JP4281931B2 - Photoelectric conversion element and photoelectrochemical cell - Google Patents

Photoelectric conversion element and photoelectrochemical cell Download PDF

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JP4281931B2
JP4281931B2 JP13502599A JP13502599A JP4281931B2 JP 4281931 B2 JP4281931 B2 JP 4281931B2 JP 13502599 A JP13502599 A JP 13502599A JP 13502599 A JP13502599 A JP 13502599A JP 4281931 B2 JP4281931 B2 JP 4281931B2
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JP2000323191A (en
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裕雄 滝沢
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富士フイルム株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/542Dye sensitized solar cells

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention has a high light absorption ability even in a long wavelength region.By metal complex dyeThe present invention relates to a photoelectric conversion element using sensitized semiconductor fine particles and a photoelectrochemical cell comprising the photoelectric conversion element.
[0002]
[Prior art]
Solar cells made of single-crystal silicon, polycrystalline silicon, amorphous silicon, or compounds such as cadmium telluride and indium copper selenide have been put into practical use or main research and development as solar cells used for photovoltaic power generation. However, in widespread use in household power sources and the like, there are problems such as high manufacturing costs, difficulty in securing raw materials, and long energy payback time, and these must be overcome. On the other hand, many solar cells using organic materials have been proposed for the purpose of increasing the area and reducing the price, but generally have a problem that conversion efficiency is low and durability is poor.
[0003]
Under such circumstances, “Nature”, 353, 737-740, 1991, and US Pat. Wet photoelectric conversion elements and solar cells using a porous thin film as a working electrode, and materials and manufacturing techniques for producing the same have been proposed. The first advantage of this wet type photoelectric conversion element is that an inexpensive oxide semiconductor such as titanium dioxide can be used without being purified to a high purity, so that an inexpensive photoelectric conversion element can be provided. Is that the absorption of the dye used is broad, so that light in almost all wavelength regions of visible light can be converted into electricity.
[0004]
However, a known ruthenium complex dye absorbs visible light, but hardly absorbs infrared light having a wavelength longer than 700 nm, and thus has a problem of low photoelectric conversion ability in the infrared region. Therefore, in order to further increase the conversion efficiency, it is desired to develop a dye having absorption ability in a wide wavelength range from visible light to infrared region and exhibiting high photoelectric conversion ability.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to use a metal complex dye having a high light absorption ability not only in the visible light region but also in the infrared region and capable of efficiently sensitizing semiconductor fine particles, and such a metal complex dye. It is providing the photoelectric conversion element which has high photoelectric conversion efficiency by this, and the photoelectrochemical cell which consists of it.
[0006]
[Means for Solving the Problems]
As a result of diligent research in view of the above-mentioned purpose, a ligand having two or more sites capable of bidentate coordination with nitrogen to a metal atom, and a nonmetal necessary for completing a 5- or 6-membered ring as necessary By coordinating a monodentate or bidentate ligand coordinated by an acyloxy group, an acylthio group, etc. to a metal complex dye formed by coordination bond with a bidentate ligand having an atom, a long wavelength A metal complex dye having an excellent light absorption ability even in the region, and semiconductor fine particles sensitized by such a metal complex dye exhibit high photoelectric conversion efficiency suitable as a photoelectric conversion element, and become a good photoelectrochemical cell I discovered this and came up with the present invention.
[0007]
The photoelectric conversion elementThe following general formula (I):
(LL1)m1(X1)m2M1(BL) M2(X2)m3(LL2)m4・ CI (I)
(However, M1And M2Each represents a metal atom, BL represents a ligand having two or more sites capable of bidentate with nitrogen to the metal atom, X1And X2Each independently represents an acyloxy group, an oxalylene group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl A monodentate coordinated by a group selected from the group consisting of a group, a carbonyl group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a halogen atom, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, and an aryloxy group Or a bidentate ligand, or a monodentate or bidentate ligand consisting of a dialkyl ketone or carbonamide,1And LL2Are each independently represented by the following general formula (II):
[Chemical 9]
(Wherein Za and Zb each independently represents a nonmetallic atom group necessary to complete a 5- or 6-membered ring), m1 and m4 are each independently 0 Or 1, m2 and m3 each independently represent an integer of 1 to 4, and when m2 or m3 is 2 or more, X1Or X2May be the same or different, and X1Each other or X2They may be linked together, and CI represents a counter ion when a counter ion is required to neutralize the charge. Semiconductor fine particles sensitized by a metal complex dye represented byIs preferred.
[0008]
The photoelectrochemical cell uses the above photoelectric conversion element.
[0009]
By satisfying the following conditionsThus, a photoelectric conversion element and a photoelectrochemical cell containing semiconductor fine particles sensitized with a metal complex dye having a more excellent light absorption ability in a long wavelength region can be obtained.
[0010]
(1) LL represented by general formula (II)1And LL2The ring formed by Za or Zb is a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring, triazole ring, thiazole ring, oxazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring and It is preferably at least one selected from the group consisting of benzothiazole rings.
[0011]
(2) In the metal complex dye represented by the general formula (I), the ligand BL is represented by the following general formulas (III-1) to (III-3):
[Chemical Formula 10]
(However, Zc, Zd, Ze, and Zf each independently represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring, and n1 represents 0 or 1).
[0012]
(3) The ring formed by Ze or Zf in the ligand BL is preferably a pyrazine ring.
[0013]
(4) In the metal complex dye represented by the general formula (I), the ligand BL includes the following general formulas B-1 to B-10:
Embedded image
Rtwenty one~ R30Each independently represents a substituent, which may be substituted on a carbon atom of any ring of B-1 to B-10. e, f, g, h, j, k and q each independently represent an integer of 0 to 8, p and r each independently represents an integer of 0 to 6, and s represents an integer of 0 to 4. ) Is preferred.
[0014]
(5) In the ligand BL represented by the general formulas B-1 to B-10, Rtwenty one~ R30Each independently represents an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, amino group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, phosphoryl group, phosphonyl group or halogen atom.
[0015]
(6) The ligand BL in the metal complex dye of the general formula (I) is preferably represented by any one of B-1 to B-4.
[0016]
(7) Ligands LL in metal complex dyes of general formula (I)1Or LL2Are each independently of the general formula (IV-1) or (IV-2):
Embedded image
(However, R1, R2, RFiveAnd R6Each independently represents a substituent, RThreeAnd RFourEach independently represents hydrogen, an alkyl group or an aryl group, a and b each independently represent an integer of 0 to 4, c and d each independently represents an integer of 0 to 2,1And R2, RThreeAnd RFour, RThreeAnd RFiveAnd RFourAnd R6May be connected to each other to form a ring. ) Is preferred.
[0017]
(8) R in general formula (IV-1) or (IV-2)1, R2, RFiveAnd R6Are preferably each independently an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, amino group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, phosphoryl group, phosphonyl group or halogen atom.
[0018]
(9) In general formula (I), X1And X2Are preferably each independently a dithiocarbamate group, acylaminooxy group, acyloxy group, oxalylene group, isocyanate group, cyanate group, isothiocyanate group, thiocyanate group, alkylthio group or arylthio group.
[0019]
(10) The metal complex dye represented by the general formula (I) preferably has at least one acidic group.
[0020]
(11) M in general formula (I)1And M2Are preferably each independently Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn or Zn.
[0021]
(12) M in general formula (I)1And M2Are preferably each independently Ru, Fe, Os or Cu.
[0022]
(13) M in general formula (I)1And M2Is preferably Ru.
[0023]
(14) The semiconductor fine particles are preferably titanium oxide fine particles.
[0024]
That is, the photoelectric conversion element of the present invention includes:Formula (V):
(LL 1 ) m1 (X 1 ) m2 Ru (BL) Ru (X 2 ) m3 (LL 2 ) m4 ・ CI (V)
(However, BL represents the following general formulas B-1 to B-4:
(However, R twenty one , R twenty two , R twenty three And R twenty four Each independently represents an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, amino group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, phosphoryl group, phosphonyl group or halogen atom, B-1 to B- It may be bonded to any ring carbon atom of 4, and e, f, g and h each independently represent an integer of 0 to 8. Is a ligand represented by any one of
X 1 And X 2 Are independently coordinated with a group selected from the group consisting of a dithiocarbamate group, an acylaminooxy group, an acyloxy group, an oxalylene group, an isocyanate group, a cyanate group, an isothiocyanate group, a thiocyanate group, an alkylthio group, and an arylthio group. Represents a bidentate or bidentate ligand;
LL 1 And LL 2 Are each independently represented by the following general formula (IV-1) or (IV-2):
(However, R 1 , R 2 , R Five And R 6 Are each independently an alkyl group (1-20 carbon atoms), an alkenyl group (2-20 carbon atoms), an aryl group (6-26 carbon atoms), a hydroxyl group, an alkoxy group (1-20 carbon atoms). , Amino groups (0-20 carbon atoms), alkoxycarbonyl groups (2-20 carbon atoms), carboxyl groups, sulfonic acid groups (-SO Three H), a phosphoryl group (0 to 20 carbon atoms), a phosphonyl group (0 to 20 carbon atoms) and a group selected from the group consisting of halogen atoms, R Three And R Four Each independently represents an alkyl group (1-20 carbon atoms), a and b each independently represent 0 or 1, c and d each independently represents an integer of 0 to 2, 1 And R 2 , R Three And R Four , R Three And R Five And R Four And R 6 May be connected to each other to form a ring. )
m1 and m4 are each independently 0 or 1, m2 and m3 each independently represent an integer of 1 to 4, and when m2 or m3 is 2 or more, X 1 Or X 2 May be the same or different, and X 1 Each other or X 2 They may be linked together, and CI represents a counter ion when a counter ion is required to neutralize the charge. Ruthenium complex dyes represented byIt contains semiconductor fine particles sensitized by the above.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
[1] Metal complex dyes
Photoelectric conversion elementThe metal complex dye used for the following general formula (I):
(LL1)m1(X1)m2M1(BL) M2(X2)m3(LL2)m4・ CI ・ ・ ・ (I)
Represented byThings are preferred. Each component will be described in detail below.
[0027]
(A) Metal atom M1, M2
M1And M2Each represents a metal atom and M1And M2May be the same or different. M1And M2Is preferably a metal capable of tetracoordination or hexacoordination, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or Zn, particularly preferably Ru, Fe, Os or Cu, and most preferably Ru.
[0028]
(B) Ligand X1, X2
In general formula (I), X1And X2Represents a monodentate or bidentate ligand, each independently an acyloxy group (preferably having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, etc.),
Oxalylene (-OC (O) C (O) O-) group,
An acylthio group (preferably having 1 to 20 carbon atoms, such as acetylthio, benzoylthio, etc.),
A thioacyloxy group (preferably having 1 to 20 carbon atoms such as thioacetyloxy (CHThreeC (S) O-), thiobenzoyloxy, etc.),
A thioacylthio group (preferably having 1 to 20 carbon atoms such as thioacetylthio (CHThreeC (S) S-), thiobenzoylthio (PhC (S) CS-), etc.),
An acylaminooxy group (preferably having 1 to 20 carbon atoms such as N-methylbenzoylaminooxy (PhC (O) N (CHThree) O-), acetylaminooxy (CHThreeC (O) NHO-), p-toluoylaminooxy, etc.),
A thiocarbamate group (preferably having 1 to 20 carbon atoms, such as N, N-diethylthiocarbamate, N, N-dimethylthiocarbamate, etc.),
Dithiocarbamate groups (preferably having 1 to 20 carbon atoms, eg N, N-dibenzyldithiocarbamate ((PhCH2)2NC (S) S-), N, N-dimethyldithiocarbamate ((CHThree)2NC (S) S-))
A thiocarbonate group (preferably having 1 to 20 carbon atoms, such as ethyl thiocarbonate, methylthiocarbonate, etc.),
Dithiocarbonate groups (preferably having 1 to 20 carbon atoms, eg ethyl dithiocarbonate (C2HFiveOC (S) S-)),
Trithiocarbonate groups (preferably having 1 to 20 carbon atoms, eg ethyl trithiocarbonate (C2HFiveSC (S) S-) etc.),
An acyl group (preferably having 1 to 20 carbon atoms, such as acetyl, benzoyl, etc.),
Carbonyl group (-CO),
Dialkyl ketones (preferably having 3 to 20 carbon atoms such as acetone ((CHThree)2CO ...), CHThreeC (O ...) CH2C (O ...) CHThreeEtc. (... represents a coordination bond), acetylacetone, etc.)
Carbonamide (preferably having 1 to 20 carbon atoms, eg CHThreeNHC (CHThree) O ..., OC (NH2) -C (NH2) O ... etc)
Thiocyanate group,
An isothiocyanate group,
Cyanate groups,
Isocyanate groups,
A halogen atom (preferably chlorine, bromine, iodine),
A cyano group,
An alkylthio group (preferably having 1 to 20 carbon atoms, such as methanethio, ethylenedithio, propylenedithio, etc.),
An arylthio group (preferably having 6 to 20 carbon atoms, such as benzenethio, 1,2-phenylenedithio, etc.),
An alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy), and
Aryloxy group (preferably having 6 to 20 carbon atoms such as phenoxy, 1,2-phenylenedioxy, etc.)
A ligand coordinated by a group selected from the group consisting of
[0029]
In the general formula (I), the ligand X1And X2M2 and m3 representing the number of each independently represent an integer of 1 to 4, preferably 1 or 2. X when m2 or m3 is 2 or more1Or X2Can be the same or different, and X1Each other or X2They may be linked together.
[0030]
When m2 and m3 are 1, X1Or X2Are preferably bidentate ligands, specifically acyloxy groups, oxalylene groups, acylthio groups, thioacyloxy groups, thioacylthio groups, acylaminooxy groups, thiocarbamate groups, dithiocarbamate groups, thiocarbonate groups. , A ligand coordinated by a dithiocarbonate group, a trithiocarbonate group, an alkylthio group or an arylthio group, or a ligand composed of a dialkyl ketone or a carbonamide.
[0031]
If m2 and m3 are 2 or more, X1Or X2Is preferably a monodentate ligand, specifically, acyl group, carbonyl group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, halogen atom, cyano group, alkylthio group, arylthio group, alkoxy group or A ligand coordinated by an aryloxy group, or a ligand composed of dialkyl ketone or carbonamide is preferred. X at this time1And X2May be the same or different, but are preferably the same.
[0032]
X1And X2Specific examples of these are shown below, but the present invention is not limited thereto. The structural formula shown here is just one of the many possible resonance structures, and the distinction between covalent bonds (represented by −) and coordinate bonds (represented by...) Is also formal. Does not represent an absolute distinction.
[0033]
Embedded image
[0034]
Embedded image
[0035]
Embedded image
[0036]
(C) Bidentate LL1, LL2
Bidentate ligand LL1And LL2Are each independently represented by the general formula (II). LL1And LL2May be the same or different, but are preferably the same. In general formula (II), Za and Zb each independently represents a nonmetallic atom group capable of forming a 5- or 6-membered ring. Za and Zb are preferably composed of an element selected from the group consisting of carbon, oxygen, hydrogen, nitrogen, sulfur, phosphorus and halogen atoms, and preferably form an aromatic ring.
[0037]
The aromatic ring independently formed by Za and Zb is preferably a pyridine ring, a pyrimidine ring, a pyrazine ring or a pyridazine ring in the case of a 6-membered ring, and a pyrazole ring, an imidazole ring or a triazole in the case of a 5-membered ring. A ring, thiazole ring, oxazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring or benzothiazole ring is preferred. Of these, a pyridine ring, an imidazole ring, and a benzimidazole ring are more preferable.
[0038]
LL1And LL2Are more preferably those independently represented by the following general formula (IV-1) or general formula (IV-2).
Embedded image
In each of general formula (IV-1) and general formula (IV-2), R1, R2, RFiveAnd R6Each independently represents a substituent, preferably an alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, i-propyl, t-butyl, benzyl, 4-carboxylmethyl, etc.), an alkenyl group (preferably 2-20 carbon atoms, such as vinyl, allyl, oleyl, etc., aryl groups (preferably 6-26 carbon atoms, such as phenyl, 2-naphthyl, 4-carboxylphenyl, etc.), hydroxyl groups, alkoxy groups (preferably 1-20 carbon atoms, such as methoxy, 2-carboxyethoxy, etc., amino groups (preferably 0-20 carbon atoms, such as amino, N, N-dimethylamino, anilino, etc.), alkoxycarbonyl groups (preferably carbon 2-20 atoms such as ethoxycarbonyl, carboxyl group, sulfonic acid group (-SOThreeH), phosphoryl group (preferably having 0 to 20 carbon atoms, for example, -OP (O) (OH)2, -OP (O) (OC2HFive)2), Phosphonyl groups (preferably having 0 to 20 carbon atoms, eg -P (O) (OH)2, -P (O) (OC2HFive)2Or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), more preferably an alkyl group, alkenyl group, hydroxyl group, alkoxy group, carboxyl group, sulfonic acid group, phosphoryl group or phosphonyl group. .
[0039]
a and b each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1.
[0040]
RThreeAnd RFourEach independently represents hydrogen, an alkyl group or an aryl group, more preferably an alkyl group. RThreeAnd RFourPreferred examples of R1Is the same. C and d each independently represent an integer of 0 to 2. R1And R2, RThreeAnd RFour, RThreeAnd RFiveAnd RFourAnd R6May be connected to each other to form a ring.
[0041]
LL of metal complex dyes represented by general formula (I)1andLL 2 Specific examples of these are shown below, but the present invention is not limited thereto.
[0042]
Embedded image
[0043]
Embedded image
[0044]
[0045]
(D) Ligand BL
In the general formula (I), BL represents a ligand having two or more sites capable of bidentate coordination with nitrogen with respect to a metal atom. When there are 3 or more sites capable of bidentate coordination, M in formula (I)1And M2In addition, it may have a coordination metal. BL is preferably represented by the general formula (III-1), (III-2) or (III-3). In the general formulas (III-1) to (III-3), Zc, Zd, Ze, and Zf each independently represent a nonmetallic atom group that can form a 5- or 6-membered ring, and include carbon, oxygen, hydrogen, nitrogen, It is preferably composed of an element selected from the group consisting of sulfur, phosphorus and halogen atoms, and more preferably forms an aromatic ring. Two or more of these rings may be bonded to each other to form a condensed ring.
[0046]
A preferred aromatic ring independently formed by Zc and Zd is the same as Za, more preferably a pyridine ring or an imidazole ring, and still more preferably a pyridine ring. The rings independently formed by Ze and Zf are preferably a pyrazine ring, a pyridazine ring or a tetrazine ring, and more preferably a pyrazine ring.
[0047]
Specific examples of the ligands represented by the general formulas (III-1) to (III-3) include those represented by the following general formulas B-1 to B-10.
Embedded image
In general formulas B-1 to B-10, Rtwenty one~ R30Each independently represents a substituent, which may be substituted on a carbon atom of any ring of B-1 to B-10. Rtwenty one~ R30Preferably represents an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, amino group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, phosphoryl group, phosphonyl group or halogen atom, more preferred examples being R1It is the same as that illustrated in.
[0048]
e, f, g, h, j, k and q each independently represents an integer of 0 to 8, p and r each independently represents an integer of 0 to 6, and s represents an integer of 0 to 4 . It is preferable that all are integers of 0-2.
[0049]
The ligand BL is preferably represented by any one of B-1 to B-4, B-7 and B-10, and more preferably represented by B-1 to B-4 or B-10. Preferably, it is represented by B-1 to B-4.
[0050]
Specific examples of the bridging ligand BL are shown below, but the present invention is not limited thereto.
[0051]
Embedded image
[0052]
Embedded image
[0053]
(E) Counter ion CI
In the general formula (I), CI represents a counter ion when a counter ion is required to neutralize the charge. Whether the dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the dye. When the substituent has a dissociable group, it may be dissociated to have a negative charge, and in this case as well, the charge of the entire molecule is neutralized by CI. Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions, etc.) and alkali metal ions. On the other hand, the anion may be either an inorganic or organic anion, such as a halogen anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion, etc.), substituted aryl sulfonate ion (eg, p-toluene). Sulfonate ions, p-chlorobenzenesulfonate ions, etc.), aryl disulfonate ions (eg, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfates Examples thereof include ions (for example, methyl sulfate ion), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, picrate ions, acetate ions, trifluoromethanesulfonate ions, and the like. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, or a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) is also used. Is possible.
[0054]
(F) Bonding group
The dye represented by the general formula (I) preferably has at least one suitable interlocking group for the surface of the semiconductor fine particles. Preferred linking groups include a carboxyl (COOH) group and a sulfonic acid (SOThreeH) group, phosphonic acid (-P (O) (OH)2) Group, phosphoric acid (-OP (O) (OH)2) Group, hydroxyl group and other acidic groups (substituents having dissociable protons), or chelating groups having π conductivity such as oxime, dioxime, hydroxyquinoline, salicylate and α-ketoenolate. Of these, a carboxyl group, a phosphoric acid group, and a phosphonic acid group are particularly preferable. These groups may form a salt with an alkali metal or the like, or may form an internal salt.
[0055]
These linking groups are BL, LL1Or LL2Is preferably contained in R1~ R6And Rtwenty one~ R30More preferably, it is contained in any of the above. 1-8 are preferable, as for the number of these coupling groups in the metal complex pigment | dye represented by general formula (I), 2-6 are more preferable, and 2-4 are especially preferable.
[0056]
(G) Specific examples of metal complex dyes
Among the above metal complex dyes, particularly preferred are the following general formula (I):
(LL1)m1(X1)m2M1(BL) M2(X2)m3(LL2)m4・ CI (I)
(However, M1And M2Each represents a metal atom capable of 4 or 6 coordination;
BL is the above general formula B-1 to B-10 (however, Rtwenty one~ R30Each independently represents a substituent and may be bonded to any ring carbon atom of B-1 to B-10, and e, f, g, h, j, k and q are each independently 0 to 0. 8 represents an integer, p and r each independently represent an integer of 0 to 6, and s represents an integer of 0 to 4. ), And
X1And X2Are each independently an acyloxy group, oxalylene group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl A monodentate coordinated with a group selected from the group consisting of a group, a carbonyl group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a halogen atom, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, and an aryloxy group Or a bidentate ligand, or a monodentate or bidentate ligand consisting of a dialkyl ketone or a carbonamide,
LL1And LL2Each independently represents the above general formula (IV-1) or (IV-2) (where R1, R2, RFiveAnd R6Each independently represents a substituent, a and b each independently represent an integer of 0 to 4, c and d each independently represents an integer of 0 to 2,11And R12, RThreeAnd RFour, RThreeAnd R15And RFourAnd R16May be connected to each other to form a ring. Represents a bidentate ligand represented by:
m1 and m4 are each independently 0 or 1,
m2 and m3 each independently represents an integer of 1 to 4, and when m2 or m3 is 2 or more, X1Or X2May be the same or different, and X1Each other or X2They may be linked together,
CI represents a counter ion when a counter ion is required to neutralize the charge. ).
[0057]
Particularly preferred metal complex dyes are represented by the following general formula (V):
(LL1)m1(X1)m2Ru (BL) Ru (X2)m3(LL2)m4・ CI (V)
A ruthenium complex dye represented by
X1And X2Each independentlyDithiocarbamate group (1-20 carbon atoms), acylaminooxy group (1-20 carbon atoms), acyloxy group (1-20 carbon atoms), oxalylene group, isocyanate group, cyanate group, isothiocyanate group, thiocyanate Groups, alkylthio groups (1-20 carbon atoms) and arylthio groups (6-20 carbon atoms)Represents a monodentate or bidentate ligand coordinated with a group selected from the group consisting of
BL is the above general formula B-1 to B-4 (however, Rtwenty one, Rtwenty two, Rtwenty threeAnd Rtwenty fourEach independently represents an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, amino group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, phosphoryl group, phosphonyl group or halogen atom, B-1 to B- It may be bonded to any ring carbon atom of 4, and e, f, g and h each independently represent an integer of 0 to 8. Is a ligand represented by any one of
LL1And LL2Are each independently the above general formula (IV-1) or (IV-2) (whereinR 1 , R 2 , R Five And R 6 Are each independently an alkyl group (1-20 carbon atoms), an alkenyl group (2-20 carbon atoms), an aryl group (6-26 carbon atoms), a hydroxyl group, an alkoxy group (1-20 carbon atoms). , Amino groups (0-20 carbon atoms), alkoxycarbonyl groups (2-20 carbon atoms), carboxyl groups, sulfonic acid groups (-SO Three H), a phosphoryl group (0 to 20 carbon atoms), a phosphonyl group (0 to 20 carbon atoms) and a group selected from the group consisting of halogen atomsRepresentsR Three And R Four Each independently represents an alkyl group (1-20 carbon atoms),a and b are independently0 or 1C and d each independently represents an integer of 0 to 2;1And R2, RThreeAnd RFour, RThreeAnd RFiveAnd RFourAnd R6May be connected to each other to form a ring. Represents a bidentate ligand represented by:
[0058]
Specific examples of such metal complex dyes are shown below, but the present invention is not limited thereto. In the following specific examples, a ligand with “′” such as L-5 ′... Is dissociated from the carboxyl group of the ligand such as L-5. It shows what became. However, L-5 ′, etc. may be in equilibrium with L-5, respectively, and the structure of the counter ion CI may be changed accordingly.
[0059]
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[0060]
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[0061]
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[0062]
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[0063]
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[0064]
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[0065]
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[0066]
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[0067]
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[0068]
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[0069]
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[0070]
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[0071]
Formula (I) The synthesis of the metal complex dye represented by Inorg. Chem. Acta.,206, 69 (1993), Inorg. Chem.,29, 1888 (1990), J. Am. Chem. Soc.,109, 2691 (1987), Inorg. Chem.,29, 4750 (1990), Inorg. Chem.,28, 1520 (1989), Inorg. Chem.,29, 167 (1990), and the like.
[0072]
When the metal complex dye of the present invention contains an alkyl group, alkenyl group, alkynyl group, alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the metal complex dye of the present invention contains an aryl group, a heterocyclic group, a cycloalkyl group or the like, these may be substituted or unsubstituted, and may be monocyclic or condensed.
[0073]
[2] photoelectric conversion elements
The photoelectric conversion element of the present invention has the above-described photosensitive layer.Represented by general formula (V)It has semiconductor fine particles sensitized with a metal complex dye. Preferably, as shown in FIG. 1, a conductive support 10, a photosensitive layer 20, a charge transfer layer 30 and a counter electrode 40 are laminated in this order, and the conductive support layer 10 is composed of a base material 11 and a conductive layer 12. The photosensitive layer 20The metal complex dye 22And the electrolyte 30 filled in the gap between the semiconductor fine particles 21. A photoelectrochemical cell is one in which this photoelectric conversion element is connected to an external circuit for work.
[0074]
The metal complex dye 22The light incident on the photosensitive layer 20 containing the semiconductor fine particles 21 sensitized by the excitation excites the dye 22 and the like, and high-energy electrons in the excited dye 22 and the like are passed to the conduction band of the semiconductor fine particles 21 and further diffused. Thus, the conductive support 10 is reached. At this time, the molecule such as the dye 22 is an oxidant. In the photoelectrochemical cell, electrons in the conductive support 10 return to an oxidant such as the dye 22 through the counter electrode 40 and the charge transfer layer 30 while working in an external circuit, and the dye 22 is regenerated. The semiconductor layer 20 functions as a negative electrode. At the boundary of each layer (for example, the boundary between the conductive layer 12 and the photosensitive layer 20 of the conductive support 10, the boundary between the photosensitive layer 20 and the charge transfer layer 30, the boundary between the charge transfer layer 30 and the counter electrode 40, etc.) The components of each layer may be diffusively mixed with each other. Each layer will be described in detail below.
[0075]
[A] Conductive support
As the conductive support, use is made of a glass or plastic substrate 11 having a conductive layer 12 containing a conductive agent on the photosensitive layer side as shown in FIG. can do. In the latter case, preferred conductive agents are metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine) Etc.). The thickness of the conductive layer 12 is preferably about 0.02 to 10 μm.
[0076]
The lower the surface resistance of the conductive support, the better. The range of the surface resistance is preferably 100Ω / □ or less, more preferably 40Ω / □ or less. The lower limit of the surface resistance is not particularly limited, but is usually about 0.1Ω / □.
[0077]
When light is irradiated from the conductive support side, the conductive support is preferably photoelectrochemically substantially transparent. “Substantially transparent” means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 70% or more. The transparent conductive support is preferably formed by applying or vapor-depositing a transparent conductive layer made of a conductive metal oxide on the surface of a transparent substrate such as glass or plastic. In particular, conductive glass in which a conductive layer made of tin dioxide doped with fluorine is deposited on a transparent substrate made of low-cost soda-lime float glass is preferable. In order to obtain a flexible photoelectric conversion element or solar cell at low cost, it is preferable to use a transparent polymer film provided with a conductive layer. Transparent polymer films include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndioctaic polyester (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr). ), Polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy and the like. In order to ensure sufficient transparency, the amount of conductive metal oxide applied is 1 m of glass or plastic support.2The amount is preferably 0.01 to 100 g.
[0078]
It is preferable to use a metal lead for the purpose of reducing the resistance of the transparent conductive support. The material of the metal lead is preferably a metal such as aluminum, copper, silver, gold, platinum, nickel, and particularly preferably aluminum and silver. The metal lead is preferably installed on a transparent substrate by vapor deposition, sputtering or the like, and a transparent conductive layer made of tin oxide doped with fluorine or an ITO film is preferably provided thereon. Moreover, it is also preferable to install a metal lead on the transparent conductive layer after providing the transparent conductive layer on the transparent substrate. The decrease in the amount of incident light due to the metal lead installation is within 10%, more preferably 1 to 5%.
[0079]
[B] Photosensitive layer
Metal complex dyeIn the photosensitive layer containing the semiconductor fine particles sensitized by the semiconductor fine particles, the semiconductor fine particles act as a so-called photoconductor, absorb light, separate charges, and generate electrons and holes. In the dye-sensitized semiconductor fine particles, light absorption and generation of electrons and holes thereby occur mainly in the dye, and the semiconductor fine particles play a role of receiving and transmitting the electrons.
[0080]
(1) Semiconductor fine particles
Semiconductor fine particles include simple semiconductors such as silicon and germanium, III-V compound semiconductors, metal chalcogenides (eg oxides, sulfides, selenides, etc.), or compounds having a perovskite structure (eg strontium titanate, titanium). Calcium oxide, sodium titanate, barium titanate, potassium niobate, etc.) can be used.
[0081]
Preferred metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxides, cadmium, zinc, lead, silver, antimony, Bismuth sulfide, cadmium, lead selenide, cadmium telluride and the like. Other compound semiconductors include phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like.
[0082]
Preferred specific examples of the semiconductor used in the present invention include Si and TiO.2, SnO2, Fe2OThree, WOThree, ZnO, Nb2OFive, CdS, ZnS, PbS, Bi2SThree, CdSe, CdTe, GaP, InP, GaAs, CuInS2, CuInSe2More preferably, TiO2, ZnO, SnO2, Fe2OThree, WOThree, Nb2OFive, CdS, PbS, CdSe, InP, GaAs, CuInS2, CuInSe2And particularly preferably TiO2Or Nb2OFiveAnd most preferably TiO2It is.
[0083]
The semiconductor used in the present invention may be single crystal or polycrystalline. Single crystals are preferable from the viewpoint of conversion efficiency, but polycrystals are preferable from the viewpoints of manufacturing cost, securing raw materials, energy payback time, and the like.
[0084]
The particle size of the semiconductor fine particles is generally on the order of nm to μm, but the average particle size of the primary particles obtained from the diameter when the projected area is converted into a circle is preferably 5 to 200 nm, more preferably 8 to 100 nm. preferable. The average particle size of the semiconductor fine particles (secondary particles) in the dispersion is preferably 0.01 to 100 μm.
[0085]
Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 5 nm or less. For the purpose of improving the light capture rate by scattering incident light, semiconductor particles having a large particle diameter, for example, about 300 nm may be mixed.
[0086]
Semiconductor fine particles are prepared by Sakuo Sakuo's "Sol-gel Method Science" Agne Jofusha (1998), Technical Information Association "Sol-gel Method Thin Film Coating Technology" (1995), etc. The described sol-gel method, Tadao Sugimoto, “Synthesis and size control of monodisperse particles by the new synthetic gel-sol method”, “Materia”, Vol. 35, No. 9, pp. 1012-1018 (1996) The gel-sol method described in the "year" is preferred. Also preferred is a method developed by Degussa to produce an oxide by high-temperature hydrolysis of chloride in an oxyhydrogen salt.
[0087]
When the semiconductor fine particles are titanium oxide, the sol-gel method, gel-sol method, and high-temperature hydrolysis method in oxyhydrogen salt of chloride are all preferred, but Kiyoshi Manabu's “Titanium oxide properties and applied technology” The sulfuric acid method and the chlorine method described in Gihodo Publishing (1997) can also be used. Furthermore, as a sol-gel method, the method described in “Journal of American Ceramic Society” such as Barb, Vol. 80, No. 12, pp. 3157-3171 (1997), and “Chemicals such as Burnside” The method described in “Materials”, Vol. 10, No. 9, pages 2419-2425 is also preferable.
[0088]
(2) Semiconductor fine particle layer
In order to apply the semiconductor fine particles on the conductive support, in addition to the method of applying a dispersion or colloidal solution of semiconductor fine particles on the conductive support, the above-described sol-gel method or the like can also be used. In consideration of mass production of photoelectric conversion elements, physical properties of semiconductor fine particle liquid, flexibility of conductive support, etc., a wet film forming method is relatively advantageous. As a wet film forming method, a coating method and a printing method are typical.
[0089]
In addition to the sol-gel method described above, a method for preparing a dispersion of semiconductor fine particles includes a method of grinding with a mortar, a method of dispersing while grinding using a mill, or a fine particle in a solvent when synthesizing a semiconductor. The method of depositing and using as it is is mentioned.
[0090]
Examples of the dispersion medium include water or various organic solvents (for example, methanol, ethanol, isopropyl alcohol, dichloromethane, acetone, acetonitrile, ethyl acetate, and the like). During dispersion, a polymer, surfactant, acid, chelating agent, or the like may be used as a dispersion aid as necessary.
[0091]
The application method is disclosed in Japanese Patent Publication No. 58-4589 as a roller method, a dip method as an application system, an air knife method, a blade method, etc. as a metering system, and the application and metering can be performed in the same part. The wire bar method, the slide hopper method, the extrusion method, the curtain method and the like described in U.S. Pat. Nos. 2,681,294, 2,714,419 and 2,767,911, are preferred. Moreover, a spin method and a spray method are also preferable as a general purpose machine. Further, as the wet printing method, intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness.
[0092]
The viscosity of the dispersion of semiconductor fine particles greatly depends on the type and dispersibility of the semiconductor fine particles, the type of solvent used, and additives such as surfactants and binders. For a high viscosity liquid (for example, 0.01 to 500 Poise), an extrusion method, a casting method, a screen printing method, or the like is preferable. For low-viscosity liquids (for example, 0.1 Poise or less), the slide hopper method, wire bar method, or spin method is preferable, and a uniform film can be obtained. If there is a certain amount of coating, coating by the extrusion method is possible even in the case of a low viscosity liquid. Thus, a wet film forming method may be selected as appropriate according to the viscosity of the coating solution, the coating amount, the support, the coating speed, and the like.
[0093]
The semiconductor fine particle layer is not limited to a single layer, but a multi-layer coating of a dispersion of semiconductor fine particles having different particle diameters, or a multi-layer coating of a coating layer containing different types of semiconductor fine particles (or different binders and additives) You can also Multi-layer coating is also effective when the film thickness is insufficient with a single coating. For multilayer coating, an extrusion method or a slide hopper method is suitable. In the case of applying multiple layers, the multiple layers may be applied at the same time, or may be successively applied several times to several dozen times. Further, screen printing can be preferably used as long as it is sequentially overcoated.
[0094]
In general, as the thickness of the semiconductor fine particle layer (same as the thickness of the photosensitive layer) increases, the amount of supported dye increases per unit projected area, and thus the light capture rate increases. Loss due to coupling also increases. Therefore, the preferable thickness of the semiconductor fine particle layer is 0.1 to 100 μm. When used in a photoelectrochemical cell, the thickness of the semiconductor fine particle layer is preferably 1 to 30 μm, and more preferably 2 to 25 μm. Semiconductor fine particle support 1m2The coating amount per unit is preferably 0.5 to 400 g, more preferably 5 to 100 g.
[0095]
After the semiconductor fine particles are applied on the conductive support, the semiconductor fine particles are preferably brought into contact with each other electronically, and heat treatment is preferably performed in order to improve the coating strength and the adhesion to the support. A preferable heating temperature range is 40 ° C. or higher and lower than 700 ° C., and more preferably 100 ° C. or higher and 600 ° C. or lower. The heating time is about 10 minutes to 10 hours. When using a support having a low melting point or softening point such as a polymer film, high temperature treatment is not preferable because it causes deterioration of the support. Moreover, it is preferable that it is as low as possible also from a viewpoint of cost. The temperature can be lowered by using a combination of small semiconductor fine particles of 5 nm or less or heat treatment in the presence of a mineral acid as described above.
[0096]
In order to increase the surface area of the semiconductor fine particles after heat treatment, increase the purity near the semiconductor fine particles, and increase the efficiency of electron injection from the dye to the semiconductor particles, for example, chemical plating using a titanium tetrachloride aqueous solution or a titanium trichloride aqueous solution is used. The electrochemical plating process used may be performed.
[0097]
The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For this reason, the surface area of the semiconductor fine particle layer coated on the support is preferably 10 times or more, more preferably 100 times or more the projected area. The upper limit is not particularly limited, but is usually about 1000 times.
[0098]
(3) Adsorption of metal complex dye on semiconductor fine particles
In order to adsorb the metal complex dye to the semiconductor fine particles, a method of immersing a conductive support having a well-dried semiconductor fine particle layer in a solution of the metal complex dye or applying a solution of the metal complex dye to the semiconductor fine particle layer. Can be used. In the former case, an immersion method, a dip method, a roller method, an air knife method or the like can be used. In the immersion method, the adsorption of the metal complex dye may be performed at room temperature, or may be performed by heating and refluxing as described in JP-A-7-249790. Examples of the latter application method include a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method. Examples of the printing method include letterpress, offset, gravure, and screen printing. The solvent can be appropriately selected according to the solubility of the metal complex dye. For example, alcohols (methanol, ethanol, t-butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated hydrocarbons (dichloromethane, dichloroethane, chloroform, chlorobenzene) Etc.), ethers (diethyl ether, tetrahydrofuran, etc.), dimethyl sulfoxide, amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), N-methylpyrrolidone, 1,3-dimethylimidazolidinone , 3-methyloxazolidinone, esters (ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2-butanone, cyclohexanone, etc.), hydrocarbons (hexane) , Petroleum ether, ben Zen, toluene, etc.) and mixed solvents thereof.
[0099]
As for the viscosity of the solution of the metal complex dye, as in the formation of the semiconductor fine particle layer, various printing methods other than the extrusion method are suitable for the high viscosity liquid (for example, 0.01 to 500 Poise), and the low viscosity liquid (for example, The slide hopper method, wire bar method, or spin method is suitable for 0.1 Poise or less), and any of them can form a uniform film.
[0100]
Thus, the dye adsorption method may be appropriately selected according to the viscosity of the metal complex dye coating solution, the coating amount, the conductive support, the coating speed, and the like. The time required for the dye adsorption after coating is preferably as short as possible when mass production is considered.
[0101]
Since the presence of the unadsorbed metal complex dye becomes a disturbance of device performance, it is preferably removed by washing immediately after the adsorption. It is preferable to use a wet cleaning tank and perform cleaning with a polar solvent such as acetonitrile or an organic solvent such as an alcohol solvent. In order to increase the adsorption amount of the dye, it is preferable to perform a heat treatment before the adsorption. In order to avoid water adsorbing on the surface of the semiconductor fine particles after the heat treatment, it is preferable to quickly adsorb the dye between 40 to 80 ° C. without returning to normal temperature.
[0102]
The total amount of metal complex dye used is the unit surface area of the conductive support (1 m2) Is preferably from 0.01 to 100 mmol. Moreover, it is preferable that the adsorption amount with respect to the semiconductor fine particle of a pigment | dye is 0.01-1 mmol per 1g of semiconductor fine particle. By using such an amount of adsorption of the metal complex dye, a sensitization effect in a semiconductor can be sufficiently obtained. On the other hand, if the amount of the dye is too small, the sensitizing effect becomes insufficient, and if the amount of the dye is too large, the dye not attached to the semiconductor floats, which causes a reduction in the sensitizing effect.
[0103]
Two or more kinds of dyes can be mixed in order to make the wavelength range of photoelectric conversion as wide as possible and increase the conversion efficiency. In this case, it is preferable to select the dye to be mixed and the ratio thereof so as to match the wavelength range and intensity distribution of the light source. In particular,Represented by general formula (V)Use two or more metal complex dyes together,Represented by general formula (V)It is possible to use a metal complex dye in combination with a conventional metal complex dye and / or a polymethine dye.
[0104]
For the purpose of reducing the interaction between metal complex dyes such as association, a colorless compound may be co-adsorbed on the semiconductor fine particles. Examples of the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, chenodeoxycholic acid). An ultraviolet absorber can also be used in combination.
[0105]
For the purpose of promoting the removal of excess metal complex dye, the surface of the semiconductor fine particles may be treated with amines after adsorbing the metal complex dye. Preferable amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquids, they may be used as they are, or may be used after being dissolved in an organic solvent.
[0106]
[C] Charge transfer layer
The charge transfer layer is a layer having a function of replenishing electrons to the oxidized metal complex dye. Typical materials that can be used for the charge transfer layer include a liquid (electrolyte) in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a polymer matrix is impregnated with a liquid in which a redox couple is dissolved in an organic solvent, and oxidation. Examples thereof include a molten salt containing a reducing pair. Furthermore, a solid electrolyte or a hole transport material can also be used.
[0107]
The electrolytic solution used in the present invention preferably comprises an electrolyte, a solvent and an additive. As electrolytes, (a) I2And iodide (LiI, NaI, KI, CsI, CaI2(B) Br in combination with a metal iodide such as tetraalkylammonium iodide, pyridinium iodide, quaternary ammonium compounds such as imidazolium iodide, etc.2And bromide (LiBr, NaBr, KBr, CsBr, CaBr2(C) Metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions, etc., in combination with metal bromides such as tetraalkylammonium bromide, pyridinium bromide, etc. (D) Sulfur compounds such as sodium polysulfide and alkylthiol-alkyldisulfides, (e) viologen dyes, hydroquinone-quinones and the like can be used. Above all, I2An electrolyte in which LiI, a pyridinium iodide, an iodine salt of a quaternary ammonium compound such as imidazolium iodide is combined is preferable. The above electrolytes may be used as a mixture. The electrolyte is in a molten state at room temperature described in EP718288, WO95 / 18456, J. Electrochem. Soc., Vol.143, No. 10, 3099 (1996), Inorg. Chem., 35, 1168-1178 (1996). The salt (molten salt) can also be used. When using a molten salt as an electrolyte, the solvent may not be used.
[0108]
A preferable electrolyte concentration is 0.1 to 15M, and more preferably 0.2 to 10M. Further, when iodine is added to the electrolyte, a preferable concentration of iodine is 0.01 to 0.5M.
[0109]
As the electrolyte solvent, it is desirable to use a compound that can exhibit excellent ionic conductivity because it has low viscosity and high ion mobility, or has a high dielectric constant and high effective carrier concentration, or both. . Examples of such solvents include the following.
[0110]
(a) Carbonates
For example, ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and the like are preferable.
[0111]
(b) Lactones
For example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, crotolactone, γ-caprolactone, δ-valerolactone and the like are preferable.
[0112]
(c) Ethers
For example, ethyl ether, 1,2-dimethoxyethane, diethoxyethane, trimethoxymethane, ethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 1,3-dioxolane, 1,4-dioxane and the like are preferable.
[0113]
(d) Alcohols
For example, methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether and the like are preferable.
[0114]
(e) Glycols
For example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin and the like are preferable.
[0115]
(f) Glycol ethers
For example, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether and the like are preferable.
[0116]
(g) Tetrahydrofurans
For example, tetrahydrofuran, 2-methyltetrahydrofuran and the like are preferable.
[0117]
(h) Nitriles
For example, acetonitrile, glutarodinitrile, propionitrile, methoxyacetonitrile, benzonitrile and the like are preferable.
[0118]
(i) Carboxylic acid esters
For example, methyl formate, methyl acetate, ethyl acetate, methyl propionate and the like are preferable.
[0119]
(j) Phosphoric acid triesters
For example, trimethyl phosphate and triethyl phosphate are preferable.
[0120]
(k) Heterocyclic compounds
For example, N-methylpyrrolidone, 4-methyl-1,3-dioxane, 2-methyl-1,3-dioxolane, 3-methyl-2-oxazolidinone, 1,3-propane sultone, sulfolane, etc.
preferable.
[0121]
(l) Other
Preferred are aprotic organic solvents such as dimethyl sulfoxide, formamide, N, N-dimethylformamide, nitromethane, and water.
[0122]
Of these, carbonate-based solvents, nitrile-based solvents, and heterocyclic compound-based solvents are preferable. These solvents may be used as a mixture of two or more if necessary.
[0123]
Further, in the present invention, bases such as ter-butylpyridine, 2-picoline, 2,6-lutidine and the like described in J. Am. Ceram. Soc., 80 (12), 3157-3171 (1997) Sexual compounds can also be added. A preferable concentration range when adding a basic compound is 0.05 to 2M.
[0124]
The electrolyte can be used after being gelled (solidified) by a method such as addition of a polymer or an oil gelling agent, polymerization of coexisting polyfunctional monomers, or a crosslinking reaction with the polymer. In the case of gelation by addition of a polymer, compounds described in Polymer Electrolyte Reviews-1, 2 (JR MacCaLLum and CA Vincent, ELSEIVER APPLIED SCIENCE) can be used, but in particular, polyacrylonitrile and polyfluoride are used. It is preferred to use vinylidene chloride. J. Chem. Soc. Japan, Ind. Chem. Sec., 46, 779 (1943), J. Am. Chem. Soc., 111, 5542 (1989), J. Chem. Chem. Soc., Chem. Commun., 1993, 390, Angew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem. Lett., 1996, 885, J. Chem. Soc., Chem. The compounds described in Commun., 545 (1997) can be used. Of these, preferred compounds are those having an amide structure in the molecular structure.
[0125]
When a gel electrolyte is formed by polymerization of polyfunctional monomers coexisting with the electrolyte, a solution is prepared from the polyfunctional monomers, polymerization initiator, electrolyte and solvent, and cast, coating, dipping, impregnation, etc. It is coated on the dye-sensitized semiconductor fine particle layer (photosensitive layer 20) by a method. As shown in FIG. 1, a method is preferred in which a gap between the dye-sensitized semiconductor fine particles 21 is filled with a sol-like electrolyte, a sol-like electrolyte layer is formed on the photosensitive layer 20, and then gelled by radical polymerization. .
[0126]
The polyfunctional monomer is preferably a compound having two or more ethylenically unsaturated groups, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol. Ethylene glycol diacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.
[0127]
The gel electrolyte may contain a monofunctional monomer in addition to the polyfunctional monomer. Monofunctional monomers include esters or amides derived from acrylic acid or α-alkylacrylic acids (eg methacrylic acid) (eg N-iso-propylacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfone) Acid, acrylamidopropyltrimethylammonium chloride, methyl acrylate, hydroxyethyl acrylate, N-propyl acrylate, N-butyl acrylate, 2-methoxyethyl acrylate, cyclohexyl acrylate, etc.), vinyl esters (eg vinyl acetate), maleic acid or fumaric acid Esters derived from (eg, dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), organic acid salts (eg, sodium salt of maleic acid, fumaric acid, p-styrenesulfonic acid, etc.) Nitriles (acrylonitrile, methacrylonitrile, etc.), dienes (eg, butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (eg, styrene, p-chlorostyrene, sodium styrenesulfonate), nitrogen-containing heterocyclic rings Vinyl compounds having quaternary ammonium salts, N-vinylformamide, N-vinyl-N-methylformamide, vinyl sulfonic acid, sodium vinyl sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers ( For example, methyl vinyl ether), olefins (ethylene, propylene, 1-butene, isobutene, etc.), N-phenylmaleimide and the like are preferable. The ratio of the polyfunctional monomer to the total amount of the monomer is preferably 0.5 to 70% by weight, and more preferably 1.0 to 50% by weight.
[0128]
The above-mentioned monomers for gel electrolytes can be found in “Experimental Methods for Polymer Synthesis” by Takayuki Otsu and Masaaki Kinoshita (Chemical Doujin) and “Lecture Polymerization Reaction Theory 1 Radical Polymerization (I)” (Chemical Doujinshi) by Otsu Takayuki. Polymerization can be performed by a radical polymerization method which is a general polymer synthesis method described. The radical polymerization of the gel electrolyte monomer can be carried out by heating, light, ultraviolet light, electron beam or electrochemically, and it is particularly preferable to carry out radical polymerization by heating.
[0129]
When the crosslinked polymer is formed by heating, preferred polymerization initiators include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2 ′. -Azo initiators such as azobis (2-methylpropionate) (dimethyl 2,2'-azobisisobutyrate), peroxide initiators such as benzoyl peroxide, and the like. A preferable addition amount of the polymerization initiator is 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the total amount of monomers.
[0130]
The weight composition range of the monomers in the gel electrolyte is preferably 0.5 to 70% by weight, more preferably 1.0 to 50% by weight.
[0131]
When gelling an electrolyte by a polymer crosslinking reaction, it is desirable to use a polymer having a crosslinkable reactive group and a crosslinking agent in combination. Preferred crosslinkable reactive groups are nitrogen-containing heterocycles (eg, pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, etc.), and preferred crosslinkers are attached to the nitrogen atom. On the other hand, it is a bifunctional or higher functional reagent (for example, alkyl halide, halogenated aralkyl, sulfonate ester, acid anhydride, acid chloride, isocyanate, etc.) capable of electrophilic reaction.
[0132]
Organic and / or inorganic hole transport materials can also be used in place of the electrolyte. Preferred organic hole transport materials for the present invention include the following.
[0133]
(a) Aromatic amines
N, N'-diphenyl-N, N'-bis (4-methoxyphenyl)-(1,1'-biphenyl) -4,4'-diamine (J. Hagen et al., Synthetic Metal 89, 2153-220 (1997)), 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) 9,9'-spirobifluorene (Nature, Vol.395, 8 Oct. 1998, pp 583-585 and WO97 / 10617), 1,1-bis {4- (di-p-tolylamino) phenyl} cyclohexane tertiary diamine compound linked with a tertiary aromatic amine unit (JP 59-194393 A) ),
Aromatic compounds containing two or more tertiary amines, such as 4,4'-bis [(N-1-naphthyl) -N-phenylamino] biphenyl, with two or more condensed aromatic rings bonded to the nitrogen atom Group amines (JP-A-5-234681),
An aromatic triamine having a starburst structure with a derivative of triphenylbenzene (US Pat. No. 4,923,774, JP-A-4-308688),
Aromatic diamines (US Pat. No. 4,764,625) such as N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine,
α, α, α ′, α′-tetramethyl-α, α′-bis (4-di-p-tolylaminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084),
p-phenylenediamine derivatives,
Triphenylamine derivatives whose whole molecule is sterically asymmetric (Japanese Patent Laid-Open No. 4-129271),
A compound in which a plurality of aromatic diamino groups are substituted on the pyrenyl group (JP-A-4-175395),
An aromatic diamine in which a tertiary aromatic amine unit is linked with an ethylene group (Japanese Patent Laid-Open No. 4-264189),
An aromatic diamine having a styryl structure (JP-A-4-90851),
Benzylphenyl compounds (Japanese Patent Laid-Open No. 4-364153),
A tertiary amine linked by a fluorene group (Japanese Patent Laid-Open No. 5-25473),
Triamine compounds (Japanese Patent Laid-Open No. 5-239455),
Pisdipyridylaminobiphenyl (JP-A-5-320634),
N, N, N-triphenylamine derivatives (JP-A-6-1972),
Aromatic diamines having a phenoxazine structure (Japanese Patent Application No. 5-290728),
Diaminophenylphenanthridine derivatives (Japanese Patent Application No. 6-45669) and the like.
[0134]
(b) Oligothiophene compound
α-octylthiophene and α, ω-dihexyl-α-octylthiophene (Adv. Mater., Vol. 9, No. 7, 5578 (1997)),
Hexadodecyl dodecithiophene (Angew. Chem. Int. Ed. Engl., 34, No. 3, 303-307 (1995)),
2,8-dihexylanthra [2,3-b: 6,7-b ′] dithiophene (JACS, Vol. 120, N0.4, 664 to 672 (1998)) and the like.
[0135]
(c) Conductive polymer
Polypyrrole (K. Murakoshi et al., Chem. Lett. 1997, p.471), and
Polyacetylene and its derivatives, poly (p-phenylene) and its derivatives, poly (p-phenylenevinylene) and its derivatives, polythienylene vinylene and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives, and polytoluidine and its derivatives Etc. (each described in “Handbook of Organic Conductive Molecules and Polymers”, Vol. 1 to 4 (by NALWA, published by WILEY)).
[0136]
In organic hole transport materials, tris (4-bromophenyl) aminium hexachloro is used to control the dopant level as described in Nature, Vol. 395, 8 Oct. 583-585 (1998). Li [(CF to add a compound containing a cation radical such as antimonate or to control the potential of the oxide semiconductor surface (compensation of the space charge layer)ThreeSO2)2A salt such as N] may be added.
[0137]
The organic hole transport material can be introduced into the electrode by techniques such as vacuum deposition, casting, coating, spin coating, dipping, electrolytic polymerization, and photoelectrolytic polymerization. When a hole transporting material is used instead of the electrolyte, a thin layer of titanium dioxide is used to prevent short circuit by using a technique such as spray pyrolysis described in Electorochim. Acta 40, 643 to 652 (1995). Is preferably coated as an undercoat layer.
[0138]
When an inorganic solid compound is used instead of an electrolyte, copper iodide (p-CuI) (J. Phys. D: Appl. Phys. 31, 1492-1496 (1998)), copper thiocyanide (Thin Solid Films 261 ( 1995), 307-310, J. Appl. Phys. 80 (8), 15 October 1996, 4749-4754, Chem. Mater. 1998, 10, 1501-1509, SemiCond. Sci. Technol. 10, 1689-1693) Can be introduced into the electrode by a technique such as a casting method, a coating method, a spin coating method, a dipping method, or an electrolytic plating method.
[0139]
The following two methods can be used to form the charge transfer layer. One is that a counter electrode is bonded to a dye-sensitized semiconductor fine particle layer via a spacer, and the open end of both is immersed in an electrolyte solution, so that the inside of the semiconductor fine particle layer and between the semiconductor fine particle layer and the counter electrode are In this method, the electrolyte solution is infiltrated into the gap. The other is a method of applying an electrolyte solution to the semiconductor fine particle layer so that the electrolyte solution penetrates into the semiconductor fine particle layer, forming a charge transfer layer on the semiconductor fine particle layer, and finally providing a counter electrode.
[0140]
In the former case, as a method of infiltrating the electrolyte solution into the gap between the semiconductor fine particle layer and the counter electrode, the atmospheric pressure method using capillary action and the upper open end of the semiconductor fine particle layer and the counter electrode (the one not immersed in the electrolyte solution) There is a decompression method that sucks up from the open end.
[0141]
In the latter case, a counter electrode is applied to the wet charge transfer layer without being dried, and measures for preventing liquid leakage at the edge portion are taken. In the case of a gel electrolyte, the counter electrode may be provided after being applied wet and solidified by a method such as polymerization, or may be solidified after providing the counter electrode. As a method of forming a layer of a wet organic hole transport material or a gel electrolyte in addition to the electrolytic solution, as in the case of semiconductor fine particle layer formation and dye adsorption, a dipping method, a roller method, a dip method, an air knife method, The extrusion method, slide hopper method, wire bar method, spin method, spray method, cast method, various printing methods, etc. can be used. In the case of a solid electrolyte or a solid hole transport material, a charge transfer layer may be formed by a dry film forming process such as a vacuum deposition method or a CVD method, and then a counter electrode may be provided.
[0142]
In the case of an electrolyte solution or a wet hole transport material that cannot be solidified, it is preferable to seal the edge portion immediately after coating. In the case of a hole transport material that can be solidified, a hole transport layer is formed by wet application. After the film is formed, it is preferably solidified by a method such as photopolymerization or thermal radical polymerization. As described above, the film application method may be appropriately selected depending on the properties of the electrolytic solution and the process conditions.
[0143]
The water content in the charge transfer layer is preferably 10,000 ppm or less, more preferably 2,000 ppm or less, and particularly preferably 100 ppm or less.
[0144]
[D] Counter electrode
The counter electrode acts as a positive electrode of the photoelectrochemical cell when the photoelectric conversion element is a photoelectrochemical cell. As the counter electrode, a substrate having a conductive layer can be used in the same manner as the conductive support, but a substrate is not necessarily required if a metal plate that can maintain sufficient strength and sealability is used. As the conductive material used for the counter electrode, metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine) Etc.). An example of a preferred counter electrode is a thin film of metal or conductive metal oxide applied or deposited on glass or plastic. The thickness of the counter electrode is not particularly limited, but is preferably 3 nm to 10 μm. When the conductive layer is made of metal, the thickness is preferably 5 μm or less, and more preferably in the range of 5 nm to 3 μm.
[0145]
Since light may be irradiated from either or both of the conductive support and the counter electrode, in order for light to reach the photosensitive layer, it is sufficient that at least one of the conductive support and the counter electrode is substantially transparent. . From the viewpoint of improving the power generation efficiency, it is preferable to make the conductive support transparent so that light is incident from the conductive support side. In this case, the counter electrode preferably has a property of reflecting light. As such a counter electrode, glass or plastic on which a metal or a conductive oxide is deposited, or a metal thin film can be used.
[0146]
As a procedure for providing the counter electrode, (a) when the charge transfer layer is formed and then provided thereon, and (b) after the counter electrode is disposed on the dye-sensitized semiconductor fine particle layer via a spacer, the gap There are two ways in which the electrolyte solution is filled in and crosslinked. In the case of (a), a conductive material is directly applied, plated or vapor deposited (PVD, CVD) on the charge transfer layer, or the conductive layer side of the substrate having the conductive layer is attached. In the case of (b), the counter electrode is assembled and fixed on the dye-sensitized semiconductor fine particle layer via a spacer, and the open end of the obtained assembly is immersed in an electrolyte solution, and capillary action or reduced pressure is used. The electrolyte solution is infiltrated into the gap between the dye-sensitized semiconductor fine particle layer and the counter electrode, and then crosslinked by heating.
[0147]
[E] Other layers
A functional layer such as a protective layer or an antireflection film may be provided on one or both of the conductive support and the counter electrode acting as an electrode. When such a functional layer is formed in multiple layers, a simultaneous multilayer coating method or a sequential coating method can be used, but the simultaneous multilayer coating method is preferable from the viewpoint of productivity. In the simultaneous multilayer coating method, the slide hopper method and the extrusion method are suitable in view of productivity and coating film uniformity. For forming these functional layers, an evaporation method, a bonding method, or the like can be used depending on the material.
[0148]
Furthermore, it is also possible to provide a layer having other necessary functions such as a protective layer and an antireflection film on the conductive support or the counter electrode of the working electrode. In the case of separating the functions by making such layers multi-layered, simultaneous multi-layer application or sequential application can be performed, but simultaneous multi-layer application is more preferable when productivity is given priority. In simultaneous multilayer coating, the slide hopper method and the extrusion method are suitable when considering productivity and film application uniformity. Moreover, these functional layers can also be provided using methods, such as vapor deposition and affixing, with the material.
[0149]
[3] photoelectrochemical cells
The photoelectrochemical cell of the present invention is one in which the photoelectric conversion element is caused to work in an external circuit. In order to prevent deterioration of components and volatilization of the contents of the photoelectrochemical cell, it is preferable to seal the side surface with a polymer or an adhesive. The external circuit itself connected to the conductive support and the counter electrode via a lead may be a known one.
[0150]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0151]
Example 1
Synthesis of metal complex dyes D-1, D-8, D-2, D-9, D-3, D-10, D-42 and D-48
The production methods and structural formulas of metal complex dyes D-1, D-8, D-2, D-9, D-3, D-10, D-42 and D-48 are as follows. However, the carboxylate ions in the metal complex dyes D-8, D-9, D-10, and D-48 are in equilibrium with the state in which protons are not dissociated (carboxyl group), and corresponding counter ions The structure of CI also changes.
[0152]
Embedded image
[0153]
Embedded image
[0154]
Embedded image
[0155]
Embedded image
[0156]
1. Synthesis of D-1 and D-8
Ruthenium (III) chloride trihydrate (10.44 g, 40 mmol) was dissolved in 50 ml of dimethyl sulfoxide (DMSO) and refluxed for 5 minutes. After concentration to 25 ml, 200 ml of acetone was added, and after cooling to room temperature, the crystals were separated by filtration and washed with acetone and ether to obtain 13.9 g (yield 72%) of Ru complex 1 yellow crystals.
[0157]
0.87 g (1.8 mmol) of Ru complex 1 and 0.54 g (1.8 mmol) of diethyl bipyridine dicarboxylate L-14 were dissolved in 5 ml of chloroform and refluxed in a nitrogen atmosphere for 4 hours. After concentration, a small amount of acetone is added to dissolve, and further ether is added to precipitate crystals. After filtration, it was washed with ether to obtain 0.85 g (yield 75%) of yellow crystals of Ru complex 3.
[0158]
0.166 g (0.264 mol) of Ru complex 2 and 0.050 g (0.29 mmol) of sodium hydroxamate 3 were dissolved in a mixed solvent consisting of 10 ml of ethanol and 10 ml of water and refluxed in a nitrogen atmosphere for 2 hours. Further, 0.028 g (0.12 mmol) of dipyridylpyrazine BL-1 was added and refluxed for 20 hours. 0.20 g NHFourPF6And concentrated, and the precipitated crystals were separated by filtration and washed with water. Purification by Sephadex column LH-20 (developing solvent: methanol) gave 0.18 g (yield 92%) of D-1 black crystals. The structure of black crystal D-1 was confirmed by MS spectrum and elemental analysis.
[0159]
0.081 g (0.05 mmol) D-1, 6 ml triethylamine, 18 ml dimethylformamide and 3 ml water were mixed and refluxed for 12 hours. After concentration, the residue was dissolved in acetonitrile and filtered to obtain 0.06 g (yield 85%) of black crystals D-8. The structure of black crystal D-8 was confirmed by MS spectrum and elemental analysis.
[0160]
2. Synthesis of D-2 and D-9
In the synthesis of D-1 and D-8 in Step 1 above, equimolar amount of potassium oxalate 4 is used instead of sodium hydroxamate 3 and NHFourPF6D-2 and D-9 were synthesized in the same manner except that the addition of was not performed. The structures of D-2 and D-9 were confirmed by MS spectrum and elemental analysis.
[0161]
3. Synthesis of D-3 and D-10
In the synthesis of D-1 and D-8 in the above step 1, D-3 and D-10 were synthesized in the same manner except that equimolar amount of sodium dithiocarbamate 5 was used instead of sodium hydroxamate 3. The structures of D-3 and D-10 were confirmed by MS spectrum and elemental analysis.
[0162]
4). Synthesis of D-42 and D-48
Instead of dipyridylpyrazine BL-1, J. Am. Chem. Soc.,109, 2691 (1987), D-42 and D-48 were synthesized in exactly the same manner except that equimolar amounts of BL-11 synthesized according to the method described in US Pat. The structures of D-42 and D-48 were confirmed by MS spectrum and elemental analysis.
[0163]
5). Synthesis of other metal complex dyes
For other metal complex dyes, X1And X2(X-1 to X-48), BL (BL-1 to BL-34) and LL1And LL2They were synthesized by appropriately combining specific examples of (L-1 to L-50). Ligand X1And X2These compounds are readily available commercially, or Inorg. Chim. Acta.,206, 69 (1993), Inorg. Chem.,29, 1888 (1990), J. Am. Chem. Soc.,109, 2691 (1987), Inorg. Chem.,29, 4750 (1990), Inorg. Chem.,28, 1520 (1989), Inorg. Chem.,29, 167 (1990), Inorg. Chem.,28, 2465 (1989), etc., or references cited therein. In addition, a substituent such as a carboxyl group can be introduced into these ligands by a general organic synthesis method.
[0164]
6). Absorption spectrum measurement
Absorption spectra in methanol were measured for D-8, D-9, D-10, D-11, D-47, D-48, D-49 and D-50 and comparative dyes 1 and 2. The absorption maximum wavelength is shown in Table 1.
[0165]
[Table 1]
[0166]
As is clear from Table 1,D-8, D-9, D-10, D-11, D-47, D-48, D-49 and D-50The absorption maximum wavelengths of the metal complex dyes were longer than those of the comparative dyes 1 and 2. Therefore,theseThe use of a metal complex dye in a photoelectrochemical cell is very preferable because it can be spectrally sensitized to light having a longer wavelength and converted into a photocurrent.
[0167]
Example 2
1. Preparation of titanium dioxide dispersion
Inside a Teflon-coated stainless steel container with an inner volume of 200 ml, titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25) 15 g, water 45 g, dispersant (Aldrich Triron X-100) 1 g, diameter 0.5 30 g of zirconia beads having a size of mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 μm. The particle size was measured with a master sizer manufactured by MALVERN.
[0168]
2. Preparation of electrode layer composed of titanium dioxide fine particles adsorbed with dye
Conductive glass plate coated with fluorine-doped tin oxide (manufactured by Nippon Sheet Glass Co., Ltd., surface resistance: approx. 10Ω / cm2The titanium dioxide dispersion was applied onto the conductive layer using a doctor blade to a thickness of 140 μm (wet thickness) and dried at 25 ° C. for 30 minutes. Next, this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. The thickness of the titanium dioxide fine particle layer is 10 μm, and the coating amount of the titanium dioxide fine particle is 15 g / m.2Met.
[0169]
After the semiconductor coated glass plate was taken out and cooled, a methanol solution of the dyes shown in Table 1 (concentration: 3 × 10-Fourmol / L) for 3 hours. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, washed with methanol, and air dried. The adsorption amount of the metal complex dye in the dye-sensitized titanium dioxide fine particle layer thus obtained is 0.1 to 10 mmol / m depending on the type.2It was in the range.
[0170]
3. Production of photoelectrochemical cell
Dye-sensitized TiO prepared as above2Electrodes (2 cm × 2 cm) made of fine particles were superposed on the platinum vapor deposition layer side of a platinum vapor deposition glass plate of the same size via a spacer (see FIG. 2). The open end of the assembly consisting of the obtained conductive glass plate / dye-sensitized semiconductor fine particle layer / platinum-deposited glass plate is supported on the electrolyte (N-methyl-2-oxazolidinone) and the supporting electrolyte (1-butyl-3-methylimidazolium) Iodide) 0.65mol / L, 0.05mol / L iodine)), and impregnated with electrolyte using capillary action in the gap between both glass plates.2Introduced into the layer. Thus, conductive glass plate 10 / dye-sensitized TiO2A photoelectrochemical cell having a laminated structure (see FIG. 1) consisting of photosensitive layer 20 / charge transfer layer 30 / platinum-deposited glass plate 40 formed by impregnating electrolyte in the voids of the fine particle layer was obtained. This process was repeated using the other dyes shown in Table 2.
[0171]
4). Measurement of photoelectric conversion efficiency
The photoelectric conversion efficiency at 800 nm of the obtained photoelectrochemical cell was measured by an IPCE (Incident Photon to Current Conversion Efficiency) measuring apparatus manufactured by Optel. Table 2 summarizes the photoelectric conversion efficiency of each metal complex dye.
[0172]
[Table 2]
[0173]
From Table 2, it can be seen that the comparative dye does not show photoelectric conversion ability for light having a wavelength of 800 nm because it has no absorption ability.Photoelectrochemical cellIt can be seen that shows a good photoelectric conversion ability. in this wayUsing a metal complex dye represented by the general formula (V)Of the present inventionPhotoelectrochemical cellAll have high photoelectric conversion ability not only in visible light but also in the infrared region.
[0174]
【The invention's effect】
As described above in detail, since the metal complex dye of the present invention has a good light absorption ability in a wide wavelength range from visible light to infrared, a photoelectric conversion element including semiconductor fine particles adsorbing such metal complex dye is It has high photoelectric conversion characteristics from visible light to infrared region. A photoelectrochemical cell comprising such a photoelectric conversion element is extremely effective as a solar cell.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view showing the structure of a photoelectric conversion device according to a preferred embodiment of the present invention.
FIG. 2 is a partial cross-sectional view showing the structure of a photoelectrochemical cell according to another preferred embodiment of the present invention.
[Explanation of symbols]
10 ... Conductive support
11 ... Board
12 ... conductive layer
20 ... Photosensitive layer
21 ... Semiconductor fine particles
22 ... Metal complex dye
30 ... Gel electrolyte layer
40 ... Counter electrode
41 ... Board
42 ... conductive layer

Claims (3)

  1. The following general formula (V):
    (LL 1 ) m1 (X 1 ) m2 Ru (BL) Ru (X 2 ) m3 (LL 2 ) m4・ CI ・ ・ ・ (V)
    (However, BL represents the following general formulas B-1 to B-4:
    (However, R 21 , R 22 , R 23 and R 24 each represent a carboxyl group and may be bonded to any ring carbon atom of B-1 to B-4, e, f, g and h are Each independently represents an integer of 1 to 8. ),
    X 1 and X 2 are the same and each represents a monodentate or bidentate ligand coordinated by a group selected from the group consisting of a dithiocarbamate group, an acylaminooxy group, an acyloxy group and an isothiocyanate group ;
    LL 1 and LL 2 are the same and have the following general formula (IV-1) or (IV-2):
    (However, R 1 and R 2 are the same and each represents an alkoxy group (1 to 20 carbon atoms) or an amino group (0 to 20 carbon atoms) , and R 3 and R 4 are the same and each represents an alkyl group ( R 5 and R 6 each represent a hydrogen atom, a and b each represent 1, and c and d each represent 2 ) .
    m1 and m4 are each 1 , m2 and m3 are each 1 or 2, and CI represents a counterion when a counterion is required to neutralize the charge. A photoelectric conversion element comprising semiconductor fine particles sensitized by a ruthenium complex dye represented by the formula:
  2. The photoelectric conversion element according to claim 1 , wherein the semiconductor fine particles are titanium oxide fine particles.
  3. A photoelectrochemical cell using the photoelectric conversion device according to claim 1 .
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WO2004102724A1 (en) * 2003-05-13 2004-11-25 Asahi Kasei Kabushiki Kaisha Photoelectric conversion element
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