyl-silyl etc.) etc.
Among described substituting group, hydrogen atom also can be removed and be replaced further by described base by the substituting group with hydrogen atom.As the example of this kind of functional group, can enumerate: alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkylsulfonyl aminocarbonyl, aryl sulfonyl amino carbonyl.As its example, can enumerate: Methylsulfonylamino carbonyl, p-methylphenyl sulfonyl amino carbonyl, acetylamino alkylsulfonyl, benzoylaminosulfonyl group.
In addition, when having plural substituting group, can be identical, also can be different.In addition, in the conceived case also can be interconnected and form ring.
In general formula (1), among aromatic nucleus represented by A ~ D, the aromatic nucleus with acidic groups is 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, assorted aromatic nucleus (the preferred pyridine ring of π-electron deficiency system, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, pyrazole ring, imidazole ring), bond has assorted aromatic nucleus (the preferred pyridine ring of π-electron deficiency system, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, pyrazole ring, imidazole ring) phenyl ring or naphthalene nucleus, the assorted aromatic nucleus of preferred π-electron deficiency system, bond has phenyl ring or the naphthalene nucleus of the assorted aromatic nucleus of π-electron deficiency system.
In general formula (1), among the aromatic nucleus preferably represented by A ~ D, the quantity with the aromatic nucleus of acidic groups is 1 or 2.
In general formula (1), among the aromatic nucleus preferably represented by A ~ D, the aromatic nucleus without acidic groups is independently 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 (having the substituting group of the proton of dissociative), 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 organic salt, inorganic salt any one.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, Si Wan Ji Phosphonium.In general formula (1), when having multiple 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: (preferred carbon number is the straight chain of 1 ~ 20 to alkyl, branch, the alkyl being substituted or being unsubstituted of ring-type, alternatively base, preferably can enumerate n-hexyl, 2-ethyl hexyl, tertiary octyl group, nonyl etc.), (preferred carbon number is the aryl being substituted or being unsubstituted of 6 ~ 20 to aryl, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the heterocyclic radical being substituted or being unsubstituted of 3 ~ 20 to heterocyclic radical, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the straight chain of 1 ~ 20 to alkoxyl group, branch, the alkoxyl group being substituted or being unsubstituted of ring-type, alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the straight chain of 1 ~ 20 to alkylthio, branch, the alkylthio being substituted or being unsubstituted of ring-type, alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the straight chain of 1 ~ 20 to aIkylsilyl groups, branch, the aIkylsilyl groups being substituted or being unsubstituted of ring-type, alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the aryloxy being substituted or being unsubstituted of 6 ~ 20 to aryloxy, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the heteroaryloxy being substituted or being unsubstituted of 3 ~ 20 to heteroaryloxy, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the arylthio being substituted or being unsubstituted of 6 ~ 20 to arylthio, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the heteroarylthio being substituted or being unsubstituted of 3 ~ 20 to heteroarylthio, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), or arylsilyl groups (preferred carbon number is the arylsilyl groups being substituted or being unsubstituted of 6 ~ 20, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.), (preferred carbon number is the heteroaryl silyl being substituted or being unsubstituted of 3 ~ 20 to heteroaryl silyl, and alternatively base, preferably can enumerate alkyl, alkylamino, alkoxyl group, alkylthio etc.).
In general formula (1), a11 ~ a14 represents the integer of more than 1.A11 ~ a14 preferably represents the integer of 1 ~ 4, more preferably represents 1 or 2.
In general formula (1), M represents 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.
Having in the aromatic nucleus of 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 of metal complex dye represented by general formula (1) preferably represented by following general formula (8) or general formula (9).Among these metal complex dyes, the metal complex dye more preferably represented by general formula (8).
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In general formula (8) and general formula (9), the implication of A, B, C, D and M is identical with A, B, C, D and M of general formula (1), and preferred scope is also identical.
In general formula (8) and general formula (9), A 1and A 2separately represent 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 acidic groups illustrated in acidic groups, preferred scope is also identical.
In general formula (8) and general formula (9), D 1~ D 3separately represent alkyl, aryl, heterocyclic radical, alkoxyl group, alkylthio, aIkylsilyl groups, aryloxy, heteroaryloxy, arylthio, heteroarylthio or arylsilyl groups, heteroaryl silyl.
In general formula (8) and general formula (9), a21 ~ a22 represents the integer of more than 1.A21 ~ a22 preferably represents the integer of 1 ~ 4, more preferably represents 1 or 2.
In general formula (8) and general formula (9), d21 ~ d23 represents the integer of more than 1.D21 ~ d23 preferably represents the integer of 1 ~ 4, more preferably represents 1 ~ 3.
Metal complex dye maximum absorption wavelength in the solution (peak value of Q band) represented by general formula (1) is preferably in the scope of 500nm ~ 1500nm, is more preferably in the scope of 600nm ~ 1200nm.In addition, the peak value of Soret spy band is preferably in the scope of 200nm ~ 600nm, is more preferably in the scope of 300nm ~ 500nm.
And then the light absorption wave band under the wavelength of more than the 400nm of the pigment represented by general formula (1) is preferably in the scope of 400nm ~ 1500nm, is more preferably in the scope of 400nm ~ 1200nm.In addition, the wavelength difference of the peak value that the peak value of Q band and Soret spy are with preferably is in the scope of 100nm ~ 400nm, is more preferably in the scope of 150nm ~ 350nm.
Below, represent the preferred concrete example of the metal complex dye represented by general formula (1), but the present invention is not limited to following concrete example.
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Below, the synthetic method of the metal complex dye represented by general formula (1) of the present invention is described.But the present invention does not limit by these methods.
Metal complex dye represented by general formula (1) of the present invention, as shown in such as following flow process (I), can make Aromatic Dinitriles compound of more than two kinds and/or diimino azole compounds carry out reacting synthesizing with the metal derivative represented by following general formula (5).Or, as shown in following flow process (II), after reacting with the metal derivative represented by general formula (6) by making Aromatic Dinitriles compound of more than two kinds and/or diimino pyrrole derivative, carry out reacting synthesizing with the metal derivative represented by general formula (5).But the present invention does not limit by these flow processs.
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In flow process (I) and flow process (II), R arepresent substituting group, R bin flow process (I), represent the assorted aromatic nucleus of π-electron deficiency system with acidic groups, in flow process (II), represent acidic groups or the assorted aromatic nucleus of π-electron deficiency system with acidic groups.N1 and N2 represents the integer of more than 1.M implication is identical with the M of general formula (1).
Metal derivative represented by general formula (5) is described.
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 monovalence such as X ' expression halogen atom, acetic acid ion, acetylacetone based, oxygen or divalence, e represents the integer of 1 ~ 4.
Metal derivative represented by general formula (6) is described.
General formula (6): M '-(Y) f
In general formula (6), M ' expression basic metal, Y represents the dentate of halogen atom, acetic acid ion, acetylacetone based, the monovalence such as alcoholate, oxygen or divalence, and f represents the integer of 1 ~ 4.
When making 2 kinds of Aromatic Dinitriles and/or diimino azole compounds carry out reaction to synthesize metal complex dye of the present invention, there is no particular restriction for its ratio of mixture, but with the preferred 1:4 ~ 4:1 of molar ratio computing.
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 the preferred 1:3 ~ 1:6 of molar ratio computing.
Flow process (I) and the reaction shown in flow process (II) are carried out usually in the presence of the solvent.There is no particular restriction for solvent, can preferably use boiling point to be more than 80 DEG C, the preferably organic solvent of more than 95 DEG C.Include, for example: 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, allyloxyethanol, 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 catalyst can be used.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 relative to Aromatic Dinitriles compound and/or diimino azole compounds 1 mole, 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 flow process (I) and the reaction shown in flow process (II), but preferably 80 DEG C ~ 300 DEG C, more preferably 90 DEG C ~ 250 DEG C, particularly preferably 110 DEG C ~ 230 DEG C.If temperature of reaction is too low, then speed of response becomes extremely slow, if temperature of reaction is too high, then likely produces the decomposition of Aromatic Dinitriles compound and/or diimino azole compounds.
The reaction times of flow process (I) and the reaction shown in 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, then unreacting material increases, if the reaction times is long, then likely produces the decomposition of Aromatic Dinitriles compound and/or diimino azole compounds.
Metal complex dye represented by general formula (1) of the present invention also can synthesis as shown in following flow process (I ') or (flow process II ').
Specifically; synthesize by such as under type: make to comprise have the Aromatic Dinitriles compound of the acidic groups (ester group) protected by protecting group and/or the Aromatic Dinitriles compound of more than two kinds of diimino azole compounds and/or diimino azole compounds, with by as described in metal derivative represented by general formula (5) react, then utilize the alkali-metal hydroxide salt represented by following general formula (7) to be hydrolyzed by generated intermediate.Or; synthesize by such as under type: make to comprise have the Aromatic Dinitriles compound of the acidic groups (ester group) protected by protecting group and/or the Aromatic Dinitriles compound of more than two kinds of diimino azole compounds and/or diimino azole compounds, with by as described in after metal derivative represented by general formula (6) reacts; react with the metal derivative represented by described general formula (5), then utilize the alkali-metal hydroxide salt represented by following general formula (7) to be hydrolyzed by generated intermediate.
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In flow process (I ') and flow process (II '), R a' represent the acidic groups protected by protecting group, R a, R b, the implication of N1, N2 and M and the R of flow process (I) and flow process (II) a, R b, N1, N2 and M implication identical.
Compound represented by general formula (7) is described.
General formula (7): M ' (OH) g
In general formula (7), M ' expression basic metal, g represents the integer of 1 ~ 2.
When make to comprise have the Aromatic Dinitriles compound of the acidic groups (ester group) protected by protecting group and/or 2 kinds of Aromatic Dinitriles compounds of diimino azole compounds and/or diimino azole compounds carry out reaction to synthesize metal complex dye of the present invention time; there is no particular restriction for its ratio of mixture, but with the preferred 1:4 ~ 4:1 of molar ratio computing.
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 the preferred 1:3 ~ 1:6 of molar ratio computing.
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 relative to intermediate t mole, preferably uses more than (t × N1) mole.
Flow process (I ') and the reaction shown in flow process (II ') are carried out usually in the presence of the solvent.There is no particular restriction for solvent, but the solvent that preferred described intermediate dissolves.Include, for example: the alcohol series solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol, or the ether series solvent such as dme, cyclopentyl methyl ether, tetrahydrofuran (THF), dioxan, the nitrile such as acetonitrile, propionitrile series solvent, or these solvents mixed solvent each other or the mixed solvent with water.In addition, the mixed solvent of water or the hydrocarbon system solvent such as these solvents and toluene, dimethylbenzene, hexane, heptane can also be used.
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 flow process (I ') and the reaction shown in flow process (II '), but preferably 20 DEG C ~ 300 DEG C, more preferably 40 DEG C ~ 200 DEG C, particularly preferably 60 DEG C ~ 150 DEG C.If temperature of reaction is too low, then speed of response becomes extremely slow, if temperature of reaction is too high, then likely produces decomposition.
The reaction times of flow process (I ') and the reaction shown in 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, then unreacting material increases, if the reaction times is long, then likely produces decomposition.
The product obtained by described reaction after processing according to the post-treating method of common organic synthesis, can be carried out refining or is not carried out refining and be made for metal complex dye of the present invention.Such as, the product that can not dissociating in autoreaction system carries out refining and provides metal complex dye of the present invention, or recrystallize, column chromatography will be utilized (such as, gel permeation chromatography (SEPHADEXTMLH-20: Pharmacia (Pharmacia) manufactures), high performance liquid chromatography (High Performance Liquid Chromatography, the operation that HPLC etc. carry out refining provides metal complex dye of the present invention after carrying out separately or combining and carry out.
Or, can be after the completion of reaction, heat up in a steamer dereaction solvent, or do not heat up in a steamer and pour out and neutralize to water or ice, or do not carry out neutralizing and the product dissociating carries out refining and provides metal complex dye of the present invention, or after the operation utilizing recrystallize, column chromatography, HPLC etc. to carry out refining being carried out separately or combining and carry out, provide metal complex dye of the present invention.
Or, can be after the completion of reaction, heat up in a steamer dereaction solvent, or do not heat up in a steamer and pour out and neutralize to water or ice, or do not carry out neutralizing and do not carry out refining to the product utilizing organic solvent/aqueous solution to extract and metal complex dye of the present invention is provided, or the operation being undertaken refining utilizing partial crystallization, column chromatography, HPLC provides metal complex dye of the present invention after carrying out separately or combining and carry out.
Moreover, in this manual, about the expression of compound (comprising complex compound, pigment), except this compound itself, also for comprising the implication of its salt, complex compound (time beyond complex compound), its ion.In addition, refer in the scope that is included in and obtains desired effect, the implication of the compound modified with the form specified.In addition, in this manual, about not stating clearly the substituting group being substituted and being unsubstituted, refer to that this base can have arbitrary substituent implication.Do not state clearly the implication being substituted the compound be unsubstituted like this too.As preferred substituting group, described substituting group T can be enumerated.
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 the photoelectrochemical cell using it, 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 the dye compound represented by following general formula (2).
Mz (LL 1) m1(LL 2) m2(X) m3cI general formula (2)
Pigment coordination on atoms metal with the structure of general formula (2) has dentate LL 1and/or dentate LL 2, and specific functional group X optionally, in the case of necessary, remain electric neutrality by CI.
In general formula (2), Mz represents 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 represents by being selected from by 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, thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio, arylthio, base in the cohort that alkoxyl group and aryloxy form comes single tooth of coordination or the dentate of two teeth, or be selected from by halogen atom, carbonyl, dialkyl ketone, 1, 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 of expression represented by following general formula (3) or the dentate of three teeth, preferably two tooth dentates.Represent dentate LL 1the m1 of quantity be the integer of 0 ~ 3, preferably 1 ~ 3, more preferably 1.When m1 is more than 2, multiple 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 22separately represent acidic groups, include, for example: (preferred carbonatoms is the hydroximic acid base of 1 ~ 20, such as-CONHOH ,-CONCH for carboxyl, sulfonic group, hydroxyl, hydroximic acid base 3oH etc.), phosphoryl (such as-OP (O) (OH) 2deng) and phosphono (such as-p (O) (OH) 2deng) and their salt.Carboxyl, phosphono be can preferably enumerate, carboxyl and their salt more preferably can be enumerated.By R 21and R 22represented acidic groups also can be substituted on any one carbon atom on pyridine ring.
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In general formula (3), R 23, R 24separately represent substituting group.As described substituent concrete example, can enumerate: (preferred carbonatoms is the alkyl of 1 ~ 20, such as methyl to alkyl, ethyl, sec.-propyl, the tertiary butyl, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-carboxymethyl etc.), (preferred carbonatoms is the thiazolinyl of 2 ~ 20, such as vinyl to thiazolinyl, allyl group, oleyl etc.), (preferred carbonatoms is the alkynyl of 2 ~ 20, such as ethynyl to alkynyl, diacetylene base, phenylene-ethynylene etc.), (preferred carbonatoms is the cycloalkyl of 3 ~ 20, such as cyclopropyl to cycloalkyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), (preferred carbonatoms is the aryl of 6 ~ 26, such as phenyl to aryl, 1-naphthyl, 4-p-methoxy-phenyl, 2-chloro-phenyl-, 3-aminomethyl phenyl etc.), (preferred carbonatoms is the heterocyclic radical of 2 ~ 20 to heterocyclic radical, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl-, 2-thiazolyl, 2-oxazolyl etc.), (preferred carbonatoms is the alkoxyl group of 1 ~ 20, such as methoxyl group to alkoxyl group, oxyethyl group, isopropoxy, benzyloxy etc.), (preferred carbonatoms is the aryloxy of 6 ~ 26, such as phenoxy group to aryloxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), (preferred carbonatoms is the alkoxy carbonyl of 2 ~ 20, such as ethoxy carbonyl to alkoxy carbonyl, 2-ethyl hexyl oxy carbonyl etc.), it is amino that (preferred carbonatoms is the amino of 0 ~ 20, such as amino, N, N-dimethylamino, N, N-diethylin, N-ethylamino, phenylamino etc.), (preferred carbonatoms is the sulfoamido of 0 ~ 20 to sulfoamido, such as N, N-dimethyl sulfonamide, N-phenyl-sulfamide etc.), (preferred carbonatoms is the acyloxy of 1 ~ 20, such as acetoxyl group to acyloxy, benzoyloxy etc.), (preferred carbonatoms is the carbamyl of 1 ~ 20 to carbamyl, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl etc.), (preferred carbonatoms is the acyl amino of 1 ~ 20, such as acetylamino to acyl amino, benzoyl-amido etc.), cyano group, or halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine 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 1during containing alkyl, thiazolinyl etc., these bases can be straight-chain, also can be branch-like, can be substituted, also can be unsubstituted.In addition, as dentate LL 1during containing aryl, heterocyclic radical etc., these bases can be monocycles, also can be contracting rings, can be substituted, also can be unsubstituted.
In general formula (3), R 25and R 26separately represent aryl or heterocyclic radical.As aryl, preferred carbonatoms be 6 ~ 30 aryl of (preferably 6 ~ 24, more preferably 6 ~ 18), include, for example: phenyl, substituted-phenyl, naphthyl, substituted naphthyl etc.As heterocyclic radical, preferred carbonatoms be 3 ~ 30 heterocyclic radical of (preferably 3 ~ 24, more preferably 3 ~ 16), include, for example: 2-thienyl, 2-pyrryl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, 3-indyl.
R 25and R 26preferably there is the heterocyclic radical of 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 26can directly bond on pyridine ring.R 25with R 26also can via L 1and/or L 2and bond is on pyridine ring.
Herein, L 1and L 2separately represent the conjugated chain of at least 1 in the cohort comprising and be selected from and be made up of the vinylidene being substituted or being unsubstituted, the ethynylene being substituted or being unsubstituted and the heterocyclic radical of divalence that is substituted or is unsubstituted.When vinylidene has substituting group, this substituting group preferred alkyl, more preferably methyl.
L 1and L 2it is independently preferably conjugated chain that carbonatoms is 2 ~ 6, more preferably vinylidene, Aden's dialkylene, ethynylene, Aden's diynyl, methyl vinylidene or dimethylethenylene, 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 double bond can be trans body, also can be cis body, it also can be their mixture.
In general formula (3), d1 and d2 represents the integer of 0 ~ 5 respectively, preferably the integer of 0 ~ 3, more preferably the integer of 0 ~ 2.
In general formula (3), d3 represents 0 or 1, preferably 1.A1 and a2 separately represents the integer of 0 ~ 3.When a1 is more than 2, R 21can be identical, also can be different, when a2 is more than 2, R 22can be identical, also can be different.A1 preferably 0 or 1, a2 preferably 0 ~ 2 integer.Especially, when d3 is 0, a2 preferably 1 or 2, when d3 is 1, a2 preferably 0 or 1.A1 and a2 and preferably 0 ~ 2 integer.
B1 and b2 separately represents the integer of 0 ~ 3, preferably the integer of 0 ~ 2.When b1 is more than 2, R 23can be identical, also can be different, and can be interconnected and form ring.When b2 is more than 2, R 24can be identical, also can be different, and can be interconnected and form ring.In addition, when b1 and b2 is more than 1, R 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 1when there is at least 1 acidic groups, the m1 in general formula (3) preferably 2 or 3, more preferably 2.
In general formula (2), LL 2two teeth of expression represented by following general formula (4) or the dentate of three teeth.LL 2preferably two tooth dentates.Represent dentate LL 2the m2 of quantity be the integer of 1 ~ 3, preferably 1 or 2.When m2 is more than 2, LL 2can be identical, also can be different.
[changing 37]
In general formula (4), Za, Zb and Zc separately represent the non-metallic atom group that can form 5 Yuans rings or 6 Yuans rings.The 5 Yuans rings formed or 6 Yuans rings can be substituted, and also can be unsubstituted, and can be monocycles, also can be contracting rings.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 ring that Za, Zb and Zc are formed has acidic groups.As acidic groups, include, for example: 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 can on the ring that directly bond is formed at Za, Zb or Zc, also can on the ring that bond is formed at Za, Zb or Zc via concatenating group.There is no particular restriction for concatenating group, can enumerate: methylene radical, vinylidene, ethynylene, arylidene, inferior heteroaryl or the concatenating group etc. combined by these concatenating groups.
In general formula (4), c represents 0 or 1.C preferably 0.
As the dentate LL represented by general formula (4) 2during containing alkyl, thiazolinyl etc., these bases can be straight-chain, also can be branch-like, can be substituted, also can be unsubstituted.In addition, LL is worked as 2during containing aryl, heterocyclic radical etc., these bases can be monocycles, also can be contracting rings, can be substituted, also can be unsubstituted.
In general formula (2), X represents the dentate of single tooth or two teeth.Represent that the m3 of quantity of dentate X represents the integer of 0 ~ 2, m3 preferably 1 or 2.When X is single tooth dentate, m3 preferably 2, when X is two tooth dentate, m3 preferably 1.When m3 is 2, X can be identical, also can be different, and X each other also can be interconnected.
Dentate X represents that (preferred carbonatoms is the acyloxy of 1 ~ 20 by being selected from by acyloxy, such as acetoxyl group, benzoyloxy, Whitfield's ointment, glycyl oxygen base, N, N-dimethylglycinamidyl oxygen base, sub-oxalyl group (-OC (O) C (O) O-) etc.), (preferred carbonatoms is the acyl sulfenyl of 1 ~ 20 to acyl sulfenyl, such as acetylthio, benzoylthio etc.), (preferred carbonatoms is the sulfo-acyloxy of 1 ~ 20 to sulfo-acyloxy, such as thioacetyl oxygen base (CH 3c (S) O-) etc.), (preferred carbonatoms is the sulfo-acyl sulfenyl of 1 ~ 20 to sulfo-acyl sulfenyl, such as thioacetyl sulfenyl (CH 3c (S) S-), thiobenzoyl sulfenyl (PhC (S) S-) etc.), (preferred carbonatoms is the acyl amino oxygen base of 1 ~ 20 to acyl amino oxygen base, such as N-methyl benzoyl amino oxygen base (PhC (O) N (CH 3) O-), acetylamino oxygen base (CH 3c (O) NHO-) etc.), (preferred carbonatoms is the thiocarbamate base of 1 ~ 20 to thiocarbamate base, such as N, N-diethyl sulfide is for carbamate groups etc.), (preferred carbonatoms is the dithiocarbamate groups of 1 ~ 20 to dithiocarbamate groups, such as N-phenyl dithiocarbamate base, N, N-dimethyldithiocarbamate base, N, N-diethyldithiocarbamate base, N, N-dibenzyl aminodithioformic acid ester group etc.), (preferred carbonatoms is the thiocarbonic acid SOH ester group of 1 ~ 20 to thiocarbonic acid SOH ester group, such as Ethyl Thiocarbonate base etc.), (preferred carbonatoms is the dithiocarbonic acid ester group of 1 ~ 20 to dithiocarbonic acid ester group, such as ethyl dithiocarbonic acid ester group (C 2h 5oC (S) S-) etc.), (preferred carbonatoms is the trithiocarbonic acid ester group of 1 ~ 20 to trithiocarbonic acid ester group, such as ethyl trithiocarbonic acid ester group (C 2h 5sC (S) S-) etc.), (preferred carbonatoms is the acyl group of 1 ~ 20 to acyl group, such as ethanoyl, benzoyl etc.), thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, (preferred carbonatoms is the alkylthio of 1 ~ 20 to alkylthio, such as methane sulfenyl, ethylene sulfenyl etc.), (preferred carbonatoms is the arylthio of 6 ~ 20 to arylthio, such as thiophenyl, 1, 2-phenylene disulfide group etc.), (preferred carbonatoms is the alkoxyl group of 1 ~ 20 to alkoxyl group, such as methoxyl group etc.) and aryloxy (preferred carbonatoms is the aryloxy of 6 ~ 20, such as phenoxy group, quinoline-8-hydroxyl etc.) base in the cohort that forms comes single tooth of coordination or the dentate of two teeth, or be selected from by halogen atom (preferred chlorine atom, bromine atoms, atomic iodine etc.), carbonyl (... CO), (preferred carbonatoms is the dialkyl ketone of 3 ~ 20 to dialkyl ketone, such as acetone ((CH 3) 2cO...) etc.), (preferred carbonatoms is 1, the 3-diketone of 3 ~ 20, such as methyl ethyl diketone (CH to 1,3-diketone 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.), (preferred carbonatoms is the benzamide of 1 ~ 20 to benzamide, such as CH 3n=C (CH 3) O-,-OC (=NH)-C (=NH) O-etc.), (preferred carbonatoms is the thiobenzamide of 1 ~ 20 to thiobenzamide, such as CH 3n=C (CH 3) S-etc.) and thiocarbamide (preferred carbonatoms is the thiocarbamide of 1 ~ 20, such as NH (...)=C (S-) NH 2, CH 3n (...)=C (S-) NHCH 3, (CH 3) 2n-C (S...) N (CH 3) 2deng) single tooth in the cohort that forms or two tooth dentates.Moreover " ... " represents coordinate bond.
Dentate X is preferably by being selected from by acyloxy, sulfo-acyl sulfenyl, acyl amino oxygen base, dithiocarbamate groups, dithiocarbonic acid ester group, 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 is selected from by halogen atom, carbonyl, dentate in the cohort that 1,3-diketone and thiocarbamide form, more particularly by being selected from by 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 is selected from by halogen atom, dentate in the cohort that 1,3-diketone and thiocarbamide form, particularly preferably by being selected from by dithiocarbamate groups, thiocyanate groups, isothiocyanate group, base in the cohort that cyanate ester based and isocyanate group forms carrys out the dentate of coordination, or is selected from the dentate in the cohort that is made up of halogen atom and 1,3-diketone, most preferably by being selected from by dithiocarbamate groups, base in the cohort that thiocyanate groups and isothiocyanate group form carrys out the dentate of coordination, or comprises the dentate of 1,3-diketone.
When dentate X contains alkyl, thiazolinyl, alkynyl, alkylidene group etc., these bases can be straight-chain, also can be 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, also can be contracting rings.
When X is two tooth dentate; X carrys out the dentate of coordination preferably by the base be selected from the cohort that is made up of 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; or the dentate be selected from the cohort that is made up of 1,3-diketone, benzamide, thiobenzamide and thiocarbamide.
When X is single tooth dentate, X carrys out the dentate of coordination preferably by the base be selected from the cohort that is made up of thiocyanate groups, isothiocyanate group, cyanate ester based, isocyanate group, cyano group, alkylthio and arylthio, or is selected from the dentate in the cohort that is made up of halogen atom, carbonyl, dialkyl ketone and thiocarbamide.
In general formula (2), during CI represents and electric charge and need counter ion time counter ion.Usually, pigment be positively charged ion or negatively charged ion or whether the tangible ionic charge of tool depend on metal, dentate and the substituting group in pigment.
Have dissociative base etc. by substituting group, the pigment represented by general formula (2) can dissociate and have negative charge.In the case, the electric charge of the pigment entirety represented by general formula (2) becomes electric neutrality by CI.
When counter ion CI is positive counter ion, such as, as counter ion CI, inorganic or organic ammonium ion (such as tetraalkyl ammonium ion, pyridinium ion etc.), alkalimetal ion and proton can be enumerated.
When counter ion CI is negative counter ion, counter ion CI can be inorganic anion, also can be organic anion.Include, for example: halide anion (such as fluoride ion, chloride ion, bromide ion, iodide ion etc.), substituted aryl azochlorosulfonate acid ion (such as tosic acid ion, p-chlorobenzenesulfonic acid ion etc.), aryl disulfonic ion (such as 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 chlorate ions, Tetrafluoroboric acid ion, phosphofluoric acid ester ion, picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion etc.And then, as equalizing charge counter ion, other pigments with the electric charge contrary with ionic polymers or pigment can be used, also can use metel complex ion (such as two benzene-1,2-bis-mercaptan nickel (III) etc.).
The pigment with the structure represented by general formula (2) has the suitable bond base (interlocking group) on more than at least 1 surface for semiconductor microactuator particle.More preferably there are 1 ~ 6 these bond bases in pigment, particularly preferably there are 1 ~ 4.In general formula (4), at least 1 in the ring that Za, Zb and Zc are formed has acidic groups, and this acidic groups plays function as bond base.The pigment with the 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, aIkylsilyl groups etc.Wherein, preferred acidic base.
There is the compound of dye compound preferably represented by following general formula (10) of the structure represented by general formula (2).
(Al) pru (B-a) (B-b) (B-c) general formula (10)
In general formula (10), Al represents the dentate of single tooth or two teeth.As the concrete example of Al, can enumerate and be selected from by 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 Al, preferred SCN or beta-diketon class.
In general formula (10), p is the integer of 0 ~ 3.P preferably 1 ~ 3 integer.
In general formula (10), B-a, B-b and B-c separately represent by following Formula B-1 ~ Formula B-10 any one represented by organic coordination base or by Formula B-1 ~ Formula B-10 any one represented by the acidic groups that has of organic coordination base be salt person.
[changing 38]
In Formula B-1 ~ Formula B-10, R 11~ R 22represent substituting group.
Alternatively base, can enumerate: the aryl being substituted or being unsubstituted or described acidic groups (these acidic groups also can form salt) that the alkyl being substituted or being unsubstituted, alkoxyl group, the carbonatoms thiazolinyl being substituted or being unsubstituted that is 2 ~ 20, the carbonatoms aralkyl being substituted or being unsubstituted that is 7 ~ 12 that halogen atom, carbonatoms are 1 ~ 12, alkoxy aryl, carbonatoms are 6 ~ 12.The moieties of alkyl and aralkyl can be straight-chain, also can be branch-like.In addition, the aryl moiety of aryl and aralkyl can be monocycle, also can be many rings (condensed ring, ring set).By R 11~ R 22represented substituting group can be substituted further, and the substituting group carrying out further replacing is as R 11~ R 22cited substituting group, is preferably replaced by acidic groups.By R 11~ R 22represented substituting group itself is preferably acidic groups or the base with acidic groups alternatively base.
E1 ~ e12 represents the integer of more than 0.Specifically, e1 and e2 separately represents the integer of 0 ~ 4, e3 represents the integer of 0 ~ 3, e4 and e5 separately represents the integer of 0 ~ 4, e6 represents the integer of 0 ~ 2, e7 and e8 separately represents the integer of 0 ~ 3, and e9 represents the integer of 0 ~ 4, and e10 ~ e12 separately represents the integer of 0 ~ 6.When e1 ~ e12 is more than 2, R 11~ R 22respectively can be identical, also can be different.Preferred e1 ~ e12 is independently the situation of 1.
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.
Below represent the concrete example with the pigment of the structure represented by general formula (2) used in 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 discharge proton.
[changing 39]
[changing 40]
Pigment represented by general formula (2) of the present invention can synthesize with reference to the method quoted in Japanese Patent Laid-Open 2001-291534 publication or this publication.
There is the scope of the preferred 300nm ~ 700nm of pigment maximum absorption wavelength in the solution of the structure of general formula (2), the more preferably scope of 400nm ~ 650nm, the particularly preferably scope of 500nm ~ 600nm.
And then the light absorption wave band of the pigment represented by general formula (2) is preferably in the scope of 300nm ~ 900nm, is more preferably in the scope of 350nm ~ 850nm.
In photo-electric conversion element of the present invention and photoelectrochemical cell, use the metal complex dye represented by general formula (1), but also can be used together the pigment of the structure with described general formula (2).By using these pigments in photo-electric conversion element and photoelectrochemical cell, the light of the wavelength had a wide reach can be utilized in photo-electric conversion element and photoelectrochemical cell, and can high conversion efficiency be guaranteed.And then, the rate of descent of efficiency of conversion can be reduced.
About metal complex dye and the allotment ratio of pigment with the structure represented by general formula (1) of the structure had represented by general formula (2), if the former is set to R, the latter is set to S, then in % by mole ratio, R/S=90/10 ~ 10/90, preferred R/S=80/20 ~ 20/80, more preferably R/S=70/30 ~ 30/70, particularly preferably R/S=60/40 ~ 40/60, most preferably R/S=55/45 ~ 45/55, usually to wait mole both uses.
(Charger transfer body)
In the preferred example of photo-electric conversion element of the present invention as shown in Figure 1, the Charger transfer body layer 3 used in photo-electric conversion element can apply the layer comprising ionogen constituent.As its redox couple, include, for example: the combination etc. of the iron complex (such as red prussiate of potash and yellow prussiate of potash) 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 the combination of its Reduction Body, poly-Hydroxybenzenes (such as Resorcinol, naphthalene quinhydrones etc.) and the combination of its oxysome, the iron complex of divalence and trivalent.Among these combinations, the combination of preferred iodine and iodide.
The nitrogenous aromatic series positively charged ion of the positively charged ion of salt compounded of iodine preferably 5 Yuans rings or 6 Yuans rings.Especially, as any one or one of the compound represented by general formula (1) and the compound represented by general formula (2) and Non-iodizedsalt time, preferred also No. WO95/18456, use, No. 8-259543, Japanese Patent Laid-Open, electrochemistry, 65th volume, No. 11, the salt compounded of iodine such as pyridinium salt, imidazole salts, triazolium salt described in 923 pages (1997) etc.
In the ionogen constituent used in photo-electric conversion element of the present invention, preferably containing heterocycle level Four salt compound and iodine.Relative to whole ionogen constituent, the content preferably 0.1 quality % ~ 20 quality % of iodine, more preferably 0.5 quality % ~ 5 quality %.
The ionogen constituent used in photo-electric conversion element of the present invention also can contain solvent.Below the 50 quality % of the preferred whole constituent of the solvent in ionogen constituent, more preferably below the 30 quality % of whole constituent, below the 10 quality % of particularly preferably 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, propylene glycol dialkyl ether, dialkylethers, 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.), aprotic polar solvent (dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide, DMSO), tetramethylene sulfone etc.), water, the aqueous electrolyte recorded in Japanese Patent Laid-Open 2002-110262, Japanese Patent Laid-Open 2000-36332 publication, Japanese Patent Laid-Open 2000-243134 publication, and Japan's public electrolyte solvent etc. showing to record in WO/00-54361 publication again.These solvents also can be use mixing two or more.
In addition, as electrolyte solvent, also can use at room temperature for liquid state and/or the fusing point that has lower than room temperature and be the salt of inertia in electrochemistry.Include, for example: 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 the ionogen constituent of photo-electric conversion element used in the present invention, also can add polymkeric substance or oleogel agent or the gelation (solidification) by methods such as the polymerization of polyfunctional monomer class or the crosslinking reactions of polymkeric substance.
When being made the gelation of ionogen constituent by interpolation polymkeric substance, compound etc. described in polymer dielectric comment (Polymer Electrolyte Reviews)-1 and polymer dielectric comment-2 (J.R. Mike lime (J.R.MacCallum) and C.A. guest gloomy (C.A.Vincent) compile in collaboration with, Ai Er Seville applied science (ELSEVIER APPLIED SCIENCE)) can be added.In the case, preferably polyacrylonitrile or poly(vinylidene fluoride) is used.
When being made the gelation of ionogen constituent by interpolation oleogel agent, as oleogel agent, Japanization association will can be used, 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), applied chemistry international version (English) (Angew.Chem.Int.Ed.Engl.), 35, 1949 (1996), Chemistry Letters (Chem.Lett.), 885, (1996), chemistry meeting will, chemical communication (J.Chem.Soc., Chem.Commun.), 545, etc. (1997) compound described in, preferred use has the compound of amide structure.
When the polymerization by polyfunctional monomer class makes the gelation of ionogen constituent, the method be preferably as follows: by polyfunctional monomer class, polymerization initiators, ionogen and solvent to prepare solution, and utilize the method such as teeming practice, coating method, pickling process, impregnation method on the electrode carrying pigment, form the dielectric substrate of colloidal sol shape, make its gelation by the radical polymerization of polyfunctional monomer is incompatible thereafter.Polyfunctional monomer class preferably has the compound of more than 2 ethene unsaturated groups, preferred Vinylstyrene, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, dimethacrylate, triethylene glycol diacrylate, TEGDMA, pentaerythritol triacrylate, Viscoat 295 etc.
Except described polyfunctional monomer class, gel electrolyte also can be formed by the polymerization of the mixture containing monofunctional monomer.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, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid 3-pentyl ester, t-amyl, the just own ester of vinylformic acid, vinylformic acid 2,2-dimethyl butyl ester, 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-methoxy acrylate, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-methoxyethoxyethyl acrylate, acrylate, vinylformic acid 3-methoxybutyl, ethyl carbitol acrylate, vinylformic acid 2-methyl-2-nitro propyl ester, vinylformic acid 2,2,2-trifluoro ethyl ester, vinylformic acid octafluoro pentyl ester, vinylformic acid 17 fluorine ester in the last of the ten Heavenly stems, methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, t-amyl methacrylate, the positive octadecyl ester of methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 2-methoxy acrylate, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 2-methoxyethoxyethyl acrylate, dimethylaminoethyl methacrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, tetrafluoropropyl propyl ester, methacrylic acid hexafluoro propyl ester, methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, diglycol carbonate ethylacrylate methyl acrylate, 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-n-butyl acryloyloxy ethyl acid amides, N tert butyl acrylamide, N,N-DMAA, N hydroxymethyl acrylamide, diacetone acrylamide, 2-acrylamide-2-methyl propane sulfonic, acrylamido propyl trimethyl ammonium chloride, Methacrylamide, N-methyl methacrylamide, 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.), N-vinyl formamide, N-vinyl-N-methyl methane amide, N-vinyl acetamide, N-vinyl-N-methylacetaniide, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, methacrylsulfonic acid sodium, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (methylvinylether etc.), ethene, propylene, butylene, iso-butylene, N-phenylmaleimide etc.
Relative to whole monomer, the allotment amount of polyfunctional monomer is preferably set to 0.5 quality % ~ 70 quality %, more preferably 1.0 quality % ~ 50 quality %.Described monomer is polymerized by the radical polymerization as general Polymer Synthesizing method described in happy work altogether refined under the grand row wood of large Tianjin " laboratory method of Polymer Synthesizing) " the grand row of (chemical same people) or large Tianjin " polyreaction opinion lecture 1 radical polymerization (I)) " (chemical same people) is incompatible.The gel electrolyte monomer used in the present invention to carry out radical polymerization, or carries out radical polymerization with electrochemical means by heating, light or electron beam, but particularly preferably carries out radical polymerization by heating.In the case, the polymerization initiators that can preferably use is 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), dimethyl 2, the azo system initiators such as 2 '-azobisisobutylonitrile acid esters, the peroxidation system initiators etc. such as lauryl peroxide, benzoyl peroxide, the peroxidation acid tert-butyl ester.Relative to monomer total amount, the preferred addition of polymerization initiators is 0.01 quality % ~ 20 quality %, more preferably 0.1 quality % ~ 10 quality %.
The weight compositing range preferably 0.5 quality % ~ 70 quality % that monomer is shared in gel electrolyte.More preferably 1.0 quality % ~ 50 quality %.When the crosslinking reaction by polymkeric substance makes the gelation of ionogen constituent, preferably add in constituent and there is the polymkeric substance and linking agent that can carry out the reactive base be cross-linked.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 the compound (electrophilic reagent) that nitrogen-atoms has that more than 2 can be carried out the functional group of nucleophillic attack, such as, be the halogenated alkyl, halogenated aralkyl, sulphonate, acid anhydrides, acyl chlorides, isocyanic ester etc. of more than two senses.
In ionogen constituent used in the present invention, metal iodide (LiI, NaI, KI, CsI, CaI can be added 2deng), metal bromide (LiBr, NaBr, KBr, CsBr, CaBr 2deng), level Four ammonium bromine salt (tetra-alkyl ammonium bromide, 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 be used in combination.
In addition, in ionogen constituent used in the present invention, also American Ceramics association magazine (J.Am.Ceram.Soc.) can be added, 80, (12), tert .-butylpyridine described in 3157-3171 (1997) or the basic cpd such as 2-picoline, 2,6-lutidine.Preferred concentration range when adding basic cpd is 0.05M ~ 2M.
In addition, as the Charger transfer body layer 3 in photo-electric conversion element of the present invention, the charge transport layer containing hole conductor material can also be used.As hole conductor material, can 9 be used, 9 '-spirobifluorene derivative etc.
In addition, as the formation of electrochemical element, can successively lamination conductive support body (electrode layer), photoelectric conversion layer (photoreceptor layers and Charger transfer body layer), hole transmission layer, conducting stratum, to electrode layer.
The hole mobile material playing function as p-type semiconductor can be used as hole transmission layer.As preferred hole transmission layer, such as, can use the hole mobile material of inorganic system or organic system.As inorganic system hole mobile material, CuI, CuO, NiO etc. can be enumerated.In addition, as organic system hole mobile material, the material of macromolecular and low molecule system can be enumerated, as the material of macromolecular, include, for example: polyvinyl carbazole, polyamine, organopolysilane etc.In addition, as the material of low molecule system, include, for example: triphenylamine derivative, diphenyl ethylene derivatives, hydrazone derivative, phenamine (phenamine) derivative etc.Wherein, organopolysilane is different from previous carbon system polymer, and it is the polymer with main chain Si chain.And, σ-electron along main chain Si delocalization (delocalization) contributes to light conduction, therefore has high hole rate of flow (reference " physical comment B (Phys.Rev.B) ", 35,2818 (1987) etc.), so preferably.
As long as the layer that conducting stratum electroconductibility in photo-electric conversion element of the present invention is good can be arranged on, be then not particularly limited, include, for example: 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, organic donor and organic receptor can preferably be used.
The material of electronics is rich in donor material preferred molecular structure.Such as, as organic donor material, the material in the π-electron system of molecule with the amido, hydroxyl, ether, selenium or the sulphur atom that are substituted or are unsubstituted can be enumerated, specifically, 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.Such as, as Organic host materials, soccerballene can be enumerated, in the π-electron system of molecule, there is nitro, cyano group, the substituent material such as carboxyl or halogen, specifically, can enumerate: [6, 6]-phenyl-C61-methyl-butyrate ([6, 6]-Phenyl-C61-Butyric Acid Methyl Ester, PCBM), benzoquinones system, the quinone systems such as naphthoquinones system, Fluorenone (fluorenone) is, tetrachlorobenzoquinone (chloranil) is, tetrabromo-quinone (bromanil) is, four cyano quinone bismethane (tetracyanoquinodimethane) is, tetracyanoethylene (tetracyanoethylene) is.
Moreover the thickness of conducting stratum is not particularly limited, but preferably can bury the degree of Porous completely.
(conductive support body)
In the preferred example of photo-electric conversion element of the present invention as shown in Figure 1, conductive support body 1 is formed sensitizing coloring matter 21 and is adsorbed on photoreceptor layers 2 on the semiconductor microactuator particle 22 of Porous.As aftermentioned, such as, the dispersion liquid of semiconductor microactuator particle be coated in conductive support body and in addition after drying, be immersed in pigment solution of the present invention, photoreceptor layers 2 can be manufactured thus.
As conductive support body, supporter itself as metal can be used to have glass or macromolecular material that electroconductibility person or surface have conductive film layer.Conductive support body is preferably transparent in fact.If transparent in fact, then mean that the transmitance of light is more than 10%, preferably more than 50%, particularly preferably more than 80%.As conductive support body, can use and the painting of the metal oxide of electroconductibility is located at glass or the macromolecular material person of forming.The glue spread of the metal oxide of electroconductibility is now at every 1m of the supporter of glass or macromolecular material 2on, preferred 0.1g ~ 100g.When using transparent conductivity supporter, light is preferably made to inject from support side.As an example of the macromolecular material preferably used, can enumerate: four cellulose acetates (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.In conductive support body, also can apply light regime function by effects on surface, include, for example the alternately lamination recorded in Japanese Patent Laid-Open 2003-123859 has the photoconduction function recorded 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 preferably metal support can be used.As one example, can enumerate: titanium, aluminium, copper, nickel, iron, stainless steel.These metals also can be alloys.More preferably titanium, aluminium, copper, particularly preferably titanium or aluminium.
Preferably make function conductive support body with blocking UV-light.The method that such as also can be listed below: make the fluorescent material that UV-light can be become visible ray be present in transparent supporting body or transparent support surface method or use the method for UV light absorber.
In conductive support body, also can give function described in Japanese Patent Laid-Open 11-250944 publication etc. further.
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 the doped with fluorine person of forming in stannic oxide etc.).
The thickness of conductive film layer preferably 0.01 μm ~ 30 μm, more preferably 0.03 μm ~ 25 μm, particularly preferably 0.05 μm ~ 20 μm.
The surface resistivity of conductive support body 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 cellar area becomes large, then the resistance value of conducting film becomes large, therefore also can configure collecting electrodes.Also gas barrier film and/or anti-ion diffuse film can be configured between conductive support body and nesa coating.As gas barrier layer, resin molding or mineral membrane can be used.
In addition, transparency electrode also can be set and Porous semi-conducting electrode photocatalyst contains layer.Transparency conducting layer also can be lamination structure, as preferred method, and such as can 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, conductive support body 1 is formed pigment 21 and is adsorbed on photoreceptor layers 2 on the semiconductor microactuator particle 22 of Porous.As aftermentioned, such as, the dispersion liquid of semiconductor microactuator particle be coated in described conductive support body and in addition after drying, be immersed in pigment solution of the present invention, photoreceptor layers 2 can be manufactured thus.
As 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, the oxide compound of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum preferably can be enumerated, Cadmium Sulfide, cadmium selenide etc.As uhligite, preferably strontium titanate, calcium titanate etc. can be enumerated.Among them, particularly preferably titanium oxide, zinc oxide, stannic oxide, Tungsten oxide 99.999.
Semi-conductor exists and conducts N-shaped that relevant current carrier is electronics and current carrier is the p-type in hole, with regard to the viewpoint of efficiency of conversion, preferably uses N-shaped in element of the present invention.In n-type semiconductor, except not there is impurity level and utilizing except proper semiconductor's (or proper semiconductor) that conduction band electron is equal with the concentration of the current carrier of valence band hole, there is the high n-type semiconductor of electron carrier density because being derived from the structure defect of 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-type semiconductor is TiO 2, ZnO, SnO 2, WO 3, and Nb 2o 3.In addition, the semiconductor material of multiple described semiconductors coupling is also preferably made.
In order to keep high by the viscosity of semiconductor microactuator particle dispersion liquid, 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 of more than 2nm, below 30nm.Also can by micropartical mixing of more than two kinds different for size distribution, in the case, the mean sizes of preferred small-particle is below 5nm.In addition, in order to make incident light scattering to promote light capture rate, also can add relative to described ultramicron median size more than the macroparticle of 50nm or be coated with other layers with low containing ratio.In the case, the preferred median size of containing ratio of macroparticle is less than 50% of the quality of the particle of below 50nm, more preferably less than 20%.Preferred more than the 100nm of median size of the macroparticle of mixing is added, more preferably more than 250nm with described object.
Preferably by the macroparticle using scattering of light, mist degree rate becomes more than 60%.Mist degree rate is represented by (diffusional permeability) ÷ (total light transmittance).
As the making method of semiconductor microactuator particle, sol-gel process described in " science of sol-gel method " Ah lattice's a kind of apple (Agune) Cheng Fengshe (1998) of preferred work flower Ji husband etc.In addition, by carrying out pyrohydrolysis to the muriate of Degussa (Degussa) company exploitation in hydrogen-oxygen salt, to make the method for oxide compound also preferred.When semiconductor microactuator particle is titanium oxide, described sol-gel method, sol-gel process, the flame hydrolysis of muriate in hydrogen-oxygen salt is all preferred, and then " titanium oxide physical property and utilisation technology " skill report hall that also can using leaves nothing usable to the invading enemy learns publishes sulfuric acid process described in (1997) and chlorine method.And then, as sol-gel method, the American Ceramics association magazine (Joumal of American Ceramic Society) of BABEI (Barbe) etc., 80th volume, No. 12, the Materials science (Chemistry of Materials) of method described in 3157 pages ~ 3171 pages (1997) or Ben Saide (Burnside) etc., the 10th volume, No. 9, method described in 2419 pages ~ 2425 pages is also preferred.
In addition, as the manufacture method of semiconductor microactuator particle, such as the manufacture method of titanium dioxide nano-particle, can preferably enumerate utilize the combustion method of the method for the flame hydrolysis of titanium tetrachloride, titanium tetrachloride, the hydrolysis of stable chalkogenide complex compound, adjacent metatitanic acid hydrolysis, form semiconductor microactuator particle by soluble portions and insoluble portion after soluble portions dissolved remove method, peroxide aqueous solution Hydrothermal Synthesis or utilize the manufacture method of titanium oxide microparticle of core/shell structure of sol-gel method.
As the crystalline texture of titanium dioxide, Detitanium-ore-type, brookite type or rutile-type can be enumerated, preferred 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 effects on surface uses additive in order to prevent anti-electron from shifting.As the example of preferred additive, can enumerate: the Charger transfer bond molecules such as fibrous material, metal, organosilicon, dodecyl Phenylsulfonic acid, silane compound and the current potential apsacline branch-shape polymer etc. such as ITO, SnO particle, whisker, fiber graphite CNT (carbon nano-tube), zinc oxide necking down bond base, Mierocrystalline cellulose.
In order to remove the surface imperfection etc. on titanium dioxide, also before pigment absorption, soda acid reduction treatment or redox process can be carried out to titanium dioxide.Also can pass through etching, oxide treatment, hydrogen peroxide treatment, Dehydroepiandrosterone derivative, ultraviolet (Ultraviolet, UV)-ozone, oxygen plasma etc. process.
(semiconductor microactuator particle dispersion liquid)
In the present invention, the semiconductor microactuator particle dispersion liquid content of the solids component beyond semiconductor microactuator particle being comprised below the 10 quality % of semiconductor microactuator particle dispersion liquid entirety is coated in described conductive support body, and moderately heat, Porous semiconductor microactuator particle coating layer (photoreceptor layers) can be obtained thus.
As the method making semiconductor microactuator particle dispersion liquid, except described sol-gel method, method etc. can be listed below: separate out as micropartical in a solvent when synthesized semiconductor and the method directly used, method micropartical irradiation ultrasonic wave etc. being ground into ultramicron or use pulverizing mill or mortar etc. are mechanically pulverized and the method ground.As dispersion solvent, water and/or various organic solvent can be used.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 such as can use a small amount of polymkeric substance as polyoxyethylene glycol, Natvosol, carboxymethyl cellulose, interfacial agent, acid, or sequestrant etc. is as dispersing auxiliary.But, preferably before the step towards masking in conductive support body, by filtration method or use the method for separatory membrane or centrifugal separation etc. the major part of these dispersing auxiliaries to be removed.The content of the solids component beyond semiconductor microactuator particle can be set to below the 10 quality % of dispersion liquid entirety by semiconductor microactuator particle dispersion liquid.This concentration preferably less than 5%, more preferably less than 3%, particularly preferably less than 1%.More preferably less than 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 set to below the 10 quality % of semiconductor microactuator particle dispersion liquid entirety.Preferably in fact only comprise semiconductor microactuator particle and dispersion solvent.
If the viscosity of semiconductor microactuator particle dispersion liquid is too high, then, on the contrary, if the viscosity of semiconductor microactuator particle dispersion liquid is too low, then there is dispersion liquid flowing and the situation that cannot be filmed in dispersion liquid cohesion and cannot being filmed.Therefore, the viscosity of dispersion liquid preferred 10Ns/m at 25 DEG C 2~ 300Ns/m 2.More preferably be 50Ns/m at 25 DEG C 2~ 200Ns/m 2.
As the coating process of semiconductor microactuator particle dispersion liquid, as the method for application system, roller method, pickling process etc. can be used.In addition, as the method for metering system, air knife method can be used, scrape the skill in using a kitchen knife in cookery etc.In addition, as can the method for the method of application system and metering system is used for a part of method, sliding hopper (slide hopper) method, extrusion process, heavy curtain method etc. described in the line disclosed in No. 58-4589, preferred Japanese Patent examined patent publication rod method, United States Patent (USP) No. 2681294 specification sheetss etc.In addition, use general-purpose machinery and undertaken being coated with by rotational method or spray method also preferred.As wet printing method, headed by 3 of relief printing plate, lithographic plate and intaglio plate large print processes, preferred intaglio plate, flexographic, screen painting etc.Corresponding to liquid viscosity or wet thickness, from these methods, select preferred film-forming method.In addition, described semiconductor microactuator particle dispersion liquid is high due to viscosity, and has toughness, and therefore cohesive force is strong sometimes, the situation that successfully cannot be combined with supporter when there is coating.In such cases, carry out the clean of surface and hydrophilization by UV ozonize, semiconductor microactuator particle dispersion liquid be coated with thus and the cohesive force on conductive support body surface increase, and the coating of semiconductor microactuator particle dispersion liquid becomes easily to be carried out.
The preferred thickness of semiconductor microactuator particle layer entirety is 0.1 μm ~ 100 μm.The thickness of semiconductor microactuator particle layer more preferably 1 μm ~ 30 μm, and then more preferably 2 μm ~ 25 μm.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 electronics contact each other of semiconductor microactuator particle and the adhesion of lifting and supporter, in addition, in order to make be coated with semiconductor microactuator particle dispersion liquid dry, and heat treated is implemented to the layer of be coated with semiconductor microactuator particle.Porous semiconductor microactuator particle layer can be formed by this heat treated.In addition, also can suitablely corresponding to the characteristic of component or purposes utilize known method to form semiconductor microactuator particle layer.Such as, can refer to material described in Japanese Patent Laid-Open 2001-291534 publication or preparation method, making method, and be referenced in this specification sheets.
In addition, except heat treated, also luminous energy can be utilized.Such as, when use titanium oxide is as the semiconductive particles period of the day from 11 p.m. to 1 a.m, the light that the semiconductor microactuator particle by giving as UV-light can absorb to make surface active, and can utilize laser etc. only to make semiconductor microactuator particle surface activate.By irradiating the light that this micropartical can absorb to semiconductive particles, the impurity being adsorbed on particle surface decomposes because of the activation of particle surface, can become preferred state in order to described object.When heat treated and UV-light being combined, preferably one side is to the sub light irradiating this micropartical and can absorb of semiconductive particles, and one side is with more than 100 DEG C, less than 250 DEG C or preferably heat with more than 100 DEG C, less than 150 DEG C.So, optical excitation is carried out to semiconductive particles, by photolysis, the impurity be mixed into in particulate sublayer is cleaned thus, and strengthen the physical engagement between micropartical.
In addition, semiconductor microactuator particle dispersion liquid is coated in described conductive support body, except heating or irradiation light, also can carries out other process.As preferred method, include, for example energising, chemical treatment etc.
Also can applying pressure after coating, as executing stressed method, method etc. described in Japanese Patent spy table 2003-500857 publication can be enumerated.As the example irradiating light, method etc. described in Japanese Patent Laid-Open 2001-357896 publication can be enumerated.As the example of plasma microwave energising, method etc. described in Japanese Patent Laid-Open 2002-353453 publication can be enumerated.As chemical treatment, include, for example method described in Japanese Patent Laid-Open 2001-357896 publication.
The method in conductive support body of being coated with by described semiconductor microactuator particle is except being coated on except the method in conductive support body by described semiconductor microactuator particle dispersion liquid, the method such as with the following method can be made: be coated in conductive support body by the precursor of semiconductor microactuator particle described in Japanese Patent No. 2664194 publication, be hydrolyzed by the moisture in air and obtain semiconductor microactuator particle film.
As precursor, include, for example: (NH 4) 2tiF 6, titanium peroxide, metal alkoxide, metal complex, metal organic acid salt etc.
In addition, can enumerate: be coated with slurry that metal organic oxygen compound (alkoxide etc.) is coexisted and formed the method for semiconductor film by heat treated, optical processing etc.; To the pH of the slurry making inorganic system precursor coexist, slurry and the method for the proterties special stipulation of TiO 2 particles of disperseing.Also can add a small amount of tackiness agent in these slurries, as tackiness agent, can enumerate: Mierocrystalline cellulose, fluoropolymer, cross-linked rubber, poly(tributoxy titanium), carboxymethyl cellulose etc.
As the technology relevant to the formation of semiconductor microactuator particle or its precursor layer, can enumerate: the method being carried out hydrophilization in addition by physical methods such as corona discharge, plasma, UV, utilize the chemical treatment of alkali or polyethylene dioxythiophene and polystyrolsulfon acid etc., the formation etc. of the joint intermediate coat of polyaniline etc.
As the method that semiconductor microactuator particle is coated with in conductive support body, also can by described (1) damp process and (2) drying process, (3) additive method using.
As (2) drying process, can preferably enumerate Japanese Patent Laid-Open 2000-231943 publication etc.
As (3) additive method, can preferably enumerate Japanese Patent Laid-Open 2002-134435 publication etc.
As drying process, evaporation or sputter, gas glue sedimentation etc. can be enumerated.In addition, electrophoretic method, electrolysis method can also be used.
In addition, also can be used in after heat resistant substrate temporarily makes film, be transferred to the method on the film of plastics etc.Preferably can be listed below method etc.: the method for transfer printing via ethylene-vinyl acetate (Ethylene Vinyl Acetate, EVA) recorded in Japanese Patent Laid-Open 2002-184475 publication; Record in Japanese Patent Laid-Open 2003-98977 publication after forming semiconductor layer conductive layer containing ultraviolet can be utilized, in the sacrificial substrate of inorganic salt that water solvent removes, be transferred on organic substrate, then remove the method for sacrificial substrate.
In order to adsorbable a large amount of pigment, semiconductor microactuator particle preferred surface amasss large semiconductor microactuator particle.Such as under the state that semiconductor microactuator particle is coated with on supporter, relative to shadow area, its surface-area preferably more than 10 times, more preferably more than 100 times.There is no particular restriction for its upper limit, but be generally about 5000 times.As the structure of preferred semiconductor microactuator particle, Japanese Patent Laid-Open 2001-93591 publication etc. can be enumerated.
Usually, the thickness of semiconductor microactuator particle layer is thicker, and the amount of the pigment that per unit area can carry more increases, and therefore the assimilated efficiency of light uprises, but the diffusion length of the electronics produced increases, and therefore combines produced loss again by electric charge and also increases.The preferred thickness of semiconductor microactuator particle layer is different according to the purposes of element, but typical thickness is 0.1 μm ~ 100 μm.When being used as photoelectrochemical cell, preferably 1 μm ~ 50 μm, more preferably 3 μm ~ 30 μm.Semiconductor microactuator particle, in order to make particle touch each other coating after on supporter, also can heat 10 minutes ~ 10 hours at the temperature of 100 DEG C ~ 800 DEG C.When using glass as supporter, masking temperature preferably 400 DEG C ~ 600 DEG C.
When using macromolecular material as supporter, preferably below 250 DEG C, be filmed post-heating.As film-forming method in the case, can be (1) damp process, (2) drying process, (3) electrophoretic method (comprising electrolysis method) any one, preferably (1) damp process or (2) drying process, more preferably (1) damp process.
Moreover semiconductor microactuator particle is at every 1m 2supporter on glue spread be 0.5g ~ 500g, more preferably 5g ~ 100g.
In order to make pigment be adsorbed on semiconductor microactuator particle, preferably make to be immersed in for a long time through fully dry semiconductor microactuator particle to comprise in the pigment absorption pigment solution of solution and pigment of the present invention.As long as the soluble solution of solution pigment of the present invention used in pigment absorption pigment solution, then can use with no particular limitation.Such as can use: ethanol, methyl alcohol, Virahol, toluene, the trimethyl carbinol, acetonitrile, acetone, propyl carbinol etc.Wherein, ethanol, toluene can preferably be used.
The pigment absorption pigment solution comprising solution and pigment of the present invention optionally can be heated to 50 DEG C to 100 DEG C.The absorption of pigment can be carried out before the coating of semiconductor microactuator particle, also can carry out after the coating of semiconductor microactuator particle.In addition, also can simultaneously coating semiconductor micropartical and pigment pigment is adsorbed.The pigment do not adsorbed is removed by cleaning.When carrying out the calcining of coated film, the absorption of pigment is preferably carried out after firing.After calcining, before being adsorbed in coated film surface particularly preferably in water, pigment is promptly adsorbed.The pigment of absorption can be a kind, also can by several used in combination.When mixing, by pigment mixing of the present invention of more than two kinds, also in the scope of harmless purport of the present invention, complex compound pigment can be mixed with pigment of the present invention.To expand the pigment of the way selection mixing of the wave band of opto-electronic conversion as far as possible.When being mixed by pigment, pigment absorption pigment solution must be made in the mode of all pigmentolysis.
The usage quantity of pigment in entirety, at every 1m 2supporter on preferably 0.01 mmole ~ 100 mmole, more preferably 0.1 mmole ~ 50 mmole, particularly preferably 0.1 mmole ~ 10 mmole.In the case, preferably the usage quantity of the metal complex dye represented by general formula (1) of the present invention is set to more than 5 % by mole.And then, when and with pigment represented by general formula (2) time, preferably the usage quantity of the pigment represented by general formula (2) is set to more than 80 % by mole.
In addition, about the adsorptive capacity of pigment for semiconductor microactuator particle, relative to semiconductor microactuator particle 1g, preferably 0.001 mmole ~ 1 mmole, more preferably 0.1 mmole ~ 0.5 mmole.
By being set to this kind of amount of pigment, the sensitizing effect in semi-conductor can be obtained fully.If in contrast, amount of pigment is few, then sensitizing effect becomes insufficient, if amount of pigment is too much, then the pigment do not adhered on the semiconductor suspends and becomes the reason that sensitizing effect is declined.
In addition, waiting pigment interaction each other to reduce association, also can make colourless co-adsorption.As carrying out co-adsorption hydrophobic compound, the sterid (such as cholic acid, trimethylacetic acid (pivalic acid)) etc. with carboxyl can be enumerated.
After pigment is adsorbed, the surface of amine to semiconductive particles also can be utilized to process.As preferred amine, 4-tert .-butylpyridine, polyvinylpyridine etc. can be enumerated.These amines can directly use in the case of a liquid, also can dissolve and use in organic solvent.
(to electrode)
The positive pole of electrode (counter electrode) as photoelectrochemical cell is played a role.The implication of electrode is usually identical with described conductive support body, but in the formation that such as intensity is adequately maintained, not necessarily to electrode.But, with regard to the viewpoint of stopping property, have electrode support more favourable.
As the material to electrode, platinum, carbon, electric conductive polymer etc. can be enumerated.As preferred example, platinum, carbon, electric conductive polymer can be enumerated.
As the structure to electrode, the structure that preferred current collection effect is high.As preferred example, Japanese Patent Laid-Open 10-505192 publication etc. can be enumerated.
Titanium oxide and stannic oxide (TiO can be used by optoelectronic pole 2/ SnO 2) etc. combined electrode.As the mixed electrods of titanium dioxide, include, for example the mixed electrods etc. that Japanese Patent Laid-Open 2000-113913 publication is recorded.As the mixed electrods beyond titanium dioxide, include, for example the mixed electrods etc. of Japanese Patent Laid-Open 2001-185243 publication, the record of Japanese Patent Laid-Open 2003-282164 publication.
(by optoelectronic pole)
In order to improve the utilization ratio etc. of incident light, tandem type can be set to by by optoelectronic pole.As the configuration example of preferred tandem type, example described in Japanese Patent Laid-Open 2000-90989, Japanese Patent Laid-Open 2002-90989 publication etc. can be enumerated.
Also light electrode layer inside can be provided with the light regime function of efficient carrying out scattering of light, reflection.Described in can preferably enumerating in Japanese Patent Laid-Open 2002-93476 publication.
As the formation of element, 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 also can be had.In the case, the 1st photoelectric conversion layer can be identical or different from the pigment used in the 2nd photoelectric conversion layer, and when pigment is different, preferred absorption spectrum is different.In addition, can be suitable for applying the structure applied in this kind of electrochemical element or component.
Between conductive support body and Porous semiconductor microactuator particle layer, in order to prevent directly contacting produced reverse current by electrolytic solution with electrode, be preferably formed against short-circuit layer.As preferred example, Japanese Patent Laid-Open 06-507999 publication etc. can be enumerated.
In order to prevent, by optoelectronic pole and the contact to electrode, preferably using pad or dividing plate.As preferred example, Japanese Patent Laid-Open 2001-283941 publication can be enumerated.
As the Sealing Method of unit, module, preferably aluminum alkoxide is used for the method for polyisobutene system thermosetting resin, novolac resin, photo-hardening (methyl) acrylate resin, epoxy resin, ionomer resin, glass powder, aluminum oxide, low melting glass slurry is carried out to the method etc. of lf.When using glass powder, also can be glass powder is mixed in the method become in the acrylic resin of tackiness agent.
[example]
Below, illustrate in greater detail the present invention according to example, but the present invention is not limited to these examples.
The synthesis of (synthesis example 1) exemplary compounds A-2b
Illustration compd A-2b is synthesized by the synthesis path shown in following.
[changing 41]
(1) synthesis of compound-1
To with adding dimethyl formamide 10mL, 6-bromo-2 in the there-necked flask of 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, stirs 4 hour till being heated to 110 DEG C under stream of nitrogen gas.After till being cooled to room temperature, in reaction solution, add diethyl ether and water extracts.In diethyl ether layer, add water and after again extracting, utilize magnesium sulfate to carry out predrying to diethyl ether layer, and being concentrated.Utilize alumina column chromatography to refine concentrated residue, obtain the compound-1 of 0.08g thus.
(2) synthesis of compound-2
To with adding amylalcohol 6mL, compound-10.16g, 4-tert-Butyl Phthalonitrile 0.38g, zinc chloride 0.14g and 1 in the there-necked flask of cooling tube, 8-diaza-bicyclo [5,4,0]-7-hendecene 0.5mL, stirs 25 hour till being heated to 140 DEG C under stream of nitrogen gas.After till being cooled to room temperature, by solvent concentration, methyl alcohol is utilized to carry out the rear leaching solid of suspension cleaning to residue.Thereafter, utilize the solid of alumina column chromatography to institute's leaching to refine, and then utilize HPLC to carry out point getting refining, obtain the compound-2 of 0.17g thus.
(3) synthesis of exemplary compounds A-2b
To with adding tetrahydrofuran (THF) 5mL, compound-20.1g and 1.0M aqueous sodium hydroxide solution 1mL in the there-necked flask of cooling tube, till being heated to 70 DEG C, stir 25 hours.After till being cooled to room temperature, by solvent concentration, in residue, add water 10mL, and at 100 DEG C, carry out the cleaning that suspends for 1 hour.After till being cooled to room temperature, by insolubles filtering, and add acetic acid in filtrate.Make pH become separated out crystallization filtering after below 7, obtain the A-2b of 0.08g thus.
Identified by the mensuration of milli quality (milli mass).
Mass measured value (m/z); (M+H) +: 915.3111
Mass calculated value (m/z); (M+H) +: 915.3113 (C 55h 47n 8o 2zn)
The synthesis of (synthesis example 2) exemplary compounds C-2b
Illustration Compound C-2b is synthesized by the synthesis path shown in following.
[changing 42]
(1) synthesis of compound-3
To with adding 2-butanone 40mL, 2,6-dimethylbenzene thiol 4.0g, 4,5-dichloro phthalonitrile 1.9g and salt of wormwood 6.03g in the there-necked flask of cooling tube, be heated to 80 DEG C under stream of nitrogen gas till, stir 4 hours.After till being cooled to room temperature, add water 150mL, and directly stir 1 hour.In obtained crystallization, add toluene 50mL, be heated to till 60 DEG C, and stir 30 minutes.Thereafter, add methyl alcohol 100mL, and slowly cool to till 5 DEG C.By separated out crystallization filtering, obtain the compound-3 of 3.0g thus.
(2) synthesis of compound-4
The compound-4 of 0.3g is obtained by the method identical with described compound-2.
(3) synthesis of exemplary compounds C-2b
The exemplary compounds C-2b of 0.09g is obtained by the method identical with described exemplary compounds A-2b.Identified by the mensuration of milli quality.
Mass measured value (m/z); (M+H) +: 1563.3311
Mass calculated value (m/z); (M+H) +: 1563.3315 (C 91h 71n 8o 2s 6zn)
The synthesis of (synthesis example 3) exemplary compounds D-12j
Illustration Compound D-12j is synthesized by the synthesis path shown in following.
[changing 43]
(1) synthesis of compound-5
To with adding dimethyl formamide 12.5mL, 2,6-diphenylphenol 4.7g, 4,5-dichloro phthalonitrile 1.25g and salt of wormwood 8.75g in the there-necked flask of cooling tube, be heated to 100 DEG C under stream of nitrogen gas till, stir 30 hours.After till being cooled to room temperature, adding water 150mL, and utilize methylene dichloride to extract.Thereafter, utilize anhydrous sodium sulphate to carry out predrying to dichloromethane layer, and concentrated.Utilize silica gel column chromatography to refine obtained residue, then utilize methyl alcohol to carry out recrystallize to obtained coarse crystallization, obtain the compound-5 of 1.6g thus.
(2) synthesis of compound-6
To with adding tetrahydrofuran (THF) 8mL, 4,5-diamino phthalonitrile 1.58g, dioxo dimethyl succinate 1.91g, acetic acid 1.0mL in the there-necked flask of cooling tube, be heated to 80 DEG C under stream of nitrogen gas till, stir 4 hours.After till being cooled to room temperature, in reaction solution, add water, and by separated out crystallization filtering.Utilize alumina chromatography to refine obtained crystallization, obtain the compound-6 of 1.15g thus.
(3) synthesis of compound-7
To with 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 of cooling tube, be heated under stream of nitrogen gas till 110 DEG C.Heat further after adding 1,8-diaza-bicyclo [5,4,0]-7-hendecene 0.3mL wherein, and stir 8 hours.By solvent concentration after till being cooled to room temperature, methyl alcohol is utilized to carry out the rear leaching solid of suspension cleaning to residue.Thereafter, utilize the solid of alumina column chromatography to institute's leaching to refine, obtain compound-7 runic of 0.20g thus.
(4) synthesis of compound-8
To with adding quinoline 5mL, compound-7 runic 0.62g, vanadium (III) 0.2g in the there-necked flask of cooling tube, heat 4 hours at 110 DEG C.After till being cooled to room temperature, adding water 20mL and acetic acid 30mL and also stir, then the leaching solid of separating out.Thereafter, utilize the solid of alumina column chromatography to institute's leaching carry out refining after, and then utilize HPLC to carry out point getting refining, obtain the compound-8 of 0.06g thus.
(5) synthesis of exemplary compounds D-12j
To with adding tetrahydrofuran (THF) 5mL, compound-80.23g, 1.0M aqueous sodium hydroxide solution 1mL in the there-necked flask of cooling tube, till being heated to 70 DEG C, stir 33 hours.After till being cooled to room temperature, by solvent concentration, in residue, add water 10mL, and at 100 DEG C, carry out the cleaning that suspends for 1.2 hours.After till being cooled to room temperature, by insolubles filtering, and add acetic acid in filtrate.Make pH become separated out crystallization filtering after below 7, obtain the exemplary compounds D-12j of 0.12g thus.Identified by the mensuration of milli quality.
Mass measured value (m/z); (M+H) +: 2183.5992
Mass calculated value (m/z); (M+H) +: 2183.6074 (C 144h 88n 10o 11v)
The synthesis of (synthesis example 4) exemplary compounds B-2b
Described compound-3 is become by the compound-9 synthesized by following synthesis path, in addition, obtain the exemplary compounds B-2b of 0.07g in the mode identical with synthesis example 2.
Identified by the mensuration of milli quality.
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]
The synthesis of (synthesis example 5) exemplary compounds E-2b
Described compound-3 is become by the compound-10 synthesized by following synthesis path, in addition, obtain the exemplary compounds E-2b of 0.05g in the mode identical with synthesis example 2.
Identified by the mensuration of milli quality.
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]
The synthesis of (synthesis example 6) comparative compound S-2
Synthesis ratio comparatively compound S-2 is carried out by the synthesis path shown in following.
[changing 46]
(1) synthesis of compound-11
To with adding dimethyl formamide 10mL, 4-iodo-phthalonitrile 0.13g, 4-(methoxycarbonyl) phenyl-boron dihydroxide 0.18g, 1 in the there-necked flask of cooling tube, 4-diaza-bicyclo [2,2,2] octane 0.5mL, cesium carbonate 0.54g and palladium (II) 0.03g, stirs 4 hour till being heated to 110 DEG C under stream of nitrogen gas.After till being cooled to room temperature, in reaction solution, add diethyl ether and water extracts.In diethyl ether layer, add water and after again extracting, utilize magnesium sulfate to carry out predrying to diethyl ether layer, and being concentrated.Utilize alumina column chromatography to refine concentrated residue, obtain the compound-11 of 0.08g thus.
(2) synthesis of compound-12
The compound-12 of 0.3g is obtained by the method identical with described compound-2.
(3) synthesis of comparative compound S-2
The comparative compound S-2 of 0.08g is obtained by the method identical with described exemplary compounds A-2b.
Identified by the mensuration of milli quality.
Mass measured value (m/z); (M+H) +: 1513.3155
Mass calculated value (m/z); (M+H) +: 1513.3159 (C 87h 69n 8o 2s 6zn)
The synthesis of (synthesis example 7) comparative compound S-1
According to the international version (Angew.Chem.Int.Ed.) of applied chemistry, 46,8358 (2007), synthesize following comparative compound S-1.
[changing 47]
The mensuration of the maximum absorption wavelength of (test example) pigment
For metal complex dye synthesized in described synthesis example 1 ~ synthesis example 7, measure maximum absorption wavelength.The results are shown in table 1.Mensuration utilizes spectrophotometer (U-4100 (trade(brand)name), Hitachi's new and high technology (Hitachi High-Technologies) company manufactures) carry out, solution uses THF: ethanol=1:1, and adjusts in the mode that concentration becomes 2 μMs.
[table 1]
Table 1
And then, in the absorption spectrum of described metal complex dye, measure the difference be arranged in less than the longest maximum absorption wavelength at wavelength place of the wavelength of 500nm and the maximum absorption wavelength of the wavelength of more than 500nm.The results are shown in table 2.The maximum absorption wavelength being arranged in the longest wavelength place of the wavelength less than 500nm is derived from Q band, and the maximum absorption wavelength in the wavelength of more than 500nm is derived from Soret spy band, and this difference is less, represents that non-absorption band is narrower and small.
[table 2]
Table 2
According to the result of table 2, compared with the pigment of comparative example, the non-absorption band of metal complex dye of the present invention is narrow and small, and be in the Soret spy band long wavelengthization in ultraviolet region, light absorption wave band is wide.
[experiment 1]
(making of photo-electric conversion element)
Photo-electric conversion element 10 as follows shown in construction drawing 1.
On the glass substrate, form stannic oxide doped with fluorine as nesa coating by sputter, utilize laser to rule to it, and nesa coating is divided into 2 parts.
Then, anatase-type titanium oxide (P-25 (trade(brand)name) that Japanese Ai Luoxier (Aerosil) company manufactures) 32g is allocated in the mixed solvent 100ml comprising 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 obtain semiconductor microactuator particle dispersion liquid.This dispersion liquid is coated on nesa coating, and carries out heating and making by optoelectronic pole at 500 DEG C.
Thereafter, similarly make with the dispersion liquid of 40:60 (mass ratio) containing silicon dioxide granule and Titanium Dioxide (Rutile) Top grade, this dispersion liquid is coated on described by optoelectronic pole, and carries out heating and forming insulativity porous insert at 500 DEG C.Then, carbon dioxide process carbon electrode is formed as to electrode.
Then, the ethanolic soln (3 × 10 of the sensitizing coloring matter of glass substrate described in following table 3 being formed with described insulativity porous insert is made -4mol/L) dipping 48 hours in.The glass being stained with sensitizing coloring matter is flooded after 30 minutes in 10% ethanolic soln of 4-tert .-butylpyridine, utilizes ethanol carry out cleaning and make its seasoning.The thickness of the photoreceptor layers obtained in this way is 10 μm, and the glue spread of semiconductor microactuator particle is 20g/m 2.Electrolytic solution uses 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 through AMl.5G spectral filter (trade(brand)name, Ao Lier (Oriel) company manufactures) and sharp wave spectral filter (sharp cut filter) (Ken Keer-42 (KenkoL-42), trade(brand)name), produce thus not containing ultraviolet simulated solar irradiation.The intensity of this light is 89mW/cm 2.This light is irradiated to made photo-electric conversion element, and utilizes current/voltage determinator (Keithley (Keithley) 238 type, trade(brand)name) to measure produced electricity.In addition, the photoelectric transformation efficiency of photo-electric conversion element under 400nm ~ 800nm made by photoelectric transformation efficiency (Incident Photon to Current Efficiency, the IPCE) determinator utilizing peck Xie Er (Peccell) company to manufacture measures.Photoelectric transformation efficiency (IPCE) under the result measured the efficiency of conversion by the photoelectrochemical cell calculated by these modes and 450nm is shown in following table 3.Be efficiency of conversion by the result of efficiency of conversion be that more than 3.5% person is evaluated as ◎, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 3]
Table 3
As shown in table 3, use the photoelectrochemical cell made by metal complex dye of the present invention, especially when using A-3c, A-12b, A-12h, A-13b, B-14b, D-2b, D-14b, E-14b as pigment, IPCE is high, as its result, the high level of efficiency of conversion display more than 3.5%.Even if when using other pigments of the present invention, efficiency of conversion is also more than 2.5%, higher level less than 3.5%.
In contrast, the efficiency of conversion of the comparative example of specimen coding 1-17 and specimen coding 1-18 is insufficient less than 2.0%.
[experiment 2]
Make ITO (tin indium oxide) film on the glass substrate, and in ito film lamination FTO (fluorine-doped tin oxide) film, make nesa coating thus.Thereafter, nesa coating is formed oxide semiconductor porous film, obtains transparent electrode plate thus.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) the ito film preparation of starting compound solution
Indium chloride (III) tetrahydrate 5.58g and tin chloride (II) dihydrate 0.23g is dissolved in ethanol 100ml, and makes ito film starting compound solution.
(2) the FTO film preparation of starting compound solution
Tin chloride (IV) pentahydrate 0.701g is made to be dissolved in ethanol 10ml, and add the saturated aqueous solution of Neutral ammonium fluoride 0.592g wherein, in Ultrasonic Cleaners, last about 20 minutes makes this mixture dissolve completely, and makes FTO film starting compound solution.
(3) making of ITO/FTO nesa coating
Be that matting is carried out on the surface of the heat resistant glass plate of 2mm to thickness, in addition after drying, this sheet glass be placed in reactor, and utilize well heater to heat.When the Heating temperature of well heater becomes 450 DEG C, under the pressure of 0.06MPa, the distance apart from sheet glass is set to 400mm and makes the ito film starting compound solution obtained in (1) carry out spraying in 25 minutes from the nozzle that bore is 0.3mm.
After the spraying of this ito film with starting compound solution, (during this period, ethanol spraying was continued to glass baseplate surface through 2 minutes, and suppress the rising of substrate surface temperature), when the Heating temperature of well heater becomes 530 DEG C, the FTO film starting compound solution obtained in (2) is made to carry out 2 points of sprayings in 30 seconds at identical conditions.Thus, obtain on heat resistant glass plate, to be formed with ito film that thickness is 530nm successively, transparent electrode plate that thickness is the FTO film of 170nm.
In order to compare, make in the same manner only make thickness be the ito film of 530nm at thickness to be 2mm heat resistant glass plate on the transparent electrode plate of film forming, and make in the same manner only make thickness be the FTO film of 180nm at thickness to be 2mm heat resistant glass plate on the transparent electrode plate of film forming.
Utilize process furnace, at 450 DEG C, heating in 2 hours is carried out to described 3 kinds of transparent electrode plates.
(4) making of photoelectrochemical cell
Then, use described 3 kinds of transparent electrode plates, make the photoelectrochemical cell of the structure shown in Fig. 2 in Japanese Patent No. 4260494 specification sheets.The formation of oxide semiconductor porous film 15 is that the titanium oxide microparticle making median size be about 230nm is dispersed in acetonitrile 100ml and makes slurry, transparency electrode 11 utilizing stick coating method be coated into thickness is 15 μm, at 450 DEG C, carry out calcining in 1 hour after drying, on this oxide semiconductor porous film 15, then carry the pigment recorded in table 4.Immersion condition in pigment solution is set to identical with described experiment 1.
And then, there is the conductive board of ito film and FTO film to be used for electrode 16 lamination on a glass, will the used for electrolyte in dielectric substrate 17 of the non-aqueous solution of iodine/iodide be comprised.The planar dimension of photoelectrochemical cell is set to 25mm × 25mm.
(5) evaluation of photoelectrochemical cell
Simulated sunlight (AM1.5) is irradiated to this photoelectrochemical cell, and obtains its efficiency of conversion.The results are shown in table 4.Be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 4]
Table 4
Known use S-1 is low as the efficiency of conversion of the specimen coding 2-10 ~ specimen coding 2-12 of sensitizing coloring matter, in contrast, use the specimen coding of metal complex dye of the present invention 2-1 ~ specimen coding 2-9 to show good result.Known with use only make the transparent electrode plate of ito film or FTO film film forming as transparent electrode plate situation compared with, 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.
[experiment 3]
FTO film configures collecting electrodes to make photoelectrochemical cell, and evaluate efficiency of conversion.Evaluate as described below, use-testing unit (i) and test unit (iv) 2 kinds of test units.
(test unit (i))
Matting is carried out to the surface of 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 heat, under the pressure of 0.06MPa, distance apart from sheet glass be set to 400mm and make FTO (fluorine-doped tin oxide) film starting compound solution prepared in experiment 2 carry out spraying in 25 minutes from the nozzle that bore is 0.3mm, and preparing the glass substrate with FTO film.On its surface, the flute profile being 5 μm by the degree of depth by etching method becomes grid circuit pattern shape.After forming pattern by photoetching, hydrofluoric acid is used to etch.In order to can coating be formed, utilize sputtering method to form metal conducting layer (Seed Layer) thereon, and then form metallic wiring layer by additivity plating (additive plating).Metallic wiring layer be from transparency carrier surface, be formed to 3 μm of height in lens-shaped till.Circuit width is set to 60 μm.From this metallic wiring layer, utilize large plastometric set (Severe Plastic Deformation, SPD) method to form FTO film as shielding layer using the thickness of 400nm, and make electrode base board (i).Moreover the section shape of electrode base board (i) becomes the section shape shown in Fig. 2 in Japanese Patent Laid-Open 2004-146425.
Dispersion liquid titanium oxide that median size is 25nm being dispersed in obtain in acetonitrile 100ml in electrode base board (i) upper coating is also in addition dry, then at 450 DEG C, carries out heat-agglomerating in 1 hour.Making it be immersed in the ethanolic soln of the pigment shown in table 5 makes pigment adsorb.Immersion condition is set to test 1 identical.Via 50 μm of thick thermoplastic polyolefin resin's sheets, itself and platinum sputter FTO substrate subtend are configured, then make resin sheet portion heat fusing be fixed by two battery lead plates.
Moreover, from the spout of electrolytic solution being opened in platinum sputter cathode side in advance, inject the methoxyacetonitrile solution that principal constituent comprises the iodized salt of 0.5M and the iodine of 0.05M, and make between electrode, to be full of this solution.And then, use epoxy sealing resin periphery and injecting electrolytic solution mouth formally to be sealed, and make test unit (i) at current-collecting terminals portion silver coating slurry.
Utilize the simulated solar irradiation of AM1.5, the efficiency of conversion of test unit (i) is evaluated.The results are shown in table 5.
(test unit (iv))
The glass substrate with FTO film of length 100mm × width 100mm is prepared with the method identical with test unit (i).On this FTO glass substrate, metallic wiring layer (golden circuit) is formed by additivity electrochemical plating.Metallic wiring layer (golden circuit) is formed in substrate surface in lattice shape, and circuit width is set to 50 μm, circuit thickness is set to 5 μm.To utilize SPD method to form thickness on its surface be 300nm FTO film as shielding layer, and makes test unit (iv).Utilize scanning electron microscope (the Scanning Electron Microscopy with Energy Dispersive X-ray of band power spectrum, SEM-EDX) section of electrode base board (iv) is confirmed, there is the end be considered to by resistance plating agent and roll caused piercing in result, and be not coated with FTO in backlight portion bottom distribution.
Use electrode base board (iv), make test unit (iv) in the same manner as test unit (i).Utilize the simulated solar irradiation of AM1.5, the efficiency of conversion of test unit (iv) is evaluated, and shows the result in table 5.
Moreover, be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 5]
Table 5
According to table 5, when using metal complex dye of the present invention, the high level of the efficiency of conversion display more than 3.5% when test unit (i).On the other hand, if observe the situation of use-testing unit (iv), then, compared with the situation of the pigment of use comparative example, when using 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 that test unit is selected rises (specimen coding 3-2, specimen coding 3-4, specimen coding 3-6, specimen coding 3-8 and specimen coding 3-10 compare with specimen coding 3-12's).
[experiment 4]
As shown in following, make photoelectrochemical cell (photocell unit) (A) ~ photoelectrochemical cell (photocell unit) (D), and the efficiency of conversion of made photocell unit is evaluated.
(photocell unit (A))
(1) oxide semiconductor film forms the preparation with coating fluid (A)
Make the titanium hydride of 5g be suspended in the pure water of 1L, last 30 minutes and add the hydrogen peroxide liquid 400g of 5 quality %, be then heated to 80 DEG C carry out dissolve and make the solution of pertitanic acid.From the total amount of this solution, point get 90 volume %, and add strong aqua pH is adjusted to 9, be then added in autoclave, carry out 5 hours hydrothermal treatment consists in saturated vapo(u)r pressure with 250 DEG C and make titania colloid particles (A).According to X-ray diffraction, the titania colloid particles (A) obtained is the high anatase-type titanium oxide of crystallinity.
Then, till the titania colloid particles (A) obtained by described mode is concentrated into 10 quality %, and mix described pertitanic acid solution, then TiO is carried out to the titanium in this mixed solution 2convert, to become TiO 2the mode of 30 quality % of quality adds the hydroxypropylcellulose forming auxiliary agent as film, and makes semiconductor film formation 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 being coated with described coating fluid (A), and making its seasoning, then use low-pressure mercury light irradiation 6000mJ/cm 2ultraviolet peroxy acid is decomposed, and film is hardened.At 300 DEG C, film is heated 30 minutes to carry out decomposition and the annealing of hydroxypropylcellulose, thus form oxide semiconductor film (A) on the glass substrate.
(3) pigment is towards the absorption on oxide semiconductor film (A)
Then, the concentration prepared as the pigment shown in the table 6 of light splitting sensitizing coloring matter is 3 × 10 -4the ethanolic soln of mol/L.100rpm turner is utilized this pigment solution to be coated on oxide semiconductor film (A) upper and in addition dry.This coating and drying step are carried out 5 times.
(4) preparation of electrolyte solution
Be in the mixed solvent of 1:5 in the volume ratio of acetonitrile and NSC 11801, make both dissolve with the concentration making tetrapropyl ammonium iodide become 0.46mol/L, the mode that makes iodine become the concentration of 0.07mol/L and make electrolyte solution.
(5) making of photocell unit (A)
Using the electrode of glass substrate as side being formed with the oxide semiconductor film (A) making pigment adsorb made in described (3), following transparent glass substrate is configured as the electrode of opposite side with its subtend, this transparent glass substrate is formed as electrode by fluorine-doped tin oxide and carries the transparent glass substrate of platinum thereon, utilize resin by side seal, and enclosed between electrode by electrolyte solution prepared in described (4), and then wire is utilized to be made photocell unit (A) by connecting between electrode.
(6) evaluation of photocell unit (A)
Solar simulator is utilized to be 100W/m to photocell unit (A) exposure intensity 2light, and measure η (efficiency of conversion).The results are shown in table 6.
(photocell unit (B))
Irradiation ultraviolet radiation makes peroxy acid decompose, after film is hardened, carry out ion exposure (the day new Electric Manufacture: ion implantation apparatus of Ar gas, irradiate 10 hours under 200eV), in addition, oxide semiconductor film (B) is formed in the mode identical with oxide semiconductor film (A).
In the same manner as oxide semiconductor film (A), the absorption of the pigment shown in oxide semiconductor film (B) carry out table 6.
Thereafter, make photocell unit (B) with the method identical with photocell unit (A), and measure efficiency of conversion.The results are shown in table 6.
(photocell unit (C))
The titanium tetrachloride of pure water to 18.3g is utilized to dilute, with TiO 2the meter that converts obtains the aqueous solution of the titanium tetrachloride containing 1.0 quality %.Faced by one, this aqueous solution stirs, and one side adds the ammoniacal liquor of 15 quality %, and obtains the white slurry that pH is 9.5.Filtration cleaning is carried out, with TiO to this slurry 2convert meter, obtains the block of the aqua oxidation titanium gel of 10.2 quality %.This block is mixed with 5 quality % hydrogen peroxide liquid 400g, is then heated to 80 DEG C carry out dissolve and makes the solution of pertitanic acid.Divide from the total amount of this solution and get 90 volume %, and pH is adjusted to 9 by interpolation strong aqua wherein, is then added in autoclave, carry out 5 hours hydrothermal treatment consists in saturated vapo(u)r pressure with 250 DEG C and make titania colloid particles (C).
Then, use the pertitanic acid solution and titania colloid particles (C) that are obtained by described mode, form oxide semiconductor film (C) in the mode identical with oxide semiconductor film (A).And then, in the mode identical with oxide semiconductor film (A), carry out the absorption as the pigment shown in the table 6 of light splitting sensitizing coloring matter.
Thereafter, make photocell unit (C) with the method identical with photocell unit (A), and measure efficiency of conversion.The results are shown in table 6.
(photocell unit (D))
The titanium tetrachloride of pure water to 18.3g is utilized to dilute, with TiO 2the meter that converts obtains the aqueous solution of the titanium tetrachloride containing 1.0 quality %.Faced by one, this aqueous solution stirs, and one side adds the ammoniacal liquor of 15 quality %, and obtains the white slurry that pH is 9.5.After filtration cleaning is carried out to this slurry, make it be suspended in pure water and be made as TiO 2the slurry of aqua oxidation titanium gel of 0.6 quality %, add after hydrochloric acid makes pH become 2 wherein, be added in autoclave, carry out 5 hours hydrothermal treatment consists in saturated vapo(u)r pressure with 180 DEG C and make titania colloid particles (D).
Then, till titania colloid particles (D) is concentrated into 10 quality %, to be converted into TiO 2after become 30 quality % mode add the hydroxypropylcellulose forming auxiliary agent as film wherein, and make semiconductor film formation coating fluid.Then, be coated with described coating fluid as on the transparent glass substrate of electrode layer being formed with fluorine-doped tin oxide, and make its seasoning, then use low-pressure mercury light irradiation 6000mJ/cm 2ultraviolet film is hardened.And then at 300 DEG C, decomposition and the annealing of hydroxypropylcellulose is carried out in heating for 30 minutes, thus forms oxide semiconductor film (D).
Then, carry out table 6 in the mode identical with oxide semiconductor film (A) shown in the absorption of pigment.
Thereafter, make photocell unit (D) with the method identical with photocell unit (A), and measure efficiency of conversion.Show the result in table 6.
Moreover, be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 6]
Table 6
Known according to table 6, compared with the photocell unit of comparative example, use the efficiency of conversion of the photocell unit of metal complex dye of the present invention high.Especially, known when metal complex dye of the present invention being used for photocell unit (A) ~ photocell unit (C), efficiency of conversion is high especially.
[experiment 5]
As shown in following, carry out preparation or the synthesis of titanium oxide, make oxide semiconductor film by obtained titanium oxide, and make photoelectrochemical cell, and it is evaluated.
(1) preparation of the titanium oxide 1 of heat treating process is utilized
Use commercially available anatase-type titanium oxide (stone originates in industry (share) manufacture, trade(brand)name ST-01), be heated to about 900 DEG C and convert the titanium oxide 1 of brookite type to.
(2) titanium oxide 2 (brookite type) of damp process and the synthesis (titanium oxide 2 (brookite type)) of titanium oxide 3 (brookite type) is utilized
Distilled water 954mL is loaded in the reactive tank with reflux cooler, and heats to 95 DEG C.Stirring velocity is remained about 200rpm by one side, and titanium tetrachloride (Ti content: 16.3 quality %, proportion is 1.59, and purity is 99.9%) aqueous solution 46mL drops in reactive tank with the speed of about 5.0mL/min by one side.Now, note not making the temperature of reaction solution decline.Its result, titanium tetrachloride concentration is 0.25mol/L (titanium oxide is scaled 2 quality %).In reactive tank, immediately start after dropwise reaction liquid to produce white Turbid, but continue to keep with the temperature under this state, drip after terminating and then heat up and be heated near boiling point till (104 DEG C), keeping in this condition making the end that reacts completely after 60 minutes.
Obtained colloidal sol is filtered, then uses the vacuum drier of 60 DEG C to make powder.X-ray diffraction method is utilized 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 obtain the crystallinity of obtained titanium oxide according to these, then the crystallinity of obtained titanium oxide is the crystallinity that brookite type is about 70.0 quality %, rutile-type is about 1.2 quality %, Detitanium-ore-type is about 28.8 quality %.In addition, utilize transmission electron microscope to observe this micropartical, the median size of 1 particle is 0.015 μm as a result.
(titanium oxide 3 (brookite type))
Utilize distilled water to dilute titanium trichloride aqueous solution (Ti content: 28 quality %, proportion is 1.5, and purity is 99.9%), make the solution of 0.25mol/L in titanium concentration conversion.Now, the mode do not risen with liquid temperature carries out ice bath cooling, and remains less than 50 DEG C.Then, this solution 500mL is fed in the reactive tank with reflux cooler, one side heat to make to 85 DEG C of one sides from ozone gas generation device purity be 80% ozone gas bubble with 1L/min, and carry out oxidizing reaction.Keep in this condition making the end that reacts completely after 2 hours.
Obtained colloidal sol is filtered, vacuum-drying and make powder.X-ray diffraction method is utilized 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 obtain the crystallinity of obtained titanium oxide according to these, then the crystallinity of obtained titanium oxide is that brookite type is about 98 quality %, rutile-type is 0 quality %, Detitanium-ore-type is 0 quality %, about 2% for amorphous.In addition, utilize transmission electron microscope to observe this micropartical, the median size of 1 particle is 0.05 μm 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 shown in the Fig. 1 with Japanese Patent Laid-Open 2000-340269 as following.
Be coated with fluorine-doped tin oxide on the glass substrate, and make conductive clear electrode.Electrode surface makes using the slurry of each Titanium particles as raw material, utilizing stick coating method to be coated into thickness is after 50 μm, carries out calcining and forming the thin layer that thickness is about 20 μm at 500 DEG C.Then, the pigment shown in preparation table 7 is 3 × 10 -4the ethanolic soln of volumetric molar concentration, makes the glass substrate of the thin layer being formed with described titanium oxide be immersed in this ethanolic soln, and at room temperature keeps 12 hours.
Use the acetonitrile solution of the salt compounded of iodine of tetrapropyl ammonium and lithium iodide as electrolytic solution, using platinum as photo-electric conversion element electrode being made to the formation shown in the Fig. 1 with Japanese Patent Laid-Open 2000-340269.Opto-electronic conversion is the light (utilizing spectral filter to end infrared rays portion) of the high pressure mercury vapour lamp described element being irradiated to 160W, and measures efficiency of conversion now.Show the result in table 7.
Moreover, be that more than 3.5% person is expressed as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be expressed as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be expressed as △ less than 2.5%, by efficiency of conversion less than 2.0% being expressed as ×.
[table 7]
Table 7
Known according to table 7, use the efficiency of conversion of the photo-electric conversion element of metal complex dye of the present invention high.
[experiment 6]
As shown in following, use the semi-conducting electrode containing the different titanium oxide of particle diameter to make photoelectrochemical cell, and evaluate its characteristic.
[preparation of slurry]
First, prepared in order to form the semiconductor layer of semi-conducting electrode or the slurry of light scattering layer that form photoelectrochemical cell by following program.
(preparation of slurry 1)
By spherical TiO 2(Detitanium-ore-type, median size: 25nm, hereinafter referred to as spherical TiO for particle 2particle 1) to be added in salpeter solution and to stir, make titania slurry thus.Then, in titania slurry, add the cellulose-based tackiness agent as tackifier, and carry out mixing and making slurry 1.
(preparation of slurry 2)
By spherical TiO 2particle 1 and other spherical TiO 2(Detitanium-ore-type, median size: 200nm, hereinafter referred to as spherical TiO for particle 2particle 2) to be added in salpeter solution and to stir, make titania slurry thus.Then, in titania slurry, add the cellulose-based tackiness agent as tackifier, and carry out mixing and making slurry 2 (TiO 2the quality of particle 1: TiO 2quality=the 30:70 of particle 2).
(preparation of slurry 3)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 5, hereinafter referred to as bar-shaped TiO for Detitanium-ore-type, diameter: 100nm for particle 2particle 1) mixing, make bar-shaped TiO 2the quality of particle 1: the slurry 3 of the quality=10:90 of slurry 1.
(preparation of slurry 4)
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 the quality=30:70 of slurry 1.
(preparation of slurry 5)
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 the quality=50:50 of slurry 1.
(preparation of slurry 6)
Described slurry 1 is mixed with the mica particle (diameter: 100nm, aspect ratio: 6, hereinafter referred to as sheet mica particle 1) of tabular, makes the quality of tabular mica particle 1: the slurry 6 of the quality=20:80 of slurry 1.
(preparation of slurry 7)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 6.3, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 30nm for particle 2particle 2) mixing, make bar-shaped TiO 2the quality of particle 2: the slurry 7 of the quality=30:70 of slurry 1.
(preparation of slurry 8)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 6.1, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 50nm for particle 2particle 3) mixing, make bar-shaped TiO 2the quality of particle 3: the slurry 8 of the quality=30:70 of slurry 1.
(preparation of slurry 9)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 5.8, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 75nm for particle 2particle 4) mixing, make bar-shaped TiO 2the quality of particle 4: the slurry 9 of the quality=30:70 of slurry 1.
(preparation of slurry 10)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 5.2, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 130nm for particle 2particle 5) mixing, make bar-shaped TiO 2the quality of particle 5: the slurry 10 of the quality=30:70 of slurry 1.
(slurry 11)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 5, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 180nm for particle 2particle 6) mixing, make bar-shaped TiO 2the quality of particle 6: the slurry 11 of the quality=30:70 of slurry 1.
(preparation of slurry 12)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 5, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 240nm for particle 2particle 7) mixing, make bar-shaped TiO 2the quality of particle 7: the slurry 12 of the quality=30:70 of slurry 1.
(preparation of slurry 13)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 4.1, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 110nm for particle 2particle 8) mixing, make bar-shaped TiO 2the quality of particle 8: the slurry 13 of the quality=30:70 of slurry 1.
(preparation of slurry 14)
By described slurry 1 and bar-shaped TiO 2(aspect ratio: 3.4, hereinafter referred to as bar-shaped TiO for anatase octahedrite, diameter: 105nm for particle 2particle 9) mixing, make bar-shaped TiO 2the quality of particle 9: the slurry 14 of the quality=30:70 of slurry 1.
[making of photoelectrochemical cell]
(photoelectrochemical cell 1)
By program shown below, make the optoelectronic pole with the formation identical with the optoelectronic pole 12 shown in the Fig. 5 recorded in Japanese Patent Laid-Open 2002-289274, and then use optoelectronic pole, make the photoelectrochemical cell 1 except this optoelectronic pole with the scale of the 10mm × 10mm of the formation identical with dye-sensitized solar cell 20.
Prepare the SnO doped with fluorine 2conducting film (thickness: 500nm) forms transparency electrode on the glass substrate.Then, by described slurry 2 screen painting at this SnO 2on conducting film, then in addition dry.Thereafter, with in air, the condition of 450 DEG C calcines.And then, use described slurry 4 to repeat this screen painting and calcining, thus at SnO 2conducting film is formed the semi-conducting electrode (area of sensitive surface: 10mm × 10mm of the formation identical with the semi-conducting electrode 2 shown in Fig. 5, thickness: 10 μm, the thickness of semiconductor layer: 6 μm, the thickness of light scattering layer: 4 μm, bar-shaped TiO contained in light scattering layer 2the containing ratio of particle 1: 30 quality %), and make not containing the optoelectronic pole of sensitizing coloring matter.
Then, the pigment shown in table 8 is made to be adsorbed on as follows on semi-conducting electrode.
First, the dehydrated alcohol that will be dewatered 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 about 1.5 mmoles/m 2pigment be adsorbed on semi-conducting electrode, and complete optoelectronic pole.
Then, preparation has platinum electrode (thickness of Pt film: the 100nm) conduct of the shape identical with described optoelectronic pole and size to electrode, and preparation contains the iodine system redox solution of iodine and lithium iodide as ionogen E.And then, the pad S (trade(brand)name: " giving up beautiful jade (Surlyn) ") that the E.I.Du Pont Company preparing to have the shape of coincideing with the size of semi-conducting electrode manufactures, as as shown in Fig. 3 of recording 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 the manufacture of semi-conducting electrode as follows, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 2 of the formation identical with the dye-sensitized solar cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 1 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.
Described slurry 2 is used as semiconductor layer formation slurry.Then, by described slurry 2 screen painting at SnO 2on conducting film, then in addition dry.Thereafter, with in air, the condition of 450 DEG C calcines, and forms semiconductor layer.
Described slurry 3 is used as the inner most layer formation slurry of light scattering layer.In addition, described slurry 5 is used as the outermost layer formation slurry of light scattering layer.Then, light scattering layer is formed on the semiconductor layer in the mode identical with dye-sensitized solar cell 1.
Then, at SnO 2conducting film is formed the semi-conducting electrode (area of sensitive surface: 10mm × 10mm of the formation identical with the semi-conducting electrode 2 shown in the Fig. 1 recorded in Japanese Patent Laid-Open 2002-289274, thickness: 10 μm, the thickness of semiconductor layer: 3 μm, the thickness of inner most layer: 4 μm, bar-shaped TiO contained in inner most layer 2the containing ratio of particle 1: 10 quality %, the thickness of outermost layer: 3 μm, bar-shaped TiO contained in outermost layer 2the containing ratio of particle 1: 50 quality %), and make not containing the optoelectronic pole of sensitizing coloring matter.In the same manner as photoelectrochemical cell 1, 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 used as semiconductor layer formation slurry, described slurry 4 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 3 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, the area of the sensitive surface of semi-conducting electrode: 10mm × 10mm, thickness: 10 μm, the thickness of semiconductor layer: 5 μm, the thickness of light scattering layer: 5 μm, bar-shaped TiO contained in light scattering layer 2the containing ratio of particle 1: 30 quality %.
(photoelectrochemical cell 4)
When manufacturing semi-conducting electrode, described slurry 2 is used as semiconductor layer formation slurry, described slurry 6 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 4 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, the area of the sensitive surface of semi-conducting electrode: 10mm × 10mm, thickness: 10 μm, the thickness of semiconductor layer: 6.5 μm, the thickness of light scattering layer: 3.5 μm, the containing ratio of sheet mica particle 1 contained in light scattering layer: 20 quality %.
(photoelectrochemical cell 5)
When manufacturing semi-conducting electrode, described slurry 2 is used as semiconductor layer formation slurry, described slurry 8 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 5 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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 used as semiconductor layer formation slurry, described slurry 9 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 6 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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 used as semiconductor layer formation slurry, described slurry 10 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 7 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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 used as semiconductor layer formation slurry, described slurry 11 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 8 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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 used as semiconductor layer formation slurry, described slurry 13 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 9 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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 used as semiconductor layer formation slurry, described slurry 14 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 10 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained 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, semi-conducting electrode (the area of sensitive surface: 10mm × 10mm only using described slurry 2 to make only to comprise semiconductor layer, thickness: 10 μm), in addition, with the program making optoelectronic pole identical with photoelectrochemical cell 1 and photoelectrochemical cell 11.
(photoelectrochemical cell 12)
When manufacturing semi-conducting electrode, described slurry 2 is used as semiconductor layer formation slurry, described slurry 7 is used as light scattering layer formation slurry, in addition, there is with the program making identical with photoelectrochemical cell 1 optoelectronic pole and the photoelectrochemical cell 12 of the formation identical with the photoelectrochemical cell 20 shown in Fig. 3 of recording in the optoelectronic pole 10 shown in Fig. 5 of recording in Japanese Patent Laid-Open 2002-289274 and Japanese Patent Laid-Open 2002-289274.Moreover, bar-shaped TiO contained in the light scattering layer of semi-conducting electrode 2the containing ratio of particle 2: 30 quality %.
[battery behavior test]
Carry out battery behavior test, efficiency eta is measured to photoelectrochemical cell 1 ~ photoelectrochemical cell 12.Battery behavior test is by using Tai Yang Mo Be device (manufacturing with hat (WACOM), trade(brand)name WXS-85H), irradiating the 1000W/m from xenon lamp that have passed through AM1.5 spectral filter 2simulated solar irradiation carry out.Use I-V tester to measure I-E characteristic, and obtain effciency of energy transfer (η/%).The results are shown in table 8.
Moreover, be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 8]
Table 8
As shown in table 8, use the efficiency of conversion of the photoelectrochemical cell of metal complex dye of the present invention high.
[experiment 7]
Becoming add metal alkoxide in metal oxide microparticle into pulp-like person is coated on conductive board, thereafter, carries out the irradiation of UV ozone, UV irradiation or dry, and makes electrode.Thereafter, make photoelectrochemical cell, and measure efficiency of conversion.
(metal oxide microparticle)
As metal oxide microparticle, use titanium oxide.Titanium oxide uses 30% be Detitanium-ore-type and the median size P25 powder (manufacture of Degussa (Degussa) company, trade(brand)name) that is 25nm for rutile-type, 70% by quality ratio.
(pre-treatment of the sub-powder of metal oxide microparticle)
Metal oxide microparticle is heat-treated, thus by the organism on surface and moisture removal in advance.When titanium oxide microparticle, the baking oven of 450 DEG C is utilized to heat 30 minutes under air.
(mensuration of amount of moisture contained in metal oxide microparticle)
Ka Er Fischer (Kcal Fisher) titration of the amount of moisture departed from when being spattered less by the weight in thermogravimetric flow measurement and be heated to 300 DEG C, contained amount of moisture in the titanium oxide be kept in the environment of temperature 26 DEG C, humidity 72%, P25 powder (Degussa (Degussa) company manufactures, trade(brand)name) is carried out quantitatively.
By Carl Fischer titration, to heated oxide titanium at 300 DEG C, P25 powder, (Degussa (Degussa) company manufactures, trade(brand)name) time the amount of moisture that departs from carry out quantitatively, contain the water of 0.253mg in the titanium oxide fine powder end of result 0.1033g.Namely, titanium oxide fine powder end is containing the moisture of the 2.5wt% that has an appointment (% by weight), therefore the sub-powder of metal oxide microparticle is with before the mixing of metal alkoxide, and utilizes the baking oven of 450 DEG C to carry out thermal treatment in 30 minutes, is kept in moisture eliminator and uses after cooling.
(preparation of metal alkoxide slurry)
As the metal alkoxide of the effect of performance bond metal oxide microparticle, use tetraisopropoxy titanium (IV) (Titanium tetraisopropoxide, TTIP) as titanium material, use four n-propoxyzirconium (IV) as zirconium raw material, use five oxyethyl group niobiums (V) as niobium raw material (being aldrich (Aldrich) company to manufacture).
Metal oxide microparticle is unduly thickening with the amorphous layer produced by the hydrolysis of metal alkoxide with the molar concentration rate of metal alkoxide and the mode that can carry out fully of particle combination each other, suitablely corresponding to the sub-diameter of metal oxide microparticle regulates.Moreover, metal alkoxide is all made the ethanolic soln of 0.1M.When titanium oxide microparticle is mixed with tetraisopropoxy titanium (IV) (TTIP), relative to titanium oxide microparticle 1g, the TTIP solution of the 0.1M of mixing 3.55g.Now, the titanium oxide concentration in the slurry obtained becomes about 22 quality %, and becomes the viscosity being suitable for being coated with.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 also becoming 22 quality % with micropartical concentration.16 quality % are set in the slurry using zinc oxide and tin oxide particles.When zinc oxide and stannic oxide, with relative to the sub-1g of metal oxide microparticle, metal alkoxide solution is that the ratio of 5.25g mixes.
In encloses container, utilize magnetic stirring apparatus metal oxide microparticle and metal alkoxide solution stirring 2 hours to be obtained and starch uniformly.
The coating process being coated with slurry on conductive board can use doctor method, screen painting method, spraying method etc., and suitable slurry viscosity is selects suitable according to coating process.Herein, the method (being similar to doctor method) be coated with by glass stick is used easily.In the case, the concentration of giving metal oxide microparticle of suitable slurry viscosity becomes the scope of general 5 quality % ~ 30 quality %.
In this example, the layer thickness of the amorphous metal oxide generated by the decomposition of metal alkoxide is in the scope of about 0.1nm ~ 0.6nm.General about 0.05nm ~ 1.3nm becomes the scope of the room temperature masking being suitable for utilizing present method.
(coating and air-dry process towards 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) on, 2 adhesion zones are attached with fixed intervals abreast as pad, then uses glass stick to be coated with each slurry prepared according to described method equably.
Coating slurry after, pigment absorption before, for or without UV ozonize, UV radiation treatment or drying treatment the condition that changes to make porous film.
(drying treatment)
By on conductive board coating after film in an atmosphere with room temperature carry out about 2 minutes air-dry.In this process, the metal alkoxide in slurry is hydrolyzed because of the moisture in air, forms titanium oxide, zirconium white, the niobium oxides of amorphous from Ti alkoxide, Zr alkoxide, Nb alkoxide respectively.
The amorphous metal oxide that generated plays by metal oxide microparticle each other and the effect that bonds of film and conductive board, therefore by means of only the air-dry porous film that just can obtain physical strength and tack excellence.
(UV ozonize)
The NL-UV253UV ozone clean machine that Japanese electronic laser (Nippon Laser & Electronics) company manufactures is used in UV ozonize.UV light source possesses 3 have open-wire line 4.5W mercuryvapour lamp at 185nm and 254nm place, sample is flatly configured in the distance of about 6.5 centimetres from light source.Ozone is produced by importing oxygen flow in reaction chamber.In this example, 2 hours these UV ozonize are carried out.Moreover, do not see the decline of the electroconductibility of ito film caused by this UV ozonize and FTO film completely.
(UV process)
To carrying out the laggard row relax of nitrogen replacement in reaction chamber, in addition, similarly carry out processing for 2 hours in the mode identical with described UV ozonize.Do not see the decline of the electroconductibility of ito film caused by this UV process and FTO film completely.
(pigment absorption)
Use the pigment shown in table 9 as sensitizing coloring matter, make the ethanolic soln of 0.5mM.In this example, porous film made in described processing procedure is immersed in the solution of sensitizing coloring matter after dry 1 hour in the baking oven of 100 DEG C, and directly at room temperature placement makes sensitizing coloring matter be adsorbed on titania surface in 50 minutes.Ethanol is utilized to clean the sample after sensitizing coloring matter absorption, and in addition air-dry.
(making of photoelectrochemical cell and battery behavior evaluation)
Using the conductive board of porous film that is formed after pigment absorption as optoelectronic pole, make it with the ITO/PET film modified Pt microparticles by sputter or FTO/ glass to electrode pair to, and manufacture experimently photoelectrochemical cell.The useful area of described optoelectronic pole is set to about 0.2cm 2.Electrolyte solution uses the I of LiI, 0.05M containing 0.5M 2, 0.5M the 3-methoxypropionitrile of tert .-butylpyridine, and to be directed into by capillary phenomenon in two interelectrode gaps.
The evaluation of battery performance (efficiency of conversion) is by fixed light subnumber (10 16cm -2) irradiate lower photoelectric current action spectrum mensuration and AM1.5 simulated solar irradiation (100mW/cm 2) irradiate lower I-V mensuration and carry out.These CEP-2000 type light splitting sensitometry devices using light splitting gauge (Bunkoukeiki) company to manufacture in measuring.Show the result in table 9.
Moreover, be that more than 2.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.0% by efficiency of conversion, be evaluated as zero less than 2.5%, be more than 1.5% by efficiency of conversion, be evaluated as △ less than 2.0%, by efficiency of conversion less than 1.5% being evaluated as ×.
[table 9]
Table 9
" pre-treatment of titanium oxide " hurdle of table 9 represents the pre-treatment (carrying out thermal treatment in 30 minutes in the baking oven of 450 DEG C) with or without titanium oxide microparticle.Moreover sample 7-6, sample 7-14 and sample 7-22 are the samples made by slurry using 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: the sample made by the slurry of TTIP=1:0.0356.
In table 9, UV ozonize, UV radiation treatment, drying treatment after the hurdle of " UV ozone ", " UV ", " drying " represents the formation with or without porous film respectively, before sensitizing coloring matter absorption.Represent treated person with "○", represent untreated person with "×".
According to the result shown in table 9, no matter use the photoelectrochemical cell of metal complex dye of the present invention with or without UV ozonize, UV radiation treatment, the drying treatment after the formation of porous film, before sensitizing coloring matter absorption, efficiency of conversion is all high.
[experiment 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 following shown No.1 ~ No.8 becomes 0.5mol/L respectively with concentration is added respectively, is dissolved in this electrolyte solution.
[changing 48]
On the glass substrate, by carrying out sputter to the stannic oxide doped with fluorine and form conducting film and as nesa coating.On this conducting film, coating (allocates anatase-type titanium oxide (P-25 (trade(brand)name) that Japanese Ai Luoxier company manufactures) 32g containing anatase-type titanium oxide dispersion of particles liquid in the mixed solvent 100ml comprising water that volume ratio is 4:1 and 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 obtained), carry out thereafter sintering and forming the photoreceptor layers that thickness is 15 μm at 500 DEG C.The benzoglyoxaline based compound electrolytic solution of No.1 ~ No.8 is dropped on this photoreceptor layers.
The frame-type pad (thickness is 25 μm) of polyethylene film is positioned on this photoreceptor layers, and utilizes platinum to cover this pad to electrode, and make photo-electric conversion element.
Using Xe lamp as light source, be 100mW/cm to obtained photo-electric conversion element exposure intensity 2light.Measure open circuit voltage and photoelectric transformation efficiency.The results are shown in table 10.
Be that more than 6.3V person is evaluated as ◎ by open circuit voltage, open circuit voltage be more than 6.0V, be evaluated as zero less than 6.3V person, open circuit voltage is more than 5.7V, is evaluated as △ less than 6.0V person, by open circuit voltage less than 5.7V person be evaluated as ×.
Be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
Moreover, also represent the result using and do not add the photo-electric conversion element of the electrolytic solution of benzoglyoxaline based compound in table 10.
[table 10]
Table 10
According to the result of table 10, use the open circuit voltage of the photo-electric conversion element of metal complex dye of the present invention and efficiency of conversion all high.
[experiment 9]
(photoelectrochemical cell 21)
By program shown below, make have the formation identical with the optoelectronic pole 10 shown in the Fig. 1 recorded in Japanese Patent Laid-Open 2004-152613 optoelectronic pole (but, semi-conducting electrode 2 is set to double-layer structural), and then use this optoelectronic pole, in addition, the photoelectrochemical cell 21 (area of the sensitive surface F2 of semi-conducting electrode 2: 1cm with the formation identical with the dye-sensitized solar cell 20 shown in the Fig. 1 recorded in Japanese Patent Laid-Open 2004-152613 is made 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 being called " the 1st layer ", being configured near being called " the 2nd layer " the layer of the side of electrode CE.
First, (Degussa (Degussa) company manufactures to use the P25 powder that median size is 25nm, trade(brand)name), and the Titanium particles that particle diameter is different from it, P200 powder (median size: 200nm, Degussa (Degussa) company manufactures, trade(brand)name), be 15 quality % with the content of the total of P25 and P200, and the mass ratio of P25 and P200 becomes the mode of P25:P200=30:70, methyl ethyl diketone is added in them, ion exchanged water, (East capital changes into company and manufactures interfacial agent, trade(brand)name: " Te Lidun-X (Triton-X) "), and carry out mixing and make the 2nd layer of slurry formed (below, be called " slurry 1 ").
And then, do not use P200, and only use P25, in addition, make the 1st layer of slurry formed (content of P1: 15 quality %, hereinafter referred to as " slurry 2 ") by the preparation procedure identical with described slurry 1.
On the other hand, prepare the SnO doped with fluorine 2conducting film (thickness: 700nm) is formed in the transparency electrode (thickness: 1.1mm) on glass substrate (transparent conductivity glass).Then, utilize rod coater that described slurry 2 is coated on this SnO 2on conducting film, then in addition dry.Thereafter, calcining in 30 minutes is carried out with 450 DEG C in atmosphere.So, the 1st layer of semi-conducting electrode 2 is formed on the transparent electrodes.
And then, use slurry 1 to repeat and described identical coating and calcining, form the 2nd layer on layer 1 thus.So, at SnO 2conducting film is formed the semi-conducting electrode 2 (area of sensitive surface: 1.0cm 2, the 1st layer with the aggregate thickness of the 2nd layer: 10 μm (thickness of the 1st layer: 3 μm, thickness of the 2nd layer: 7 μm)), and to make not containing the optoelectronic pole of the state of sensitizing coloring matter.
Then, the ethanolic soln (concentration of sensitizing coloring matter: 3 × 10 as the sensitizing coloring matter shown in the table 11 of sensitizing coloring matter is prepared -4mol/L).Described optoelectronic pole is immersed in this solution, and places 20 hours with the temperature condition of 80 DEG C, and sensitizing coloring matter is adsorbed.Thereafter, in order to promote open circuit voltage Voc, after the semi-conducting electrode after being adsorbed by pigment flood 15 minutes in the acetonitrile solution of 4-tert .-butylpyridine, making its drying remaining in the stream of nitrogen gas of 25 DEG C, and completing described optoelectronic pole 10.
Then, make have the shape identical with described optoelectronic pole and size to electrode CE.First, hexahydrated for Platinic chloride aqueous isopropanol is dropped on transparent conductivity glass, after carrying out drying in an atmosphere, carry out 30 minutes calcination processing with 450 DEG C, obtain platinum sintering thus to electrode CE.Moreover, in this is to electrode CE, be provided with the hole (diameter is 1mm) of the injection of ionogen E in advance.
Then, make zinc iodide, iodate-1,2-dimethyl-3-propyl imidazole, iodine and 4-tert .-butylpyridine are dissolved in and become in the methoxyacetonitrile of 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, pad S (the trade(brand)name: " coughing Milan (Himilan) " that Mitsui Du Pont polymeric chemical (the Du Pont-Mitsui Polychemicals) company preparing to have the shape of coincideing with the size of semi-conducting electrode manufactures, ethylene/methacrylic acid random copolymers ionomeric membrane), as as shown in Fig. 1 of recording in Japanese Patent Laid-Open 2004-152613, make optoelectronic pole with to electrode via pad subtend, and by thermo-welding, both laminatings are obtained the framework (not filling ionogen) of battery.
Then, after aqueous ionogen is injected in framework to the hole of electrode, utilize the component plugging hole with pad same story, and then hole is sealed by this component thermo-welding in the hole of electrode, and complete photoelectrochemical cell 21.
(photoelectrochemical cell 22)
Iodate zinc concentration in aqueous ionogen is set to 50mmol/L, in addition, makes photoelectrochemical cell 22 with the program identical with photoelectrochemical cell 21 and condition.
(photoelectrochemical cell 23)
Interpolation lithium iodide replaces the zinc iodide in aqueous ionogen, and the concentration of the lithium iodide in aqueous ionogen is set to 20mmol/L, in addition, makes photoelectrochemical cell 23 with the program identical with photoelectrochemical cell 21 and condition.
(photoelectrochemical cell 24)
Interpolation lithium iodide replaces the zinc iodide in aqueous ionogen, and the concentration of the lithium iodide in aqueous ionogen is set to 100mmol/L, in addition, makes photoelectrochemical cell 24 with the program identical with photoelectrochemical cell 21 and condition.
(battery behavior evaluation test)
By following program, photoelectric transformation efficiency (η (%)) is measured to photoelectrochemical cell 21 ~ photoelectrochemical cell 24.
Battery behavior evaluation test uses Tai Yang Mo Be device (to manufacture with hat (WACOM), trade(brand)name: " WXS-85-H type "), the illuminate condition of the simulated solar irradiation from xenon source that have passed through AM spectral filter (AMl.5) is being set to 100mW/cm 2(illuminate condition of so-called " 1Sun ") condition determination under carry out.
For each photoelectrochemical cell, use I-V tester at room temperature to measure I-E characteristic, and obtain photoelectric transformation efficiency η [%] according to these I-E characteristics." fresh " of obtained result as table 11 (illuminate condition of 1Sun) is represented.In addition, by 60 DEG C, 1Sun irradiates, under operation condition under 10 Ω loads, the result that photoelectric transformation efficiency η [%] durability evaluation that institute is investigated out after 300 hours at 80 DEG C of photoelectrochemical cell 21 ~ photoelectrochemical cell 24 is tested also is shown in table 11.
Moreover, be that more than 3.5% person is evaluated as ◎ by the efficiency of conversion of Fresh, be more than 2.5% by the efficiency of conversion of Fresh, be evaluated as zero less than 3.5%, be more than 2.0% by the efficiency of conversion of Fresh, be 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 clear and definite in the result shown according to table 11, even if the photoelectrochemical cell of known use metal complex dye of the present invention is when being added into zinc iodide in ionogen, efficiency of conversion and weather resistance are also excellent.
[experiment 10]
1. the preparation of titanium oxide dispersion
Be in the stainless steel container of 200ml, add titanium dioxide particle (Japanese Ai Luoxier (share) manufacture to internal capacity inner side being coated with to fluoro-resin, trade(brand)name: Degussa P-25) 15g, water 45g, (aldrich company manufactures dispersion agent, trade(brand)name: special power dragon X-100 (Triron X-100)) 1g, diameter is zirconium oxide bead (manufacture of Ni Kaduo (Nikkato) company) 30g of 0.5mm, sand mill (sand grinder mill) (manufacture of Ai Maikesi (Aimex) company) is used 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 μm.Moreover particle diameter is that Ma Shitesaizhe (Mastersizer) (trade(brand)name) manufactured by Malvern (MALVERN) company is measured.
2. be adsorbed with the making of the titanium oxide microparticle sublayer (electrode A) of pigment
Prepare the conductive glass plate (Asahi Glass (Asahi Glass) (share) manufacture, trade(brand)name: TCO Glass-U, the surface resistivity: about 30 Ω/m that are coated with the 20mm × 20mm of fluorine-doped tin oxide 2), after pad adhesion zone being attached to the two ends part of the width of 3mm (from the end) of its conductive layer side, use glass stick by described dispersion liquid coating on the electrically conductive.After Coating dispersions, by adhesion zone peel off, and at room temperature carry out 1 day air-dry.Then, this semi-conductor coated glass plate is fed in electric furnace (the retort furnace FP-32 type that large and science (Yamato Scientific) (share) manufactures), and at 450 DEG C, carries out calcining in 30 minutes.After taking-up semi-conductor coated glass plate is also cooled, the ethanolic soln (concentration: 3 × 10 of the sensitizing coloring matter shown in table 12 -4mol/L) dipping 3 hours in.The semi-conductor coated glass plate being adsorbed with sensitizing coloring matter is flooded after 15 minutes in 4-tert .-butylpyridine, utilizes ethanol to clean, and make its seasoning, and obtain the titanium oxide microparticle sublayer (electrode A) being adsorbed with sensitizing coloring matter.The thickness of the dye-sensitized titanium oxide microparticle sublayer of electrode A is 10 μm, and the glue spread of titanium oxide microparticle is 20g/m 2.In addition, the adsorptive capacity of pigment corresponds to its kind and is 0.1mmol/m 2~ 10mmol/m 2scope in.
3. the making of dye-sensitized solar cell
3 kinds of dye-sensitized solar cells of dye-sensitized solar cell a ~ dye-sensitized solar cell c are made by following method.In these dye-sensitized solar cells, use the sensitizing coloring matter shown in table 12, following nitrogen containing polymer α and following electrophilic reagent β, and obtain specimen coding 10-1 ~ specimen coding 10-15.
The making of (a) dye-sensitized solar cell a
As solvent, the volume ratio using acetonitrile and 3-methyl-2-oxazolidone is the mixture of 90/10.Iodine and the salt compounded of iodine as the 1-methyl-3-hexyl imidazolium of electrolytic salt is added in this solvent, and the solution of the iodine of the electrolytic salt made containing 0.5mol/L and 0.05mol/L.Relative to (solvent+nitrogen containing polymer compound+salt) 100 mass parts, in this solution, add the following nitrogen containing polymer compound α of 10 mass parts.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]
On the other hand, there is the platinum film side to electrode of the sheet glass of platinum to be positioned on the dye-sensitized titanium oxide microparticle sublayer of described electrode A via pad by comprising evaporation, 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 at 80 DEG C, and carry out crosslinking reaction.So, as as shown in Fig. 2 of Japanese Patent Laid-Open 2000-323190 publication, 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 the of the present invention dye-sensitized solar cell a-1 (specimen coding 10-1) to electrode 40 of platinum film 42 and sheet glass 41.
In addition, except changing except pigment as shown in table 12, obtained dye-sensitized solar cell a-2 ~ dye-sensitized solar cell a-5 by repeating said steps.
The making of (b) dye-sensitized solar cell b
The electrode A (20mm × 20mm) comprising the titanium oxide microparticle sublayer making sensitizing coloring matter adsorb in this way is superimposed upon on the platinum evaporation sheet glass of formed objects via pad.Then, utilize capillary phenomenon that electrolytic solution (being the iodine 0.05mol/L of mixture as solvent, the solution of lithium iodide 0.5mol/L of 90/10 using the volume ratio of acetonitrile and 3-methyl-2-oxazolidone) is infiltrated in the gap of two sheet glass, and make dye-sensitized solar cell b-1 (specimen coding 10-2).In addition, except changing except pigment as shown in table 12, obtained dye-sensitized solar cell b-2 ~ dye-sensitized solar cell b-5 by repeating said steps.
The making (ionogen described in Japanese Patent Laid-Open 9-27352 publication) of (c) dye-sensitized solar cell c
Electrolytic solution is coated on and comprises in the electrode A (20mm × 20mm) of the titanium oxide microparticle sublayer making sensitizing coloring matter adsorb in this way, and make its impregnation.Moreover, electrolytic solution is that (Japanese oil chemistry (share) manufactures by making lithium iodide 500mg be dissolved in containing six glycolmethacrylates, Blemmer PE-350) 1g, ethylene glycol 1g and (Japanese vapour Ba-Jia Ji (Ciba-Geigy) (share) manufactures as the 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone of polymerization initiators, Da Luoke 1173 (Darocurl173)) 20mg mixed solution in, and carry out vacuum stripping in 10 minutes and obtain.Then, under being placed in decompression by making the porousness titanium oxide layer of described mixing solutions impregnation, remove the bubble in porousness titanium oxide layer thus, after promoting the infiltration of monomer, gel-filled uniformly in the fine emptying aperture of porousness titanium oxide layer by macromolecular compound after being polymerized by UV-irradiation.Make winner in this way expose 30 minutes in iodine environment, iodine is diffused to after in macromolecular compound, superposition platinum evaporation sheet glass, and obtain dye-sensitized solar cell c-1 (specimen coding 10-3).In addition, except changing except pigment as shown in table 12, obtained photoelectrochemical cell c-2 ~ photoelectrochemical cell c-5 by repeating said steps.
4. the mensuration of photoelectric transformation efficiency
Make the light of the xenon lamp (oxtail motor (share) manufacture) of 500W through AM1.5 spectral filter (manufacture of Ao Lier (Oriel) company) and sharp wave spectral filter (trade(brand)name: Ken Keer-42 (KenkoL-42)), formed thus not containing ultraviolet simulated solar irradiation.Light intensity is set to 89mW/cm 2.
Be connected crocodile clip at the conductive glass plate 10 of described photoelectrochemical cell respectively with on platinum evaporation sheet glass 40, and each crocodile clip be connected on current/voltage determinator (Keithley SMU238 type).From conductive glass plate 10 side, simulated solar irradiation is irradiated to it, and utilize current/voltage determinator to measure the electricity produced.The rate of descent of the efficiency of conversion when initial value (fresh) of the efficiency of conversion (η) of the photoelectrochemical cell obtained therefrom and 300 hours Continuous irradiation is gathered and is shown in table 12.
Moreover, be that more than 3.5% person is evaluated as ◎ by the efficiency of conversion of Fresh, be more than 2.5% by the efficiency of conversion of Fresh, be evaluated as zero less than 3.5%, be more than 2.0% by the efficiency of conversion of Fresh, be evaluated as △ less than 2.5%, by the efficiency of conversion of Fresh less than 2.0% being evaluated as ×.
[table 12]
Table 12
As clear and definite in the result shown according to table 12, use the initial value of the efficiency of conversion of the photoelectrochemical cell of metal complex dye of the present invention to be qualified level, and then the rate of descent of efficiency of conversion after 300 hours is also low, and the weather resistance that display is excellent.
[experiment 11]
Use by the suspension prepared by sol-gel method, and utilize screen painting to be coated on FTO glass, and calcine TiO at 450 DEG C 2porous layer.It is made to be immersed in metal complex dye A-2b of the present invention or to compare 10 of pigment S-1 -4in mol/L ethanolic soln, pigment is made to adsorb thus.
Make 2 of 100mg, 2 ', 7,7 '-four (diphenylamino)-9,9 '-spiral shell two fluorenes is dissolved in the chloroform of 5ml.Solution is coated in dyestuff surface lightly, makes this solution infiltrate in the pore of layer thus.Then, one of solution be directly placed in surface and at room temperature carry out drying.Then, 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 2 of 100nm, 2 ', the layer of 7,7 '-four (diphenylamino)-9,9 '-spiral shell two fluorenes.And then, be that the layer gold of 200nm is as being overlayed on electrode on this coating supporter using thickness in evaporation coating device.
The sample so prepared is arranged in the Optical devices comprising high-voltage lamp, spectral filter, lens and stand (mounting).Intensity is changed by the use of spectral filter and the movement of lens.At layer gold and SnO 2layer on contact is installed, and during sample is irradiated in be arranged on the device shown in current-flow test set.In order to measure, use suitable spectral filter blocking wavelength less than the light of 430nm.And then, to make the intensity of radioactive rays and about 1000W/m 2roughly consistent mode setting device.
At layer gold and SnO 2layer installs contact, in addition, in during sample is irradiated, two contacts is connected on potentiostat.Use the electric current producing about 90nA in the sample of S-1 not applying external voltage, but produce the electric current of about 190nA in the sample using metal complex dye A-2b of the present invention.
According to this result, use the efficiency of conversion of the photoelectrochemical cell of metal complex dye of the present invention excellent.
Moreover when any one sample, if do not irradiate, then electric current all disappears.
[experiment 12]
In the series unit made in the same manner as the example 1 of Japanese Patent Laid-Open 2000-90989, also can confirm, compared with the photoelectrochemical cell that pigment S-1 is compared in use, to use the efficiency of conversion of the photoelectrochemical cell of metal complex dye A-2b of the present invention high.
[experiment 13]
Titanium isopropoxide 125ml is dropped in 0.1M-aqueous nitric acid (manufacture of bank field chemistry (Kishida Chemical) limited-liability company) 750ml, heat 8 hours at 80 DEG C and hydrolysis reaction is carried out, making sol solutions thus.Obtained sol solutions is kept 15 hours with 250 DEG C in titanium autoclave, makes grain growth, thereafter, carry out ultrasonic wave dispersion in 30 minutes, obtain thus and contain the colloidal solution that average primary particle diameter is the Titanium particles of 20nm.
Utilize vaporizer, the obtained colloidal solution containing Titanium particles is concentrated into after till titanium oxide becomes the concentration of 10wt% lentamente, to add the polyethylene glycol of 40% relative to the mass ratio range of titanium oxide, (bank field chemistry limited-liability company manufactures, weight average molecular weight: 200000), and stir, obtain the suspension being dispersed with Titanium particles thus.
Utilize doctor method to be coated on by prepared titanium oxide suspension and be formed with SnO 2film as the nesa coating side of the glass substrate of nesa coating, and obtains the film that area is about 10mm × 10mm.At 120 DEG C to this film carry out 30 minutes predrying, and then under oxygen atmosphere, carry out calcining in 30 minutes with 500 DEG C, and form the oxidation titanium film that the thickness becoming the 1st layer of Porous semiconductor layer of the 1st layer of Porous photoelectric conversion layer is about 10 μm.
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 manufactures) 0.4g is added in distilled water 20ml, and utilizes hydrochloric acid to be adjusted to pH=1.And then, add zirconium oxide bead, utilize coating oscillator to carry out 8 hours dispersion treatment to this mixing solutions.Thereafter, to add the polyethylene glycol of 40% relative to the mass ratio range of titanium oxide, (bank field chemistry limited-liability company manufactures, weight average molecular weight: 200000), and stirs, and obtains the suspension being dispersed with Titanium particles thus.
Be formed the 1st layer of Porous semiconductor layer oxidation titanium film glass substrate the 1st layer of Porous semiconductor layer on, utilize doctor method be coated with prepared by titanium oxide suspension, and obtain film.At 80 DEG C to this film carry out 20 minutes predrying, and then under oxygen atmosphere, carry out calcining in 60 minutes with about 500 DEG C, and form the oxidation titanium film 1 that the thickness becoming the 2nd layer of Porous semiconductor layer of the 2nd layer of Porous photoelectric conversion layer is about 22 μm.Measure the mist degree rate of Porous semiconductor layer, result is 84%.
Make the merocyanine system pigment S-3 represented by following formula dissolve in ethanol as the pigment (the 1st pigment) in the sensitivity maximum absorbing wavelength region had at short wavelength side in absorption spectrum, and to make concentration be 3 × 10 -4the absorption pigment solution of the 1st pigment of mol/L.
[changing 51]
The glass substrate making to possess nesa coating and Porous semiconductor layer floods 10 minutes heating to the absorption pigment solution of the 1st pigment of about 50 DEG C, and the 1st pigment is adsorbed on Porous semiconductor layer.Thereafter, utilize dehydrated alcohol by cleaning glass substrate several times, at about 60 DEG C, then carry out drying in about 20 minutes.Then, make glass substrate in 0.5N-hydrochloric acid, flood about 10 minutes, utilize thereafter ethanol to clean, and the 1st pigment be adsorbed on the 2nd layer of Porous semiconductor layer is departed from.And then, at about 60 DEG C, drying in about 20 minutes is carried out to glass substrate.
Then, make the described pigment S-1 or metal complex dye A-12b of the present invention that compares dissolve in ethanol as the pigment (the 2nd pigment) in the sensitivity maximum absorbing wavelength region had at long wavelength side in absorption spectrum, and to make concentration be 3 × 10 -4the absorption pigment solution of the 2nd pigment of mol/L.
Under room temperature, normal pressure, make the glass substrate possessing nesa coating and Porous semiconductor layer flood 15 minutes in the absorption pigment solution of the 2nd pigment, and the 2nd pigment is adsorbed on Porous semiconductor layer.Thereafter, utilize dehydrated alcohol by cleaning glass substrate several times, at about 60 DEG C, then carry out drying in about 20 minutes., measure the mist degree rate of Porous semiconductor layer, result is 84% (situation of pigment S-1 is compared in use), 85% (using the situation of metal complex dye A-12b of the present invention) herein.
Then, become 0.5mol/L to make the concentration of iodate dimethyl propyl imidazoles, make the concentration of lithium iodide become 0.1mol/L, make the concentration of iodine become the mode of 0.05mol/L, make them be dissolved in 3-methoxypropionitrile solvent, and make oxidation-reduction quality electrolytic solution.With the Porous semiconductor layer side of glass substrate, with the mode of the platinum side subtend of the collateral support body of electrode is arranged, prepared oxidation-reduction quality electrolytic solution is injected between the two, and utilize the sealing material of epoxy system resin by environmental seal, and complete coloring matter sensitization type photoelectrochemical cell, described glass substrate possesses the Porous semiconductor layer that the 1st pigment and the 2nd pigment are adsorbed, and described comprising the collateral support body of electrode possesses platinum as the ito glass to electrode layer.
In addition, 2nd layer of Porous semiconductor layer is set to and the 1st layer of layer that Porous semiconductor layer is identical, namely the titanium oxide suspension of formation the 1st layer of Porous semiconductor layer is utilized to form the 2nd layer of Porous semiconductor layer, in addition, oxidation titanium film 2 is made in the same manner as oxidation titanium film 1, use this oxidation titanium film 2 similarly to make photoelectrochemical cell, and measure mist degree rate.Its result, the mist degree rate of Porous photoelectric conversion layer is 15% (situation of pigment S-1 is compared in use), 16% (using the situation of metal complex dye A-12b of the present invention).
Will at condition determination: AM-1.5 (100mW/cm 2) under table 13 is shown in the result that obtained photoelectrochemical cell is evaluated.
Moreover, be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 13]
Table 13
As clear and definite in the result shown according to table 13, the photoelectric transformation efficiency of the photoelectrochemical cell of known use metal complex dye of the present invention is excellent.
[experiment 14]
Use hard glass pearl, and make commercially available Titanium particles (Di Hua company manufactures, and median size is 20nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make titanium oxide suspension in 6 hours by coating oscillator.Then, use doctor, this titanium oxide suspension is coated on make fin oxide condutire layer adhere in advance sheet glass (electrode layer) on, carry out at 100 DEG C 30 minutes predrying after, in electric furnace, carry out calcining in 40 minutes with 500 DEG C, and form oxidation titanium film (semiconductor material) on a glass.
In addition, make the sensitizing coloring matter shown in table 14 dissolve and obtain light sensitizing coloring matter solution in ethanol.The concentration of this light sensitizing coloring matter solution is 5 × 10 -4mol/L.
Then, the described sheet glass being formed with membranaceous titanium oxide is fed in this solution, carry out the absorption of 60 minutes pigments at 60 DEG C after, in addition dry, form the photoelectric conversion layer comprising semiconductor material and sensitizing coloring matter thus on a glass.And then, photoelectric conversion layer is coated with the toluene solution (1%) of the polyvinyl carbazole (weight average molecular weight is 3,000) as hole mobile material, and carries out drying under reduced pressure and form hole transmission layer.And then, make to be dissolved in 100mL acetone as the ethyl carbazole 1.95g of Intermolecular charge transfer complex and 5-nitro naphthoquinones 2.03g, 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.
Tai Yang Mo Be device is utilized to be 100W/m to obtained photo-electric conversion element exposure intensity 2light.Show the result in table 14.
Moreover, be that more than 1.5% person is evaluated as ◎ by efficiency of conversion, be more than 1.0% by efficiency of conversion, be evaluated as zero less than 1.5%, be more than 0.5% by efficiency of conversion, be evaluated as △ less than 1.0%, by efficiency of conversion less than 0.5% being evaluated as ×.
[table 14]
Table 14
As clear and definite in the result shown according to table 14, the efficiency of conversion of the photoelectrochemical cell of known use metal complex dye of the present invention is excellent.
[experiment 15]
The formation of (1) the 1st photoelectric conversion layer
Use hard glass pearl, and make commercially available Titanium particles (Di Hua company manufactures, and median size is 30nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make titanium oxide suspension in 6 hours by coating oscillator.Then, use doctor, this titanium oxide suspension be coated on the sheet glass being attached with fin oxide condutire layer in advance, carry out at 100 DEG C 30 minutes predrying after, in electric furnace, carry out calcining in 40 minutes with 500 DEG C, and obtain oxidation titanium film.
In addition, make [the cis-dithio cyanine-N-two (2 of the pigment represented by following S-4,2 '-bipyridyl-4,4 '-dicarboxylic acid) ruthenium (cis-dithiocyanine-N-bis (2,2 '-bipyridyl-4,4 '-dicarboxylic acid) ruthenium)] dissolve in ethanol.
[changing 52]
The concentration of this pigment is 3 × 10 -4mole.
Then, the described sheet glass being formed with membranaceous titanium oxide is fed in this solution, carries out after the absorption of 720 minutes pigments in addition dry at 60 DEG C, and form the 1st photoelectric conversion layer, thus obtain Sample A.
The formation of (2) the 2nd photoelectric conversion layers
Use granulated glass sphere, and make commercially available nickel oxide particle (An Tian chemical company manufactures, and median size is 100nm) 4.0g and diethylene glycol monomethyl ether 20ml disperse to make nickel oxide suspension in 8 hours by coating oscillator.Then, use doctor, by this nickel oxide suspension on the sheet glass being attached with fin oxide condutire layer in advance, carry out at 100 DEG C 30 minutes predrying after, in electric furnace, carry out calcining in 30 minutes with 300 DEG C, and obtain nickel oxide film.
In addition, the sensitizing coloring matter shown in table 15 is made to be dissolved in dimethyl sulfoxide (DMSO).The concentration of this pigment is 1 × 10 -4mole.
Then, the described sheet glass being formed with membranaceous nickel oxide is fed in this solution, carries out after the absorption of 60 minutes pigments in addition dry at 70 DEG C, and form the 2nd photoelectric conversion layer, thus obtain sample B.
(3) making of photo-electric conversion element
Sample B is positioned in described Sample A.Between described 2 electrodes, add liquid electrolyte, 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 tetrapropyl ammonium iodide and iodine become 0.46mol/L, 0.06mol/L with respective concentration is dissolved in the person of forming in the mixed solvent (volume ratio is for 1:4) of acetonitrile/NSC 11801.
In addition, towards and possess described Sample A as the electrode of side and carry platinum and add liquid electrolyte as between the transparent conductivity sheet glass to electrode, utilize resin by after its side seal, conducting wire, and make photo-electric conversion element (element forms D).
Tai Yang Mo Be device is utilized to be 1000W/m to obtained photo-electric conversion element exposure intensity 2light, and measure efficiency of conversion.The results are shown in table 15.
Moreover, be that more than 6.5% person is evaluated as ◎ by efficiency of conversion, be more than 6.0% by efficiency of conversion, be evaluated as zero less than 6.5%, be more than 5.0% by efficiency of conversion, be evaluated as △ less than 6.0%, by efficiency of conversion less than 5.0% being evaluated as ×.
[table 15]
Table 15
As clear and definite in the result shown according to table 15, the efficiency of conversion of the photoelectrochemical cell of known use metal complex dye of the present invention is excellent.And then, known except metal complex dye of the present invention, and use other sensitizing coloring matters, efficiency of conversion promotes further thus.
[experiment 16]
The production example of the coloring matter sensitization type photoelectrochemical cell using polymer electrolyte is described.
About the masking liquid making oxidation titanium film, use granulated glass sphere, and (Di Hua company manufactures, and trade(brand)name AMT-600, Detitanium-ore-type crystallization, median size is 30nm, and specific surface area is 50m to make commercially available Titanium particles by coating oscillator 2/ g) 4.0g and diethylene glycol monomethyl ether 20mL disperses 7 hours, and makes titanium oxide suspension.By SnO 2make on substrate on the glass substrate as nesa coating, use doctor, with the area of the thickness of about 11 μm, about 10mm × 10mm, this titanium oxide suspension is coated on nesa coating side, carry out at 100 DEG C 30 minutes predrying after, calcining in 40 minutes is carried out under oxygen with 460 DEG C, its result, makes the oxidation titanium film that thickness is about 8 μm.
Then, make the sensitizing coloring matter shown in table 16 with concentration 3 × 10 -4mol/L is dissolved in dehydrated alcohol and makes absorption pigment solution.This absorption pigment solution and the transparency carrier that possesses oxidation titanium film and the nesa coating obtained in this way are fed in container respectively, and this absorption pigment solution is permeated about 4 hours, make pigment adsorb thus.Thereafter, utilize washes of absolute alcohol several times, and at about 60 DEG C, carry out drying in about 20 minutes.
Then, use among the monomeric unit represented by following general formula (105), be methyl using R, monomer that A is 8 polyethylene oxide bases and 2 poly(propylene oxide) bases is as centronucleus and comprise the monomeric unit of butane four base, make monomer solution.
[changing 53]
(in formula, R represents hydrogen atom or methyl, and A carries out the residue of bond by carbon atom with ester group, and n represents the integer of 2 ~ 4)
This monomeric unit is made to be dissolved in propylene carbonate with the concentration of 20wt% (following, be recited as PC (Propylene Carbonate)) in, in addition, the azobis isobutyronitrile (Azobisisobutyronitrile, AIBN) as thermopolymerization initiator is made to make monomer solution relative to monomeric unit with the dissolving of the concentration of 1wt%.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 possessed on the transparency carrier of nesa coating is loaded wherein, then utilize rotor pump to carry out vacuumizing for about 10 minutes.
Monomer solution is injected in beaker by remaining vacuum state one side in vacuum vessel by one side, makes this monomer solution impregnation about 15 minutes and monomer solution is infiltrated fully in titanium oxide.Polyethylene dividing plate, PET film and pressing plate are set and utilize fixture to fix.Thereafter, at about 85 DEG C, carry out heating in 30 minutes, carry out thermopolymerization thus and make macromolecular compound.
Then, the oxidation-reduction quality electrolytic solution containing being immersed in macromolecular compound is made.Oxidation-reduction quality electrolytic solution is using PC as solvent, makes concentration be the lithium iodide of 0.5mol/L and concentration to be the iodine of 0.05mol/L to dissolve to make.Make the macromolecular compound being made into described oxidation titanium film in this solution, flood about 2 hours, make oxidation-reduction quality electrolytic solution infiltrate thus and make polymer electrolyte to macromolecular compound.
Thereafter, the conductive board possessing platinum film is set, utilizes the sealing agent of epoxy environmental seal to be made element A.
In addition, after pigment absorption is carried out to oxidation titanium film, do not carry out monomer process, direct court and to injecting redox electrolytes liquid between electrode and sealing, and make element B, described redox electrolytes liquid is using PC as solvent, the redox electrolytes liquid made by the iodine that the lithium iodide making concentration be 0.5mol/L and concentration are 0.05mol/L dissolves.
Use element A, element B, utilize Tai Yang Mo Be device exposure intensity to be 1000W/m 2light, and measure efficiency of conversion.Show the result in table 16.
Moreover, be that more than 3.5% person is evaluated as ◎ by efficiency of conversion, be more than 2.5% by efficiency of conversion, be evaluated as zero less than 3.5%, be more than 2.0% by efficiency of conversion, be evaluated as △ less than 2.5%, by efficiency of conversion less than 2.0% being evaluated as ×.
[table 16]
Table 16
As clear and definite in the result shown according to table 16, the efficiency of conversion of the photo-electric conversion element of known use metal complex dye of the present invention is excellent.
[experiment 17]
(making of photo-electric conversion element)
Photo-electric conversion element 10 as follows shown in construction drawing 1.
Using the mode identical with example 1 make be formed insulativity porous insert by optoelectronic pole and as the carbon dioxide process carbon electrode to electrode.
Then, make described in be formed with insulativity porous insert the sensitizing coloring matter (mixing multiple or independent) described in following table 17 of glass substrate ethanolic soln in dipping 5 hours.The glass being stained with sensitizing coloring matter is flooded after 30 minutes in 10% ethanolic soln of 4-tert .-butylpyridine, utilizes ethanol carry out cleaning and make its seasoning.The thickness of the photoreceptor layers obtained in this way is 10 μm, and the glue spread of semiconductor microactuator particle is 20g/m 2.Electrolytic solution uses the methoxypropionitrile solution of iodate dimethyl propyl imidazoles (0.5mol/L), iodine (0.1mol/L).
(mensuration of efficiency of conversion)
The efficiency of conversion of the photoelectrochemical cell obtained is measured in the same manner as experiment 1.The results are shown in table 17.
Moreover, be that more than 7.5% person is evaluated as ◎ by efficiency of conversion, be more than 7.3% by efficiency of conversion, be evaluated as zero less than 7.5%, be more than 7.1% by efficiency of conversion, be evaluated as △ less than 7.3%, by efficiency of conversion less than 7.1% being evaluated as ×.
[table 17]
Table 17
Below represent the structure of sensitizing coloring matter S-5, sensitizing coloring matter S-6.
[changing 54]
[changing 55]
As clear and definite in the result shown according to table 17, the efficiency of conversion of the photoelectrochemical cell of known use metal complex dye of the present invention is excellent.And then, known except metal complex dye of the present invention, and use other sensitizing coloring matters, efficiency of conversion promotes further thus.
[experiment 18]
1. the making of electrode 1A
The sensitizing coloring matter be adsorbed on titanium oxide microparticle sublayer is become the sensitizing coloring matter shown in table 18, in addition, makes electrode 1A in the mode identical with experiment 10.
2. the making of dye-sensitized solar cell
The platinum evaporation glass of the electrode 1A (20mm × 20mm) with formed objects that comprise the titanium oxide microparticle sublayer making sensitizing coloring matter adsorb in this way is superposed.Then, utilize capillary phenomenon, the following ionogen constituent containing 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, lamination comprises the conductive support body 1 (be provided with conductive layer on the transparency carrier of glass person) of conductive glass successively, photoreceptor layers 2, Charger transfer body layer 3, comprise the transparency carrier (not shown) to electrode 4 and glass of platinum, and make by comprising according to a Ke Tai 828 (Epikote828) (trade(brand)name, japan epoxy resin (Japan Epoxy Resins) company manufactures), the dye-sensitized solar cell that diameter is the sealing agent sealing of the glass spheres of 25 μm is dispersed with roughly equably in the resin combination of stiffening agent and plastics slurry.But, when the viscosity of ionogen constituent is high and when being difficult to utilize capillary phenomenon to make ionogen constituent permeate, ionogen constituent is heated to 50 DEG C, be coated with after on Titanium oxide electrode, under this electrode is placed in decompression, after ionogen constituent fully permeates and air in electrode spills, superposition platinum evaporation glass (to electrode) and similarly make dye-sensitized solar cell.
[changing 56]
3. the mensuration of photoelectric transformation efficiency
Make the light of the xenon lamp (oxtail motor (share) manufacture) of 500W through 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 not containing ultraviolet simulated solar irradiation.The intensity of this light is 70mW/cm 2.At 50 DEG C, this simulated solar irradiation is irradiated to the dye-sensitized solar cell 16-1 made in this way ~ dye-sensitized solar cell 16-10, and utilize current/voltage determinator (Keithley SMU238 type) to measure the electricity produced.In addition, the rate of descent of the efficiency of conversion after the rate of descent and the Continuous irradiation light of 500 hours being kept at the efficiency of conversion of dark place after 1000 hours at 85 DEG C is also determined at.Their result is shown in table 18.
[table 18]
Table 18
According to table 18, compared with dye-sensitized solar cell 16-8 ~ dye-sensitized solar cell 16-9, the initial value of the efficiency of conversion of the dye-sensitized solar cell 16-1 made by metal complex dye of the present invention ~ dye-sensitized solar cell 16-7 is used all to show high level.And then compared with known and dye-sensitized solar cell 16-8 ~ dye-sensitized solar cell 16-9, the rate of descent of the efficiency of conversion after being kept at dark place and after Continuous irradiation light is low, excellent in te pins of durability.
The present invention and its example are together illustrated, as long as but contriver does not specify, then do not want the invention of contriver to be limited in any details of explanation, and think the spirit of the invention shown in the scope should not violating the claim of enclosing and scope and make an explanation widely.
The present invention advocates the right of priority based on the Japanese Patent Patent 2010-174315 having carried out patent application in Japan on August 3rd, 2010, herein in addition with reference to and quote its content as the part recorded in this specification sheets.

Claims (8)

1. a metal complex dye, is characterized in that: represented by following general formula (1),
[changing 1]
In general formula (1), R 11~ R 14represent carbon number be 1 ~ 20 straight chain or the alkyl be unsubstituted of branch, carboxyl any one, wherein at least 1 represents carboxyl; A11 ~ a14 represents 1 or 2; M represents copper, zinc, tin, nickel, iron, cobalt, silicon, palladium, chloro-aluminium, magnesium, gallium, titanyl oxygen or vanadium oxygen oxygen; A ~ D represents aromatic nucleus; Among aromatic nucleus represented by A ~ D, the aromatic nucleus with carboxyl is phenylbenzene phenyl ring, phenyl naphthalene nucleus, anthracene nucleus, phenanthrene ring, thiazolyl phenyl ring, 1,3,4-thiadiazolyl group phenyl ring, 3-thiazolyl naphthalene nucleus, benzothiazole ring, pyridine ring, pyrimidine ring, pyrazine ring, imidazole ring, or bond has phenyl ring or the naphthalene nucleus of pyridine ring, pyrimidine ring, pyrazine ring or imidazole ring, the aromatic nucleus without carboxyl is phenyl ring.
2. metal complex dye according to claim 1, is characterized in that: in general formula (1), among the aromatic nucleus of described A ~ D, and the quantity with the aromatic nucleus of carboxyl is 1.
3. a pigment for use with photoelectric conversion element, is characterized in that: comprise metal complex dye according to claim 1 and 2.
4. a photo-electric conversion element, is characterized in that: comprise photoreceptor layers, and this photoreceptor layers has metal complex dye according to claim 1 and 2 and semiconductor microactuator particle.
5. photo-electric conversion element according to claim 4, is characterized in that: described photoreceptor layers and then the metal complex dye contained represented by following general formula (10),
(A1) pru (B-a) (B-b) (B-c) general formula (10)
A1 is for being selected from by 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; P is the integer of 0 ~ 3; B-a, B-b and B-c separately represent by following Formula B-1 ~ Formula B-10 any one represented by organic coordination base or by Formula B-1 ~ Formula B-10 any one represented by the acidic groups that has of organic coordination base be salt person;
In Formula B-1 ~ Formula B-10, R 11~ R 22represent halogen atom, carbonatoms be 1 ~ 12 alkyl, alkoxyl group, the carbonatoms thiazolinyl that is 2 ~ 20, the carbonatoms aralkyl that is 7 ~ 12, alkoxy aryl, carbonatoms be 6 ~ 12 aryl or carboxyl;
E1 and e2 separately represents the integer of 0 ~ 4, e3 represents the integer of 0 ~ 3, e4 and e5 separately represents the integer of 0 ~ 4, e6 represents the integer of 0 ~ 2, e7 and e8 separately represents the integer of 0 ~ 3, and e9 represents the integer of 0 ~ 4, and e10 ~ e12 separately represents the integer of 0 ~ 6, when e1 ~ e12 is more than 2, R 11~ R 22respectively can be identical, also can be different;
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 carboxyl.
6. the photo-electric conversion element according to claim 4 or 5, is characterized in that: have by described photoreceptor layers, Charger transfer body and to electrode with the structure of this sequential lamination in conductive support body.
7. the photo-electric conversion element according to claim 4 or 5, is characterized in that: described metal complex dye is adsorbed on described semiconductor microactuator particle.
8. a photoelectrochemical cell, is characterized in that: comprise the photo-electric conversion element according to any one of claim 4 to 7.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108028137A (en) * 2015-09-17 2018-05-11 富士胶片株式会社 Photoelectric conversion element, dye-sensitized solar cell, dye composition, and oxide semiconductor electrode

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5906522B2 (en) * 2012-05-18 2016-04-20 新日鉄住金化学株式会社 Phthalocyanine dye, dye-sensitized solar cell and photoelectric conversion element using phthalocyanine dye
GB2503003B (en) * 2012-06-13 2015-07-22 Dyesol Uk Ltd Processing titanium dioxide
JP6608187B2 (en) * 2015-06-22 2019-11-20 山本化成株式会社 Sensitizing dye, semiconductor electrode, photoelectric conversion element, and dye-sensitized solar cell
CN106848065A (en) * 2017-02-07 2017-06-13 晋芳芳 A kind of plane perovskite photovoltaic cell using metal phthalocyanine compound as electron transfer layer
CN111316451B (en) * 2017-11-17 2023-07-21 富士胶片株式会社 Photoelectric conversion elements, photosensors, imaging elements, compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6432270A (en) * 1987-07-28 1989-02-02 Toyo Ink Mfg Co Planographic printing plate
US6043428A (en) * 1997-06-23 2000-03-28 Sharp Kabushiki Kaisha Photoelectric material using organic photosensitising dyes and manufacturing method thereof
JP2009193763A (en) * 2008-02-13 2009-08-27 Konica Minolta Holdings Inc Semiconductor for photoelectric conversion material, photoelectric conversion element, and solar cell
WO2010050574A1 (en) * 2008-10-29 2010-05-06 富士フイルム株式会社 Photoelectrochemical cell

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4623768B2 (en) * 1997-06-23 2011-02-02 シャープ株式会社 Photoelectric conversion material, method for producing the same, and photoelectric conversion device
EP1985668B1 (en) * 2006-02-10 2011-09-21 Nippon Kayaku Kabushiki Kaisha Novel porphyrazine dye, ink, ink set, and colored material
WO2010136178A1 (en) * 2009-05-26 2010-12-02 Corus Uk Limited The preparation of a dye compound and a method for making the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6432270A (en) * 1987-07-28 1989-02-02 Toyo Ink Mfg Co Planographic printing plate
US6043428A (en) * 1997-06-23 2000-03-28 Sharp Kabushiki Kaisha Photoelectric material using organic photosensitising dyes and manufacturing method thereof
JP2009193763A (en) * 2008-02-13 2009-08-27 Konica Minolta Holdings Inc Semiconductor for photoelectric conversion material, photoelectric conversion element, and solar cell
WO2010050574A1 (en) * 2008-10-29 2010-05-06 富士フイルム株式会社 Photoelectrochemical cell

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Asymmetrical, Water-Soluble Phthalocyanine Dyes for Covalent Labeling of Oligonucleotides;Robert P. Hammer等;《Bioconjugate Chem.》;20021101;第13卷(第6期);第1244-1252页 *
Synthesis of sterically hindered phthalocyanines and their applications to dye-sensitized solar cells;Seunghun Eu等;《Dalton Transactions》;20080630(第40期);第5476-5483页 *
Synthesis, spectral and aggregation properties of a novel water-soluble tetracarboxynaphthalocyaninatozinc;Xiaobing Wang等;《Dyes and Pigments》;19930331;第41卷(第3期);第193-198页 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108028137A (en) * 2015-09-17 2018-05-11 富士胶片株式会社 Photoelectric conversion element, dye-sensitized solar cell, dye composition, and oxide semiconductor electrode
CN108028137B (en) * 2015-09-17 2020-02-21 富士胶片株式会社 Photoelectric conversion element, dye-sensitized solar cell, pigment composition, and oxide semiconductor electrode

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