Semiconductor particle sensitized with methine dye

[0003] The present invention relates to a semiconductor particle having a surface on which a methine dye is adsorbed. The invention also relates to a photoelectric material using the particles and a photoelectric conversion device using the material.

[0004] A photoelectric material (photovoltaic element) is used in various photosensors, copying machines and photovoltaic devices. The photoelectric materials are constructed according to a method using a metal as a photosensor, a method using a semiconductor as a photosensor, a method using an organic pigment or a dye as a photosensor or a complex method.

[0005] The semiconductor photosensor method uses semiconductor particles spectrally sensitized with a dye. U.S. Pat. Nos. 4,684,537, 4,927,721, 5,084,365, 5,350644, 5,463,057, 5,525,440 and Japanese Patent Provisional Publication No. 7(1995)-249790 disclose the semiconductor particles spectrally sensitized with a dye. The spectral sensitizing dyes used in the publications are usually ruthenium complexes, which are rather expensive.

[0006] Japanese Patent Provisional Publication No. 7(1995)-249790 further describes that a methine dye such as a cyanine dye or a merocyanine dye can be used as a spectral sensitizing dye for the semiconductor particles. The methine dye has been researched and developed as a spectral sensitizing dye for silver halide grains of a silver halide photo graphic material. Various methine dyes are practically used in a large scale in the technical field of the silver halide photography. Therefore, many methine dyes, which are inexpensive and excellent in optical characteristics are known in the silver halide photography.

[0007] In a silver halide photographic material, a methine dye is used as a spectral sensitizing dye, a filter dye, an antiirradiation dye or an antihalation dye. The silver halide photographic material is usually sensitive to a visible light to form a visible image. Therefore, the photographic methine dye usually has the maximum absorption within the visible wavelength region. However, the visible, light has a low photoelectric conversion efficiency.

[0008] An object of the present invention is to improve the photoelectric conversion efficiency.

[0009] Another object of the invention is to provide a semiconductor particle sensitized with an infrared wavelength. region.

[0010] A further object of the invention is to provide a photoelectric material and a photoelectric conversion device having a high photovoltaic effect.

[0011] A furthermore object of the invention is to provide a new methine dye having the maximum absorption within the infrared region.

[0012] The present invention provides a semiconductor particle having a surface on which a methine dye is adsorbed, wherein the methine dye is represented by the formula (I):

[0013] in which Q¹is a tetravalent aromatic group; each of X¹and X²independently is a single bond or —CR³═CR⁴—; when X¹is a single bond, Y¹is —O—, —S—, —Se—, —NR⁵—, —CR⁶R⁷— or —CR⁸═CR⁹—; when X¹is —CR³═CR⁴—, Y¹is a single bond; when X²is a single bond, Y²is —O—, —S—, —Se—, —NR⁵—, —CR⁶R⁷— or —CR⁸═CR⁹—; when X²is —CR³═CR⁴—, Y²is a single bond; each of R¹and R²independently is an aliphatic group or an aromatic group; each of R³, R⁴, R⁵, R⁶, R⁷, R⁸and R⁹independently is hydrogen or an alkyl group; each of P¹and P²independently is ═L¹—Bo, ═L²═Ak or ═L³—Ar; L¹is a methine chain having an odd number of methines; Bo is an onium form of a basic nucleus; L²is a methine chain having an even number of methines; Ak is an acidic nucleus of a keto type; L³is a methine chain having an odd number of methines; and Ar is an aromatic nucleus.

[0014] The invention also provides a photoelectric material comprising a conductive support and a light-sensitive layer containing semiconductor particles spectrally sensitized with a methine dye, wherein the methine dye is represented by the formula (I).

[0015] The invention further provides a photoelectric conversion device comprising a photoelectric material, a charge transfer layer and a counter electrode, said photoelectric material comprising a conductive support and a light-sensitive layer containing semiconductor particles spectrally sensitized with a methine dye, wherein the methine dye is represented by the formula (I).

[0016] The invention furthermore provides a methine compound represented by the formula (Va):

[0017] in which each of X¹⁰¹and X¹⁰²independently is a single bond or —CR¹⁰³═CR¹⁰⁴—; when X¹⁰¹is a single bond, Y¹⁰¹is —O—, —S—, —Se—, —NR¹⁰⁵—, —CR¹⁰⁶R¹⁰⁷— or —CR¹⁰⁸═CR¹⁰⁹—; when X¹⁰¹is —CR¹⁰³═CR¹⁰⁴—, Y¹⁰¹is a single bond; when X¹⁰²is a single bond, Y¹⁰²is —O—, —S—, —Se—, —NR¹⁰⁵—, —CR¹⁰⁶R¹⁰⁷— or —CR¹⁰⁸═CR¹⁰⁹—; when X¹⁰²is —CR¹⁰³═CR¹⁰⁴—, Y¹⁰²is a single bond; each of R¹⁰¹and R¹⁰²independently is an aliphatic group or an aromatic group; each of R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸and R¹⁰⁹independently is hydrogen or an alkyl group; each of X¹⁰³and X¹⁰⁴independently is a double bond or ═CR¹¹³—CR¹¹⁴═; when X¹⁰³is a double bond, Y¹⁰³is —O—, —S—, —Se—, —NR¹¹⁵—, —CR¹¹⁶R¹¹⁷— or —CR¹¹⁸═CR¹¹⁹—; when X¹⁰³is ═CR¹¹³—CR¹¹⁴═, Y¹⁰³is a single bond; when X¹⁰⁴is a double bond, Y¹⁰⁴is —O—, —S—, —Se—, —NR¹¹⁵—, —CR¹¹⁶R¹¹⁷— or —CR¹¹⁸═CR¹¹⁹—; when X¹⁰⁴is ═CR¹¹³—CR¹¹⁴═, Y¹⁰⁴is a single bond; each of R¹¹¹and R¹¹²independently is an aliphatic group or an aromatic group; each of R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁶, R¹¹⁷, R¹¹⁸and R¹¹⁹independently is hydrogen or an alkyl group; each of the benzene rings A and B may be condensed with another benzene ring; and the benzene rings A, B and the condensed benzene rings may have a substituent group.

[0018] The invention still furthermore provides a methine compound represented by the formula (Vb):

[0019] in which each of X¹²¹and X¹²²independently is a single bond or —CR¹²³═CR¹²⁴—; when X¹²¹is a single bond, Y¹²¹is —O—, —S—, —Se—, —NR¹²⁵—, —CR¹²⁶R¹²⁷— or —CR¹²⁸═CR¹²⁹—; when X¹²¹is —CR¹²³═CR¹²⁴—, Y¹²¹is a single bond; when X¹²²is a single bond, Y¹²²is —O—, —S—, —Se—, —NR¹²⁵—, —CR¹²⁶R¹²⁷— or —CR¹²⁸═CR¹²⁹—; when X¹²²is —CR¹²³═CR¹²⁴—, Y¹²²is a single bond; each of R¹²¹and R¹²²independently is an aliphatic group or an aromatic group; each of R¹²³, R¹²⁴, R¹²⁵, R¹²⁶, R¹²⁷, R¹²⁸and R¹²⁹independently is hydrogen or an alkyl group; each of X¹²³and X¹²⁴independently is a double bond or ═CR¹³³—CR¹³⁴═; when X¹²³is a double bond, Y¹²³is —O—, —S—, —Se—, —NR¹³⁵—, —CR¹³⁶R¹³⁷— or —CR¹³⁸═CR¹³⁹—; when X¹²³is ═CR¹³³—CR¹³⁴═, Y¹²³is a single bond; when X¹²⁴is a double bond, Y¹²⁴is —O—, —S—, —Se—, —NR¹³⁵—, —CR¹³⁶R¹³⁷— or —CR¹³⁸═CR¹³⁹—; when X¹²⁴is ═CR¹³³—CR¹³⁴═, Y¹²⁴is a single bond; each of R¹³¹and R¹³²independently is an aliphatic group or an aromatic group; each of R¹³³, R¹³⁴, R¹³⁵, R¹³⁶, R¹³⁷, R¹³⁸and R¹³⁹independently is hydrogen or an alkyl group; each of the benzene rings C and D may be condensed with another benzene ring; and the benzene rings C, D and the condensed benzene rings may have a substituent group.

[0020] The present inventors have found that the methine dye represented by the formula (I) has a large absorption within the infrared region. An infrared ray has a high photoelectric conversion efficiency, compared with the visible light.

[0021] The semiconductor particles can be strongly sensitized to the infrared ray by using adsorbing the methine dye represented by the formula (I) on the surface of the particles. A photovoltaic effect of a photoelectric material and a photoelectric conversion device are improved by using the semiconductor particles sensitized to the infrared ray. As a result, an inexpensive and excellent photoelectric material or photoelectric conversion device can be obtained by using the semiconductor particles of the present invention.

[0022] The FIGURE schematically illustrates a photoelectric conversion device (photo-electrochemical cell).

[0023] [Methine Dye]

[0024] The methine dye used in the present invention is represented by the formula (I).

[0025] In the formula (I), Q¹is a tetravalent aromatic group. The aromatic group has an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring. Examples of the aromatic heterocyclic rings include anthraquinone ring, carbazole ring, pyridine ring, pyrazine ring, quinoline ring, thiophene ring, furan ring, xanthene ring and thianthrene ring. The aromatic group can further have a substituent group. Examples of the substituent groups include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.

[0026] The aromatic hydrocarbon ring is preferred to the aromatic heterocyclic ring. Q¹most preferably is the tetravalent residue of benzene ring.

[0027] In the formula (I), each of X¹and X²independently is a single bond or —CR³═CR⁴—. Each of X¹and X²preferably is a single bond.

[0028] When X¹is a single bond, Y¹is —O—, —S—, —Se—, —NR⁵—, —CR⁶R⁷— or —CR⁸═CR⁹—, preferably is —O—, —S—, —NR⁵— or —CR⁶R⁷—, and more preferably is —S— or —CR⁶R⁷—. When X¹is —CR³═CR⁴—, Y¹is a single bond.

[0029] When X²is a single bond, Y²is —O—, —S—, —Se—, —NR⁵—, —CR⁶R⁷— or —CR⁸═CR⁹—, preferably is —O—, —S—, —NR⁵— or —CR⁶R⁷—, and more preferably is —S— or —CR⁶R⁷—. When X²is —CR³═CR⁴—, Y²is a single bond.

[0030] Each of R³, R⁴, R⁵, R⁶, R⁷, R⁸and R⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0031] In the formula (I), each of R¹and R²independently is an aliphatic group or an aromatic group.

[0032] The aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group.

[0033] The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0034] The alkyl moiety of the substituted alkyl group is the same as the above-described alkyl group. Examples of the substituent groups include an aromatic group, an alkoxy group having 1 to 6 carbon atoms, carboxyl, sulfo, a phosphoric group (—PO(OH)₂or —OPO(OH)₂) and a boric group (—(OH)₂or —OB(OH)₂). The carboxyl, the sulfo, the phosphoric group and the boric group can be in the dissociated form (to release proton) or in the form of a salt.

[0035] The alkenyl group can have a cyclic or branched structure. The alkenyl group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 6 carbon atoms.

[0036] The alkenyl moiety of the substituted alkenyl group is the same as the above-described alkenyl group. Examples of the substituent groups are the same as the substituent groups of the substituted alkyl group.

[0037] The alkynyl group can have a cyclic or branched structure. The alkynyl group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 6 carbon atoms.

[0038] The alkynyl moiety of the substituted alkynyl group is the same as the above-described alkynyl group. Examples of the substituent groups are the same as the substituent groups of the substituted alkyl group.

[0039] The aromatic group means an aryl group or a substituted aryl group.

[0040] The aryl group preferably is phenyl or naphthyl.

[0041] The aryl moiety of the substituted aryl group is the same as the above-described aryl group. Examples of the substituent groups include an aliphatic group, an alkoxy group having 1 to 6 carbon atoms, carboxyl, sulfo, a phosphoric group (—PO(OH)₂or —OPO(OH)₂) and a boric group (—B(OH)₂or —OB(OH)₂). The carboxyl, the sulfo, the phosphoric group and the boric group can be in the dissociated form (to release proton) or in the form of a salt.

[0042] In the formula (I), each of P¹and P²independently is ═L¹—Bo, ═L²═Ak or ═L³—Ar.

[0043] L¹is a methine chain having an odd number of methines. The number of the methines preferably is 1, 3, 5, 7 or 9, more preferably is 1, 3, 5 or 7, and most preferably is 3, 5 or 7.

[0044] The methine chain may have a substituent group. The substituent group preferably is an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl).

[0045] Two or more substituent groups of the methine chain may be combined to form an unsaturated aliphatic ring (e.g., cyclopentene ring, cyclohexene ring, isophorone ring, squarylium ring, croconium ring). Where the methine chain has only one substituent group, the sole substituent group is preferably attached to the centered (meso-positioned) methine.

[0046] Examples of the methine chains having an odd number of methines are shown below.

[0047] Bo is an onium form of a basic nucleus. The onium forms of the basic nucleus is preferably represented by the following formula.

[0048] in which X is a double bond or ═CRb—CRb═; when X is a double bond, Y is —O—, —S—, —Se—, —NRb—, —CRbRb— or —CRb═CRb—; when X is ═CRb—CRb═, Y is a single bond; Ra is an aliphatic group or an aromatic group; Rb is hydrogen or an alkyl group; the benzene ring E may be condensed with another benzene ring; and the benzene ring E and the condensed benzene rings may have a substituent group.

[0049] Examples of the aliphatic group, the aromatic group, the alkyl group and the substituent groups are the same as those described about R¹and R².

[0050] L²is a methine chain having an even number of methines. The number of the methines preferably is 2, 4, 6 or 8, and more preferably is 2, 4 or 6.

[0051] The methine chain may have a substituent group. The substituent group preferably is an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl). Two or more substituent groups of the methine chain may be combined to form an unsaturated aliphatic ring (e.g., cyclopentene ring, cyclohexene ring, isophorone ring, squarylium ring, croconium ring).

[0052] Examples of the methine chains having an even number of methines are shown below.

[0053] Ak is an acidic nucleus of a keto type. The acidic nucleus of the keto type is preferably represented by the following formula.

[0054] in which X is —NRb—, —O—, —S— or —Se—; Y is ═O, ═S, ═N—Rb or ═C(CN)₂; Ra is an aliphatic group or an aromatic group; and Rb is hydrogen or an alkyl group.

[0055] Examples of the aliphatic group, the aromatic group, the alkyl group and the substituent groups are the same as those described about R¹and R².

[0056] L³is a methine chain having an odd number of methines. Examples of the methine chains are the same as those described about L¹.

[0057] Ar is an aromatic nucleus. The aromatic nucleus is an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring. Examples of the aromatic heterocyclic rings include anthraquinone ring, carbazole ring, pyridine ring, pyrazine ring, quinoline ring, thiophene ring, furan ring, xanthene ring and thianthrene ring. The aromatic group can have a substituent group. Examples of the substituent groups include hydroxyl, amino an alkyl group having 1 to 6 carbon atoms and an alkylamino group having 1 to 6 carbon atoms (e.g., dimethylamino).

[0058] The aromatic hydrocarbon ring is preferred to the aromatic heterocyclic ring. Ar most preferably is phenyl or a substituted phenyl group.

[0059] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R¹, R², Bo, Ak or Ar. Examples of the acidic groups include carboxyl, sulfo, a phosphoric group (—PO(OH)₂or —OPO(OH)₂) and a boric group (—B(OH)₂or —OB(OH)₂). The carboxyl, the sulfo, the phosphoric group and the boric group can be in the dissociated form (to release proton) or in the form of a salt.

[0060] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye.

[0061] Examples of the charge balance cations include an alkali metal ion (e.g., sodium ion, potassium ion) and an ammonium ion (e.g., tetraalkylammonium ion, pyridinium ion).

[0062] Examples of the charge balance anions include a halide ion (e.g., chloride ion, bromide ion, fluoride ion, iodide ion), an arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), an aryldisulfonate ion (e.g., 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), an alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetra luoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion.

[0063] An ionic polymer, an ionic dye or a metal complex ion (e.g., bisbenzene-1,2-dithiolate nickel(III)) can also be used as the charge balance ion.

[0064] The methine dye is preferably represented by the formula (II), (III) or (IV).

[0065] In the formula (II), Q²is a tetravalent aromatic group. Examples of the tetravalent aromatic groups are the same as those described about the formula (I).

[0066] In the formula (II), each of X¹¹and X¹²independently is a single bond or —CR¹³═CR¹⁴—. Each of X¹¹and X¹²preferably is a single bond

[0067] When X¹¹is a single bond, Y¹¹is —O—, —S—, —Se—, —NR¹⁵—, —CR¹⁶R¹⁷— or —CR¹⁸═CR¹⁹—, preferably is —O—, —S—, —NR¹⁵— or —CR¹⁶R¹⁷—, and more preferably is —S— or —CR¹⁶R¹⁷—. When X¹¹is —CR¹³═CR¹⁴—, Y¹¹is a single bond.

[0068] When X¹²is a single bond, Y¹²is —O—, —S—, —Se—, —NR¹⁵—, —CR¹⁶R¹⁷— or —CR¹⁸═CR¹⁹—, preferably is —O—, —S—, —NR¹⁵— or —CR¹⁶R¹⁷—, and more preferably is —S— or —CR¹⁶R¹⁷—. When X¹²is —CR¹³═CR¹⁴—, Y¹²is a single bond.

[0069] Each of R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸and R¹⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0070] In the formula (II), each of R¹¹and R¹²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0071] In the formula (II), each of L¹¹and L¹²independently is a methine chain having an odd number of methines. Examples of the methine chains are the same as those described about the formula (I). The methine chain (L¹¹or L¹²) preferably contains a squarylium ring.

[0072] In the formula (II), each of Bo¹and Bo²independently is an onium form of a basic nucleus. Examples of the onium forms of the basic nuclei are the same as those described about the formula (I).

[0073] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R¹¹, R¹², Bo¹or Bo². Examples of the acidic groups are the same as those described about the formula (I).

[0074] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0075] In the formula (III), Q³is a tetravalent aromatic group. Examples of the tetravalent aromatic groups are the same as those described about the formula (I).

[0076] In the formula (III), each of X²¹and X²²independently is a single bond or —CR²³═CR²⁴—. Each of X²¹and X²²preferably is a single bond

[0077] When X²¹is a single bond, Y²¹is —O—, —S—, —Se—, —NR²⁵—, —CR²⁶R²⁷— or —CR²⁸═CR²⁹—, preferably is —O—, —S—, —NR²⁵— or —CR²⁶R²⁷—, and more preferably is —S— or —CR²⁶R²⁷—. When X²¹is —CR²³═CR²⁴—, Y²¹is a single bond.

[0078] When X²²is a single bond, Y²²is —O—, —S—, —Se—, —NR²⁵—, —CR²⁶R²⁷— or —CR²⁸═CR²⁹—, preferably is —O—, —S—, —NR²⁵— or —CR²⁶R²⁷—, and more preferably is —S— or —CR²⁶R²⁷—. When X²²is —CR²³═CR²⁴—, Y²²is a single bond.

[0079] Each of R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸and R²⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0080] In the formula (III), each of R²¹and R²²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0081] In the formula (III), each of L²¹and L²²independently is a methine chain having an even number of methines. Examples of the methine chains are the same as those described about the formula (I). The methine chain (L²¹or L²²) preferably contains a squarylium ring.

[0082] In the formula (III), each of Ak¹and Ak²independently is an acidic nucleus of a keto type. Examples of the acidic nuclei of the keto type are the same as those described about the formula (I).

[0083] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R²¹, R²², Ak¹or Ak². Examples of the acidic groups are the same as those described about the formula (I).

[0084] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0085] In the formula (IV), Q⁴is a tetravalent aromatic group. Examples of the tetravalent aromatic groups are the same as those described about the formula (I).

[0086] In the formula (IV), each of X³¹and X³²independently is a single bond or —CR³³═CR³⁴—. Each of X³¹and X³²preferably is a single bond.

[0087] When X³¹is a single bond, Y³¹is —O—, —S—, —Se—, —NR³⁵—, —CR³⁶R³⁷— or —CR³⁸═CR³⁹—, preferably is —O—, —S—, —NR³⁵— or —CR³⁶R³⁷—, and more preferably is —S— or —CR³⁶R³⁷—. When X³¹is —CR³³═CR³⁴—, Y³¹is a single bond.

[0088] When X³²is a single bond, Y³²is —O—, —S—, —Se—, —NR³⁵—, —CR³⁶R³⁷— or —CR³⁸═CR³⁹—, preferably is —O—, —S—, —NR³⁵— or —CR³⁶R³⁷—, and more preferably is —S— or —CR³⁶R³⁷—. When X³²is —CR³³═CR³⁴—, Y³²is a single bond.

[0089] Each of R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸and R³⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0090] In the formula (IV), each of R³¹and R³²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0091] In the formula (IV), each of L³¹and L³²independently is a methine chain having an odd number of methines. Examples of the methine chains are the same as those described about the formula (I). The methine chain (L³¹or L³²) preferably contains a squarylium ring.

[0092] In the formula (IV), each of Ar¹and Ar²independently is an aromatic nucleus. Examples of the aromatic nuclei are the same as those described about the formula (I).

[0093] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R³¹, R³², Ar¹or Ar². Examples of the acidic groups are the same as those described about the formula (I).

[0094] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0095] The methine dye is more preferably represented by the formula (IIa), (IIb), (IIIa), (IIIb), (IVa) or (IVb).

[0096] In the formula (IIa), each of X⁴¹and X⁴²independently is a single bond or —CR⁴³═CR⁴⁴—. Each of X⁴¹and X⁴²preferably is a single bond.

[0097] When X⁴¹is a single bond, Y⁴¹is —O—, —S—, —Se—, —NR⁴⁵—, —CR⁴⁶R⁴⁷— or —CR⁴⁸═CR⁴⁹—, preferably is —O—, —S—, —NR⁴⁵— or —CR⁴⁶R⁴⁷—, and more preferably is —S— or —CR⁴⁶R⁴⁷—. When X⁴¹is —CR⁴³═CR⁴⁴—, Y⁴¹is a single bond.

[0098] When X⁴²is a single bond, Y⁴²is —O—, —S—, —Se—, —NR⁴⁵—, —CR⁴⁶R⁴⁷— or —CR⁴⁸═CR⁴⁹—, preferably is —O—, —S—, —NR⁴⁵— or —CR⁴⁶R⁴⁷—, and more preferably is —S— or —CR⁴⁶R⁴⁷—. When X⁴²is —CR⁴³═CR⁴⁴—, Y⁴²is a single bond.

[0099] Each of R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸and R⁴⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0100] In the formula (IIa), each of R⁴¹and R⁴²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0101] In the formula (IIa), each of Bo³and Bo⁴independently is an onium form of a basic nucleus. Examples of the onium forms of the basic nuclei are the same as those described about the formula (I).

[0102] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁴¹, R⁴², Bo³or Bo⁴. Examples of the acidic groups are the same as those described about the formula (I).

[0103] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0104] In the formula (IIb), each of X⁵¹and X⁵²independently is a single bond or —CR⁵³═CR⁵⁴—. Each of X⁵¹and X⁵²preferably is a single bond.

[0105] When X⁵¹is a single bond, Y⁵¹is —O—, —S—, —Se—, —NR⁵⁵—, —CR⁵⁶R⁵⁷— or —CR⁵⁸═CR⁵⁹—, preferably is —O—, —S—, —NR⁵⁵— or —CR⁵⁶R⁵⁷—, and more preferably is —S— or —CR⁵⁶R⁵⁷—. When X⁵¹is —CR⁵³═CR⁵⁴—, Y⁵¹is a single bond.

[0106] When X⁵²is a single bond, Y⁵²is —O—, —S—, —Se—, —NR⁵⁵—, —CR⁵⁶R⁵⁷— or —CR⁵⁸═CR⁵⁹—, preferably is —O—, —S—, —NR⁵⁵— or —CR⁵⁶R⁵⁷—, and more preferably is —S— or —CR⁵⁶R⁵⁷—. When X⁵²is —CR⁵³═CR⁵⁴—, Y⁵²is a single bond.

[0107] Each of R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸and R⁵⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0108] In the formula (IIb), each of R⁵¹and R⁵²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0109] In the formula (IIb), each of Bo⁵and Bo⁶independently is an onium form of a basic nucleus. Examples of the onium forms of the basic nuclei are the same as those described about the formula (I).

[0110] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁵¹, R⁵², Bo⁵or Bo⁶. Examples of the acidic groups are the same as those described about the formula (I).

[0111] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0112] In the formula (IIIa), each of X⁶¹and X⁶²independently is a single bond or —CR⁶³═CR⁶⁴—. Each of X⁶¹and X⁶²preferably is a single bond.

[0113] When X⁶¹is a single bond, Y⁶¹is —O—, —S—, —Se—, —NR⁶⁵—, —CR⁶⁶R⁶⁷— or —CR⁶⁸═CR⁶⁹—, preferably is —O—, —S—, —NR⁶⁵— or —CR⁶⁶R⁶⁷—, and more preferably is —S— or —CR⁶⁶R⁶⁷—. When X⁶¹is —CR⁶³═CR⁶⁴—, Y⁶¹is a single bond.

[0114] When X⁶²is a single bond, Y⁶²is —O—, —S—, —Se—, —NR⁶⁵—, —CR⁶⁶R⁶⁷— or —CR⁶⁸═CR⁶⁹—, preferably is —O—, —S—, —NR⁶⁵— or —CR⁶⁶R⁶⁷—, and more preferably is —S— or —CR⁶⁶R⁶⁷—. When X⁶²is —CR⁶³═CR⁶⁴—, Y⁶²is a single bond.

[0115] Each of R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸and R⁶⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0116] In the formula (IIIa), each of R⁶¹and R⁶²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0117] In the formula (IIIa), each of Ak³and Ak⁴independently is an acidic nucleus of a keto type. Examples of the acidic nuclei of the keto type are the same as those described about the formula (I).

[0118] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁶¹, R⁶², Ak³or Ak⁴. Examples of the acidic groups are the same as those described about the formula (I).

[0119] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0120] In the formula (IIIb), each of X⁷¹and X⁷²independently is a single bond or —CR⁷³═CR⁷⁴—. Each of X⁷¹and X⁷²preferably is a single bond.

[0121] When X⁷¹is a single bond, Y⁷¹is —O—, —S—, —Se—, —NR⁷⁵—, —CR⁷⁶R⁷⁷— or —CR⁷⁸═CR⁷⁹—, preferably is —O—, —S—, —NR⁷⁵— or —CR⁷⁶R⁷⁷—, and more preferably is —S— or —CR⁷⁶R⁷⁷—. When X⁷¹is —CR⁷³═CR⁷⁴—, Y⁷¹is a single bond.

[0122] When X⁷²is a single bond, Y⁷²is —O—, —S—, —Se—, —NR⁷⁵—, —CR⁷⁶R⁷⁷— or —CR⁷⁸═CR⁷⁹—, preferably is —O—, —S—, —NR⁷⁵— or —CR⁷⁶R⁷⁷—, and more preferably is —S— or —CR⁷⁶R⁷⁷—. When X⁷²is —CR⁷³═CR⁷⁴—, Y⁷²is a single bond.

[0123] Each of R⁷³, R⁷⁴, R⁷⁵, R⁷⁶, R⁷⁷, R⁷⁸and R⁷⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0124] In the formula (IIIb), each of R⁷¹and R⁷²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0125] In the formula (IIIb), each of Ak⁵and Ak⁶independently is an acidic nucleus of a keto type. Examples of the acidic nuclei of the keto type are the same as those described about the formula (I).

[0126] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁷¹, R⁷², Ak⁵or Ak⁶. Examples of the acidic groups are the same as those described about the formula (I).

[0127] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0128] In the formula (IVa), each of X⁸¹and X⁸²independently is a single bond or —CR⁸³═CR⁸⁴—. Each of X⁸¹and X⁸²preferably is a single bond.

[0129] When X⁸¹is a single bond, Y⁸¹is —O—, —S—, —Se—, —NR⁸⁵—, —CR⁸⁶R⁸⁷— or —CR⁸⁸═CR⁸⁹—, preferably is —O—, —S—, —NR⁸⁵— or —CR⁸⁶R⁸⁷—, and more preferably is —S— or —CR⁸⁶R⁸⁷—. When X⁸¹is —CR⁸³═CR⁸⁴—, Y⁸¹is a single bond.

[0130] When X⁸²is a single bond, Y⁸²is —O—, —S—, —Se—, —NR⁸⁵—, —CR⁸⁶R⁸⁷— or —CR⁸⁸═CR⁸⁹—, preferably is —O—, —S—, —NR⁸⁵— or —CR⁸⁶R⁸⁷—, and more preferably is —S— or —CR⁸⁶R⁸⁷—. When X⁸²is —CR⁸³═CR⁸⁴—, Y⁸²is a single bond.

[0131] Each of R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸and R⁸⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0132] In the formula (IVa), each of R⁸¹and R⁸²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0133] In the formula (IVa), each of Ar³and Ar⁴independently is an aromatic nucleus. Examples of the aromatic nuclei are the same as those described about the formula (I).

[0134] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁸¹, R⁸², Ar³or Ar⁴. Examples of the acidic groups are the same as those described about the formula (I).

[0135] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0136] In the formula (IVb), each of X⁹¹and X⁹²independently is a single bond or —CR⁹³═CR⁹⁴—. Each of X⁹¹and X⁹²preferably is a single bond.

[0137] When X⁹¹is a single bond, Y⁹¹is —O—, —S—, —Se—, —NR⁹⁵—, —CR⁹⁶R⁹⁷— or —CR⁹⁸═CR⁹⁹—, preferably is —O—, —S—, —NR⁹⁵— or —CR⁹⁶R⁹⁷—, and more preferably is —S— or —CR⁹⁶R⁹⁷—. When X⁹¹is —CR⁹³═CR⁹⁴—, Y⁹¹is a single bond.

[0138] When X⁹²is a single bond, Y⁹²is —O—, —S—, —Se—, —NR⁹⁵—, —CR⁹⁶R⁹⁷— or —CR⁹⁸═CR⁹⁹—, preferably is —O—, —S—, —NR⁹⁵— or —CR⁹⁶R⁹⁷—, and more preferably is —S— or —CR⁹⁶R⁹⁷—. When X⁹²is —CR⁹³═CR⁹⁴—, Y⁹²is a single bond.

[0139] Each of R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸and R⁹⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0140] In the formula (IVb), each of R⁹¹and R⁹²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0141] In the formula (IVb), each of Ar⁵and Ar⁶independently is an aromatic nucleus. Examples of the aromatic nuclei are the same as those described about the formula (I).

[0142] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R⁹¹, R⁹², Ar⁵or Ar⁶. Examples of the acidic groups are the same as those described about the formula (I).

[0143] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0144] The methine dye is most preferably represented by the formula (Va) or (Vb).

[0145] In the formula (Va), each of X¹⁰¹and X¹⁰²independently is a single bond or —CR¹⁰³═CR¹⁰⁴—. Each of X¹⁰¹and X¹⁰²preferably is a single bond.

[0146] When X¹⁰¹is a single bond, Y¹⁰¹is —O—, —S—, —Se—, —NR¹⁰⁵—, —CR¹⁰⁶R¹⁰⁷— or —CR¹⁰⁸═CR¹⁰⁹—, preferably is —O—, —S—, —NR¹⁰⁵— or —CR¹⁰⁶R¹⁰⁷—, and more preferably is —S— or —CR¹⁰⁶R¹⁰⁷—. When X¹⁰¹is —CR¹⁰³═CR¹⁰⁴—, Y¹⁰¹is a single bond.

[0147] When X¹⁰²is a single bond, Y¹⁰²is —O—, —S—, —Se—, —NR¹⁰⁵—, —CR¹⁰⁶R¹⁰⁷— or —CR¹⁰⁸═CR¹⁰⁹—, preferably is —O—, —S—, —NR¹⁰⁵— or —CR¹⁰⁶R¹⁰⁷—, and more preferably is —S— or —CR¹⁰⁶R¹⁰⁷—. When X¹⁰²is —CR¹⁰³═CR¹⁰⁴—, Y¹⁰²is a single bond.

[0148] Each of R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸and R¹⁰⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0149] In the formula (Va), each of R¹⁰¹and R¹⁰²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0150] In the formula (Va), each of X¹⁰³and X¹⁰⁴independently is a double bond or ═CR¹¹³—CR¹¹⁴═. Each of X¹⁰³and X¹⁰⁴preferably is a double bond.

[0151] When X¹⁰³is a double bond, Y¹⁰³is —O—, —S—, —Se—, —NR¹¹⁵—, —CR¹¹⁶R¹¹⁷— or —CR¹¹⁸═CR¹¹⁹—, preferably is —O—, —S—, —NR¹¹⁵— or —CR¹¹⁶R¹¹⁷—, and more preferably is —S— or —CR¹¹⁶R¹¹⁷—. When X¹⁰³is ═CR¹¹³—CR¹¹⁴═, Y¹⁰³is a single bond.

[0152] When X¹⁰⁴is a double bond, Y¹⁰⁴is —O—, —S—, —Se—, —NR¹¹⁵—, —CR¹¹⁶R¹¹⁷— or —CR¹¹⁸═CR¹¹⁹—, preferably is —O—, —S—, —NR¹¹⁵— or —CR¹¹⁶R¹¹⁷—, and more preferably is —S— or —CR¹¹⁶R¹¹⁷—. When X¹⁰⁴is ═CR¹¹³—CR¹¹⁴═, Y¹⁰⁴is a single bond.

[0153] Each of R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁶, R¹¹⁷, R¹¹⁸and R¹¹⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0154] In the formula (Va), each of R¹¹and R¹¹²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0155] Each of the benzene rings A and B may be condensed with another benzene ring. The benzene rings A, B and the condensed benzene rings may have a substituent-group. Examples of the substituent groups are the same as those described about the formula (I).

[0156] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R¹⁰¹, R¹⁰², R¹¹¹, R¹¹², the benzene rings A, B or the condensed benzene rings. Examples of the acidic groups are the same as those described about the formula (I).

[0157] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0158] In the formula (Vb), each of X¹²¹and X¹²²independently is a single bond or —CR¹²³═CR¹²⁴—. Each of X¹²¹and X¹²²preferably is a single bond.

[0159] When X¹²¹is a single bond, Y¹²¹is —O—, —S—, —Se—, —NR¹²⁵—, —CR¹²⁶R¹²⁷— or —CR¹²⁸═CR¹²⁹—, preferably is —O—, —S—, —NR¹²⁵— or —CR¹²⁶R¹²⁷—, and more preferably is —S— or —CR¹²⁶R¹²⁷—. When X¹²¹is —CR¹²³═CR¹²⁴—, Y¹²¹is a single bond.

[0160] When X¹²²is a single bond, Y¹²²is —O—, —S—, —Se—, —NR¹²⁵—, —CR¹²⁶R¹²⁷— or —CR¹²⁸═CR¹²⁹—, preferably is —O—, —S—, —NR¹²⁵— or —CR¹²⁶R¹²⁷—, and more preferably is —S— or —CR¹²⁶R¹²⁷—. When X¹²²is —CR¹²³═CR¹²⁴—, Y¹²²is a single bond.

[0161] Each of R¹²³, R¹²⁴, R¹²⁵, R¹²⁶, R¹²⁷, R¹²⁸and R¹²⁹independently is hydrogen or an alkyl group. The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0162] In the formula (Vb), each of R¹²¹and R¹²²independently is an aliphatic group or an aromatic group. Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0163] In the formula (Vb), each of X¹²³and X¹²⁴independently is a double bond or ═CR¹³³—CR¹³⁴═. Each of X¹²³and X¹²⁴preferably is a double bond.

[0164] When X¹²³is a double bond, Y¹²³is —O—, —S—, —Se—, —NR¹³⁵—, —CR¹³⁶R¹³⁷— or —CR¹³⁸═CR¹³⁹—, preferably is —O—, —S—, —NR¹³⁵— or —CR¹³⁶R¹³⁷—, and more preferably is —S— or —CR¹³⁶R¹³⁷—. When X¹²³is ═CR¹³³—CR¹³⁴═, Y¹²³is a single bond.

[0165] When X¹²⁴is a double bond, Y¹²⁴is —O—, —S—, —Se—, —NR¹³⁵—, —CR¹³⁶R¹³⁷— or —CR¹³⁸═CR¹³⁹—, preferably is —O—, —S—, —NR¹³⁵— or —CR¹³⁶R¹³⁷—, and more preferably is —S— or —CR¹³⁶R¹³⁷—. When X¹²⁴is ═CR¹³³—CR¹³⁴═, Y¹²⁴is a single bond.

[0166] Each of R¹³³, R¹³⁴, R¹³⁵, R¹³⁶, R¹³⁷, R¹³⁸and R¹³⁹independently is hydrogen or an alkyl group The alkyl group can have a cyclic or branched structure. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0167] In the formula (Vb), each of R¹³¹and R¹³²independently is an aliphatic group or an aromatic group Examples of the aliphatic groups and the aromatic groups are the same as those described about the formula (I).

[0168] Each of the benzene rings C and D may be condensed with another benzene ring; and the benzene rings C, D and the condensed benzene rings may have a substituent group. Examples of the substituent groups are the same as those described about the formula (I).

[0169] The methine dye preferably has an acidic group as a substituent group. The acidic group is more preferably is a substituent group of R¹²¹, R¹²², R¹³¹, R¹³², the benzene rings C, D or the condensed benzene rings. Examples of the acidic groups are the same as those described about the formula (I).

[0170] The methine dye can have a charge balance ion. The kind (cation or anion) and number of the charge balance ion depend on the kind and number of an ionic group of the methine dye. Examples of the charge balance ions are the same as those described about the formula (I).

[0171] Examples of the methine dyes are shown below.

[0172] The methine dye is usually tautomeric. The present specification defines and describes an embodiment that the inside nucleus, such as Q¹in the formula (I), is the normal form of a basic nucleus, and the outside nucleus, such as Bo in the formula (I), is the onium form of a basic nucleus. The normal form of the basic nucleus is tautomeric to the onium form. Therefore, the present invention also includes another embodiment that the inside nucleus is the onium form of a basic nucleus, and the outside nucleus is the normal form of a basic nucleus.

[0173] For example, the dye (1) is tautomeric to the following dye (1-a).

[0174] Further, the squarylium ring in the methine chain can also be represented as an aromatic ring. Therefore, the present invention also includes an embodiment having a squarylium ring represented as an aromatic ring.

[0175] For example, the dye (6) can also be represented by the following formula (6-b).

[0176] The synthesis methods of methine dyes are described in Ukrainskii Khimicheskii Zhurnal, Vol. 40, No. 3, pages 253 to 258; and Dyes and Pigments, Vol. 21, pages 227 to 234. The starting materials of the dyes (such as quaternary salt of benzbisthiazole) can be synthesized according to a method described in Chemisahe Veihite, Vol. 95, pages 616 to 619.

[0177] Synthesis examples of the methine dyes are shown below. The other methine dyes can be synthesized in a similar manner by referring to the above-mentioned publications.

[0178]

[0179] In 3 ml of 1-butanol and 1 ml of toluene, 0.15 g of the compound (A-1) and 0.14 g of the compound (B-1) were mixed. The mixture was stirred at 140° C. for 4 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.10 g of the methine dye (6). The λmax was 748 nm (ε=250,000 in methanol).

[0180]

[0181] In 5 ml of 1-butanol and 5 ml of toluene, 0.20 g of the compound (A-1) and 0.20 g of the compound (B-2) were mixed. The mixture was stirred at 120° C. for 10 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.10 g of the methine dye (7). The λmax was 768 nm (ε=290,000 in methanol).

[0182]

[0183] In 10 ml of 1-butanol and 10 ml of toluene, 0.17 g of the compound (A-2) and 0.40 g of the compound (B-3) were mixed. The mixture was stirred at 120° C. for 6 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.10 g of the methine dye (13). The λmax was 762 nm (ε=250,000 in methanol).

[0184]

[0185] In 20 ml of 1-butanol and 20 ml of toluene, 0.35 g of the compound (A-3) and 0.62 g of the compound (B-3) were mixed. The mixture was stirred at 120° C. for 6 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.20 g of the methine dye (16). The λmax was 717 nm (ε=198,000 in methanol).

[0186]

[0187] In 3 ml of 1-butanol and 1 ml of toluene, 0.12 g of the compound (A-4) and 0.13 g of the compound (B-4) were mixed. The mixture was stirred at 140° C. for 4 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.10 g of the methine dye (29). The λmax was 768 nm (ε=230,000 in methanol).

[0188]

[0189] In 3 ml of 1-butanol and 1 ml of toluene, 0.12 g of the compound (A-5) and 0.10 g of the compound (B-5) were mixed. The mixture was stirred at 140° C. for 4 hours. The obtained crystals were filtered off with suction, and purified in a Sephadex column chromatography to obtain 0.06 g of the methine dye (33). The λmax was 808 nm (ε=180,000 in methanol).

[0190] [Semiconductor Particle]

[0191] The semiconductor used in the particle has a specific resistance in the range of 10⁻²to 10⁹Ω·cm at ordinary temperature based on conduction electron or positive hole. The simply measured value of the specific resistance is preferably in the range of 10⁻²to 10⁵Ω·cm.

[0192] The semiconductor preferably is a simple substance (e.g., silicon, germanium), a metal chalcogenide (e.g., oxide, sulfide, selenide, telluride) or a perovskite (e.g., strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate). The metal used as the metal oxide preferably is titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum. The metal used as the metal sulfide preferably is cadmium, zinc, lead, silver, antimony or bismuth. The metal used as selenide preferably is cadmium or lead. The metal used as the metal telluride preferably is cadmium. Further, a metal phosphide (e.g., indium phosphide, cadmium phosphide), gallium-arsenic alloy, copper-indium selenide and copper indium sulfide can also be used as the semiconductor.

[0193] The semiconductor preferably is Si, TiO₂, SnO₂, Fe₂O₃, WO₃, ZnO, Nb₂O₅, CdS, ZnS, PbS, Bi₂S₃, CdSe, CdTe, GaP, InP, GaAs, CuInS₂or CuInSe₂, more preferably is TiO₂, SnO₂, Fe₂O₃, WO₃, ZnO, Nb²O⁵, CdS, PbS, CdSe, InP, GaAs, CuInS₂or CuInSe₂, and most preferably is TiO₂.

[0194] The semiconductor particle can be in the form of polycrystal. However, monocrystal has a high conversion efficiency compared with polycrystal. The particle size is preferably in the range of several nanometers to several micrometers, more preferably in the range of 5 to 200 nm, and most preferably in the range of 8 to 100 nm. The particles size corresponds to the diameter of a circle having the same area as the projected area of the particle. The average size of the particles contained in a dispersion (secondary particle size) is preferably in the range of 0.01 to 100 μm. The semiconductor particles can have a small particle size (5 nm or less) to obtain the large surface area. The semiconductor particles can also have a large particle size (100 nm or more) to scatter and capture incident light. The small particles and the large particles can be used in combination.

[0195] The semiconductor particles preferably have a large surface area to adsorb a large amount of the methine dye. The semiconductor particles preferably have a shape of a rough surface to obtain the large surface area. The ratio of the surface area to the projected area (i.e., roughness factor described in U.S. Pat. No. 4,927,721) is preferably more than 10, and more preferably more than 100. The particles having the large surface area can be prepared, for example by aggregation of fine semiconductor particles to form secondary particles.

[0196] A methine dye can be adsorbed on semiconductor particles by immersing well-dried particles in a solution of the methine dye. The solution of the methine dye can be heated at 50 to 100° C.

[0197] In the preparation of a photoelectric material (described below), the methine dye can be adsorbed on the semiconductor particles after coating the particles (forming a light-sensitive layer). Further, the methine dye can be adsorbed on the semiconductor particles by coating the dye and the particles simultaneously. Not adsorbed methine dye is removed by washing. Where the light-sensitive layer is formed by heating, the adsorption of the methine dye is preferably conducted after heating. The adsorption is more preferably conducted immediately after burning before the surface of the light-sensitive layer adsorbs water (or absorbs moisture).

[0198] Two or more methine dyes can be used in combination at the adsorption process. The methine dye having a phosphoric substituent group can be used in combination with another methine dye. The methine dye can also be used in combination with a complex dye (described in U.S. Pat. Nos. 4,684,537, 5,084,365, 5,350644, 5,463,057, 5,525,440 and Japanese Patent Provisional Publication No. 7(1995)-249790). Where the semiconductor particles are used in a photoelectric conversion device, Two or more methine dyes are preferably used in combination to obtain a broad wave-length region of the photovoltaic effect.

[0199] In the case that two or more methine dyes are used in combination, an interaction between the dyes such as association is reported. A colorless substance can be further adsorbed on the semiconductor particles to reduce the interaction. The colorless substance preferably is hydrophobic. The colorless hydrophobic substance preferably is a steroid compound having carboxyl (e.g., cholic acid).

[0200] The coated amount of the methine dye is preferably in the range of 0.01 to 100 mmol per m². The amount of the adsorbed methine dye is also preferably in the range of 0.01 to 1 mmol based on the amount of the semiconductor particles.

[0201] After the adsorption of the methine dye, the surface of the semiconductor particles can be treated with an amine. Examples of the amines include pyridine, 4-t-butylpyridine and polyvinyl pyridine. Where the amine is liquid, the semiconductor particles adsorbing the methine dye are immersed in the liquid amine to conduct the surface treatment. Where the amine is solid, the amine is dissolved in an organic solvent to obtain a solution, and the semiconductor particles adsorbing the methine dye are immersed in the solution of the amine to conduct the surface treatment.

[0202] [Photoelectric Material (Photovoltaic element)]

[0203] The photoelectric material is an electrode comprising a conductive support and a light-sensitive layer containing semiconductor particles spectrally sensitized with a methine dye. Two or more light-sensitive layers can be provided on the conductive support. Two or more methine dyes or two or more semiconductor particles can be contained in one light-sensitive layer.

[0204] The conductive support of the photoelectric material is made of a conductive material such as a metal plate, or is made by forming a conductive layer on an insulating material such as a glass plate or a plastic film. The conductive layer can be formed by using a metal (e.g., platinum, gold, silver, copper, aluminum, rhodium, indium), carbon or a conductive metal oxide (e.g., indium-tin complex oxide, fluorine doped tin oxide). The thickness of the conductive layer is preferably in the range of 0.02 to 10 μm.

[0205] The surface resistance of the conductive support is preferably not larger than 100 Ω per square, and more preferably not larger than 40 Ω per square. The lower limit of the surface resistance is usually 0.1 Ω per square.

[0206] The conductive support preferably is transparent. The light transmittance is preferably not less than 10%, more preferably not less than 50%, and most preferably not less than 70%. A conductive layer containing a conductive metal oxide is preferably formed on a glass plate or a plastic film to obtains a transparent conductive support. The coating amount of the conductive metal oxide is preferably in the range of 0.01 to 100 g per 1 m²of the support. The conductive layer is preferably made of tin dioxide doped with fluorine atom. The glass plate is preferably made of a soda lime float glass. The plastic film is preferably made of triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Polyacrylate (PAr), polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), polycyclicolefine and polyphenoxy bromide. Where the transparent conductive support is used, light preferably incidents on the side of the support.

[0207] A light-sensitive layer containing semiconductor particles can be formed by coating a dispersion or a colloidal solution of the semiconductor particle on the conductive support. A light-sensitive layer containing semiconductor particles can also be formed by coating a precursor of the semiconductor particles (e.g., titanium tetra isopropoxide, titanium tetrabutoxide, titanium tetrachloride) on the conductive support, and hydrolyzing the precursor by a moisture in the air. A dispersion of the semiconductor particles can be prepared by grinding a semiconductor in a mortar or a mill. A dispersion of the semiconductor particles can also be obtained by precipitating the semiconductor particles in a process of synthesizing the semiconductor. Water or an organic solvent (e.g., methanol, ethanol, dichloromethane, acetone, acetonitrile, ethyl acetate) can be used as a dispersing medium. A dispersing aid such as a polymer, a surface active agent, an acid or a chelating agent can be used in the dispersing process.

[0208] If a light-sensitive layer containing semiconductor particles is thick, the amount of the methine dye per area is increased to improve light absorption efficiency. On the other hand, the diffusion length of electron is increased with the increase of the thickness of the layer to further increase the charge recombination loss. The light-sensitive layer containing semiconductor particles usually has a thickness in the range of 0.1 to 100 μm. In a photoelectric conversion device, the light-sensitive layer has a thickness preferably in the range of 1 to 30 μm, and more preferably in the range of 2 to 25 μm. The coating amount of the semiconductor particles is preferably in the range of 0.5 to 400 g, and more preferably in the range of 5 to 500 g based on 1 m²of the support.

[0209] After the light-sensitive layer is formed on the conductive support, the layer can be subjected to a heating treatment to adhere the semiconductor particles with each other. The heating temperature is preferably in the range of 40 to 700° C., and more preferably in the range of 100 to 600° C. The heating time is preferably in the range of 10 minutes to 10 hours.

[0210] After the heating treatment, the conductive support can be subjected to a chemical plating treatment or a photochemical plating treatment to increase the surface area of the semiconductor particles or to increase the purity of the semiconductor. The chemical plating treatment can be conducted by using an aqueous solution of titanium tetrachloride. The electrochemical plating treatment can be conducted by using an aqueous solution of titanium trichloride.

[0211] As is described above, the absorption of the methine dye on the semiconductor particles is preferably conducted after the heating treatment.

[0212] [Photoelectric Conversion Device (Photo cell)]

[0213] The photoelectric material can be used in various sensors or photoelectric conversion devices. The semiconductor particles sensitized with the methine dye according to the present invention are particularly effective in a photoelectric conversion device.

[0214] The figure schematically illustrates a photoelectric conversion device.

[0215] As is shown in figure, the photoelectric conversion device comprises a photoelectric material (1), a charge transfer layer (2) and a counter electrode (3). The photoelectric material (1) functions as a negative electrode of the photoelectric conversion device. The photoelectric material (1) comprises a conductive support (11) and a light-sensitive layer (12). The light-sensitive layer (12) contains semiconductor particles (122) having a surface on which a methine dye (121) is adsorbed.

[0216] Light (4) incidents on the light-sensitive layer (12) through the transparent conductive support (11). Light excites the methine dye (121). The excited methine dye has an electron (e) of a high energy. The electron (e) is transferred from the methine dye (121) to a conductive band formed by semiconductor particles (122) in the light-sensitive layer. The electron (e) was further diffused to the conductive support (12). After the electron (e) was removed, the molecule of the methine dye (121) is changed to an oxidation product. The electron (e) was further transferred from the photoelectric material (1), namely the negative electrode to an outer circuit (5). After the electron (e) works in the outer circuit (5), the electron (e) is transferred to the counter (positive) electrode (3). The electron (e) is return to the oxidation product of the methine dye through the charge transfer layer (2).

[0217] As is described in the figure, the charge transfer layer has a function of supplying the electron to the oxidation product of the methine dye.

[0218] The charge transfer layer contains an oxidation-reduction pair. The charge transfer layer can be formed by using a solution of the oxidation-reduction pair in an organic solvent, a gel electrolyte in which a polymer matrix is impregnated with the solution of the oxidation-reduction pair or a melting salt containing the oxidation-reduction pair. A solid electrolyte or a hole transfer material can also be used in the charge transfer layer.

[0219] Examples of the oxidation-reduction pairs include a combination of iodine and iodide (e.g., LiI, NaI, KI, CsI, CaI₂, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide), a combination of bromine and bromide (e.g., LiBr, NaBr, KBr, CsBr, CaBr₂, tetraalkylammonium iodide, pyridinium iodide), a combination of an alkylviologen (e.g., methylviologen chloride, hexylviologen bromide, benzylviologen tetrafluoroborate) and a reduction product thereof, a combination of a polyhydroxybenzene (e.g., hydroquinone, naphthohydroquinone) and an oxidation product thereof, and a combination of a divalent iron complex (e.g., potassium hexacyanoferrate(II)) and a trivalent iron complex (e.g., potassium hexacyanoferrate(III)). The combination of iodine and iodide is particularly preferred.

[0220] The organic solvent preferably is a polar but not proton donating solvent (e.g., acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, sulfolane, 1,3-dimethylimidazoline, 3-methyloxazolidinone). The polymer of the electrolyte matrix preferably is polyacrylonitrile or polyvinylidene fluoride. The melting salt preferably is a mixture of lithium iodide and anther lithium salt (e.g., lithium acetate, lithium perchlorate). A polymer such as polyethylene oxide can be added to the melting salt to add fluidize the salt at room temperature. The amount of the polymer is preferably in the range of 1 to 50 wt. %.

[0221] The concentration of the oxidation-reduction pair is so adjusted that the pair functions as a carrier of an electron. The total concentration of the oxidation-reduction pair is preferably not less than 0.01 mol per liter, more preferably not less than 0.1 mol per liter, and most preferably not less than 0.3 mol per liter. The upper limit of the concentration is usually 5 mol per liter.

[0222] An aromatic amine, a polypyrrole or a polythiophene can be used as a hole transfer material

[0223] As is described in the figure, the counter electrode function as a positive electrode of the photoelectric conversion device. The counter electrode can be prepared by the materials described about the conductive support of the photoelectric material.

[0224] At least one of the conductive support and the counter electrode should be substantially transparent so that light reaches the light-sensitive layer. In the photoelectric conversion device, the conductive support is preferably transparent, and light preferably incidents on the side of the support. Where the conductive support is transparent, the counter electrode preferably reflects light. The counter electrode preferably is a glass plate or a plastic film having a surface on which a metal or a conductive metal oxide is evaporated, and particularly preferably is a glass plate having a surface on which platinum is evaporated. The thickness of the metal or metal oxide layer is preferably not larger than 5 μm, and more preferably in the range of 5 nm to 3 μm.

[0225] The side of the photoelectric conversion device is preferably sealed with a polymer or an adhesive to prevent evaporation of the components.

[0226] (Preparation of titanium dioxide dispersion)

[0227] A titanium dioxide dispersion (titanium dioxide concentration: 11 wt. %) was prepared according to a conventional method (described in Journal of American Ceramic A Society, Vol. 80, page 3,157, except that the autoclave temperature was 230° C.). The average particle size of the titanium dioxide particles was about 10 nm.

[0228] Polyethylene glycol (molecular weight; 20,000, Wako Pure Chemicals Industries, Ltd.) was added to the titanium dioxide dispersion. The amount of polyethylene glycol was 30 wt. % of the titanium dioxide.

[0229] (Preparation of photoelectric material)

[0230] A conductive glass coated with fluorine doped tin oxide (surface resistance: about 10 Ω per square, Asahi Glass Co., Ltd.) was used as the conductive support. On the conductive layer (tin oxide layer), the titanium dioxide dispersion was coated by a doctor blade to form a layer having the thickness of 140 μm. The layer was dried at 25° C. for 30 minutes, placed in an electric furnace (muffle furnace FP-32, Yamato Science Co., Ltd.), and burned at 450° C. for 30 minutes. The coating amount of the titanium dioxide was 15 g per m², and the thickness was 10 μm.

[0231] After the glass plate was cooled, the plate was immersed in an ethanol solution (3×10⁻⁴mol per liter) of the methine dye set forth in Table 1 for 3 hours. The glass plate was further immersed in 4-t-butylpyridine for 15 minutes. The plate was washed with ethanol, and dried. The amount of the dye was preliminary determined to obtain the best result within the range of 0.1 to 10 mmol per m².

[0232] (Preparation of photoelectric conversion device)

[0233] The above-prepared photoelectric material was laminated with a glass plate having evaporated platinum (counter electrode). The size of the glass plate was the same as the size of the photoelectric material. An electrolyte was introduced into the gap between the two plates by capillary phenomenon. The electrolyte contains 0.05 mol per liter of iodide and 0.5 mol per liter of lithium iodide in a mixture of acetonitrile and N-methyl-2-oxazolidine. The volume ratio of the acetonitrile to N-methyl-2-oxazo-lidinone was 90 to 10.

[0234] (Measurement of the maximum photoelectric conversion wavelength and photoelectric conversion efficiency)

[0235] The photoelectric conversion efficiency was measured by using a machine (Optel) for measuring an incident photon to current conversion efficiency (IPCE). The maximum photoelectric conversion wavelength and the IPCE are set forth in Table 1.