CN102803394A - Novel organic dye and its manufacturing method - Google Patents

Abstract

The organic dye of the present invention is used as a dye-sensitized photoelectric conversion element in a dye-sensitized solar cell (DSSC), and exhibits higher molar absorption coefficient, Jsc (short-circuit photocurrent density), and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell.

Description

Novel organic dye and its manufacturing method

technical field

The invention relates to a novel dye-sensitized photoelectric conversion element organic dye used in a dye-sensitized solar cell (dye-sensitized solar cell, DSSC) and a manufacturing method thereof.

Background technique

After the research group of Michael Gratzel of the Swiss National Institute of Technology Lausanne (EPFL) developed the dye-sensitized nanoparticle titanium oxide solar cell in 1991, a lot of research on this field has been carried out. Dye-sensitized solar cells are expected to be able to replace conventional amorphous silicon-based solar cells because they have higher efficiency and significantly lower manufacturing costs than conventional silicon-based solar cells. Unlike silicon-based solar cells, dye-sensitized solar cells are photoelectrochemical solar cells that use dyes that generate electron-hole pairs by absorbing visible light and transition metal oxides that transfer the generated electrons. .

Conventionally, ruthenium metal complexes exhibiting high photoelectric conversion efficiency have been widely used as dyes for dye-sensitized solar cells, but the ruthenium metal complexes have a disadvantage of being too expensive.

It has recently been found that metal-free organic dyes exhibiting excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intramolecular charge-transfer (CT) system absorption can replace expensive ruthenium metal complexes Since it is used as a dye for dye-sensitized solar cells, research on metal-free organic dyes is intensively carried out.

Organic dyes generally have a structure of electron donor-electron acceptor residues linked by π-bond units. In most organic dyes, amine derivatives act as electron donors, and 2-cyanoacrylic acid or rhodanine residues act as electron acceptors. Equivalent π-bond system connection.

In general, by changing the structure of the amine unit as an electron donor, the electronic properties such as the absorption spectrum that induces a shift to the blue side are changed, and the absorption spectrum and redox potential are adjusted by changing the length of the π-bond. (redox potential).

However, most of the currently known organic dyes exhibit low conversion efficiency and low drive stability compared to ruthenium metal complex dyes, so research aimed at changing such electron donors and acceptors is currently underway. Efforts are being made to develop new dyes that have significantly improved molar absorptivity compared to conventional organic dyes and exhibit high photoelectric conversion efficiency, depending on the type or π-bond length.

Contents of the invention

technical problem

The object of the present invention is to provide a dye-sensitized photoelectric conversion element that exhibits higher molar absorptivity and photoelectric conversion efficiency than conventional metal complex dyes, thereby greatly improving the efficiency of dye-sensitized solar cells. organic dyes.

Another object of the present invention is to provide a method for producing the above-mentioned organic dye.

Yet another object of the present invention is to provide a dye-sensitized photoelectric conversion element exhibiting significantly improved photoelectric conversion efficiency, Jsc (short circuit photocurrent density) and molar absorptivity by containing the above-mentioned organic dye, and A solar cell whose efficiency is remarkably improved by containing it.

Solution to the problem

According to the above object, the present invention provides organic dyes for dye-sensitized photoelectric conversion elements represented by the following chemical formula 1 or 2:

[chemical formula 1]

[chemical formula 2]

In the above formula,

A is C or N, but when A is N, b and c are 0,

B is O, S, CR ¹ R ² or NR ³ , at this time, R ¹ to R ³ are each independently hydrogen or C1-12 alkyl,

Ar ₁ to Ar ₅ are each independently a substituted or unsubstituted C ₆ -C ₅₀ aryl group, at this time, A ₁ to Ar ₃ can be connected to each other to form a ring,

a is 0 or 1,

b and c are independently 0 or 1, but when c is 1, b must be 1,

d is 0 or 1,

e is 0 or 1,

An each independently selected from

中的1种以上，此时L各自独立地选自O、S、CR⁶R⁷、SiR⁸R⁹和NR¹⁰中，R⁴和R⁵各自独立地选自氢、取代或非取代的C_1-12烷基、取代或非取代的C_6-30芳基和取代或非取代的C_6-20杂芳基中、或者可以相互连接而形成环，R⁶至R¹⁰各自独立地为氢或取代或非取代的C_1-12烷基，n为1至10的整数。Sp each independently selected from

At this time, each L is independently selected from O, S, CR ⁶ R ⁷ , SiR ⁸ R ⁹ and NR ¹⁰ , and R ⁴ and R ⁵ are each independently selected from hydrogen, substituted or unsubstituted C _1-12 alkyl, substituted or unsubstituted C _6-30 aryl and substituted or unsubstituted C _6-20 heteroaryl, or can be connected to each other to form a ring, R ⁶ to R ¹⁰ are each independently hydrogen Or substituted or unsubstituted C _1-12 alkyl, n is an integer from 1 to 10.

In addition, the present invention provides the manufacture method of above-mentioned organic dye, comprising:

(1) the step of making the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out coupling reaction to manufacture the compound of chemical formula 5;

(2) reacting the compound of the chemical formula 5 with BuLi or CF ₃ COOH in an organic solvent to produce a compound of the following chemical formula 6; and

(3) A step in which the compound of chemical formula 6 is subjected to a binding reaction with a compound providing an anchoring group in CH ₃ CN in the presence of piperidine:

[chemical formula 3]

[chemical formula 4]

Y——Sp——Z

[chemical formula 5]

[chemical formula 6]

In the above formula,

The rings W are each independently

X is Br or

Y is *——B(OH) ₂ or *——CHO,

Z is H or

A, Ar ₁ to Ar ₄ , a, b, c, e and Sp are the same as defined above.

According to still another object described above, the present invention provides a dye-sensitized photoelectric conversion element characterized by comprising oxide semiconductor fine particles and the above-mentioned organic dye supported on the oxide semiconductor fine particles.

According to still another objective above, the present invention provides a dye-sensitized solar cell, which is characterized by comprising the above-mentioned dye-sensitized photoelectric conversion element.

Invention effect

The dye compound of the present invention is used in dye-sensitized solar cells (DSSC), and exhibits higher molar absorptivity, Jsc (short-circuit photocurrent density) and photoelectric conversion efficiency than previous dyes, thereby greatly improving the efficiency of solar cells.

Detailed ways

Hereinafter, the present invention will be described in more detail.

Throughout this specification, "alkyl" refers to a linear or branched saturated _C1 to _C6 hydrocarbon radical chain. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hexyl, but are not limited thereto.

Throughout this specification, "alkoxy" means -ORa group, where Ra is the same alkyl as defined above. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and the like, but are not limited thereto.

Throughout the present specification, "aryl" refers to an optionally substituted benzene ring or a ring system formed by combining one or more arbitrary substituents. As examples of the above-mentioned arbitrary substituents, substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclyl, aryl, with or without Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy and aroyloxy groups having 1 to 3 fluorine substituents. The above-mentioned ring or ring system may be arbitrarily combined with an aromatic ring (including a benzene ring), a carbocyclic ring or a heterocyclic ring having one or more substituents or no substituent. Examples of "aryl" include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracenyl, phenanthrenyl and their substituted derivatives.

唑基、吲哚基、异吲哚基、嘌呤基、呋喃、噻吩基、苯并呋喃、苯并噻吩基、咔唑基、咪唑基、噻唑基、异

唑基、吡唑基、异噻唑基、喹啉基、异喹啉基、哒嗪基、嘧啶基、吡嗪基(它们可以被取代或非取代)等，但不限于此。Throughout this specification, "heteroaryl" refers to a monocyclic 5- to 6-membered aromatic ring having one or more heteroatoms such as oxygen, sulfur, and nitrogen in the ring, or refers to a heteroaromatic ring, an aromatic ring, a heteroaryl ring, Aromatic rings such as rings or carbocycles combined on more than one ring (eg, bicyclic or tricyclic ring systems). Specific examples of heteroaryl groups include pyridyl, pyrrolyl,

Azolyl, indolyl, isoindolyl, purinyl, furan, thienyl, benzofuran, benzothienyl, carbazolyl, imidazolyl, thiazolyl, iso

Azolyl, pyrazolyl, isothiazolyl, quinolinyl, isoquinolyl, pyridazinyl, pyrimidinyl, pyrazinyl (they may be substituted or unsubstituted), etc., but not limited thereto.

Throughout this specification, "substituted" or "substituted" means that at least one hydrogen on the compound or functional group is selected from halogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, hydroxyl, carboxyl , Carbamoyl, alkoxycarbonyl, nitro, haloalkyl, amino, alkylcarbonylamino, cycloalkyl, cyano and thiol are substituted by substituents.

Throughout the specification, "*" used in the chemical structural formula indicates a bonding site.

The organic dye according to the present invention is characterized in that it has the structure of the following chemical formula 1 or 2, so that when it is used as a dye-sensitized photoelectric conversion element for a dye-sensitized solar cell (DSSC), it shows an improved molar absorptivity, Jsc (short-circuit light current density) and photoelectric conversion efficiency:

[chemical formula 1]

[chemical formula 2]

In the above formula,

A is C or N, but when A is N, b and c are 0,

B is O, S, CR ¹ R ² or NR ³ , at this time, R ¹ to R ³ are each independently hydrogen or C1-12 alkyl,

Ar ₁ to Ar ₅ are each independently a substituted or unsubstituted C ₆ -C ₅₀ aryl group, at this time, A ₁ to Ar ₃ can be connected to each other to form a ring,

a is 0 or 1,

b and c are independently 0 or 1, but when c is 1, b must be 1,

d is 0 or 1,

e is 0 or 1,

An each independently selected from

Sp each independently selected from

中的1种以上，此时L各自独立地选自O、S、CR⁶R⁷、SiR⁸R⁹和NR¹⁰中，R⁴和R⁵各自独立地选自氢、取代或非取代的C_1-12烷基、取代或非取代的C_6-30芳基和取代或非取代的C_6-20杂芳基中、或者可以相互连接而形成环，R⁶至R¹⁰各自独立地为氢或取代或非取代的C_1-12烷基，n为1至10的整数。

At this time, each L is independently selected from O, S, CR ⁶ R ⁷ , SiR ⁸ R ⁹ and NR ¹⁰ , and R ⁴ and R ⁵ are each independently selected from hydrogen, substituted or unsubstituted C _1-12 alkyl, substituted or unsubstituted C _6-30 aryl and substituted or unsubstituted C _6-20 heteroaryl, or can be connected to each other to form a ring, R ⁶ to R ¹⁰ are each independently hydrogen Or substituted or unsubstituted C _1-12 alkyl, n is an integer from 1 to 10.

Preferably, in the above chemical formula 1 or 2,

A is C or N, but when A is N, b and c are 0,

B is S or CR ¹ R ² , at this time, R ¹ and R ² are each independently hydrogen or methyl,

Ar ₁ to Ar ₅ are each independently a C ₆ -C ₅₀ aryl group, or a C ₆ -C ₅₀ aryl group substituted by an alkyl or alkoxy group, more preferably a phenyl group, a methoxyphenyl group or a bis Methylfluorenyl,

a is 0 or 1,

b and c are independently 0 or 1, but when c is 1, b must be 1,

d is 0 or 1,

e is 0 or 1,

An for

中。Sp selected from

middle.

As a specific example of the organic dye according to the present invention, one of the following Chemical Formulas 7 to 122 is preferable.

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

[chemical formula 11]

[chemical formula 12]

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

[chemical formula 27]

[chemical formula 28]

[chemical formula 29]

[chemical formula 30]

[chemical formula 31]

[chemical formula 32]

[chemical formula 33]

[chemical formula 34]

[chemical formula 35]

[chemical formula 36]

[chemical formula 37]

[chemical formula 38]

[chemical formula 39]

[chemical formula 40]

[chemical formula 41]

[chemical formula 42]

[chemical formula 43]

[chemical formula 44]

[chemical formula 45]

[chemical formula 46]

[chemical formula 47]

[chemical formula 48]

[chemical formula 49]

[chemical formula 50]

[chemical formula 51]

[chemical formula 52]

[chemical formula 53]

[chemical formula 54]

[chemical formula 55]

[chemical formula 56]

[chemical formula 57]

[chemical formula 58]

[chemical formula 59]

[chemical formula 60]

[chemical formula 61]

[chemical formula 62]

[chemical formula 63]

[chemical formula 64]

[chemical formula 65]

[chemical formula 66]

[chemical formula 67]

[chemical formula 68]

[chemical formula 69]

[chemical formula 70]

[chemical formula 71]

[chemical formula 72]

[chemical formula 73]

[chemical formula 74]

[chemical formula 75]

[chemical formula 76]

[chemical formula 77]

[chemical formula 78]

[chemical formula 79]

[chemical formula 80]

[chemical formula 81]

[chemical formula 82]

[chemical formula 83]

[chemical formula 84]

[chemical formula 85]

[chemical formula 86]

[chemical formula 87]

[chemical formula 88]

[chemical formula 89]

[chemical formula 90]

[chemical formula 91]

[chemical formula 92]

[chemical formula 93]

[chemical formula 94]

[chemical formula 95]

[chemical formula 96]

[chemical formula 97]

[chemical formula 98]

[chemical formula 99]

[chemical formula 100]

[chemical formula 101]

[chemical formula 102]

[chemical formula 103]

[chemical formula 104]

[chemical formula 105]

[chemical formula 106]

[chemical formula 107]

[chemical formula 108]

[chemical formula 109]

[chemical formula 110]

[chemical formula 111]

[chemical formula 112]

[chemical formula 113]

[chemical formula 114]

[chemical formula 115]

[chemical formula 116]

[chemical formula 117]

[chemical formula 118]

[chemical formula 119]

[chemical formula 120]

[chemical formula 121]

[chemical formula 122]

Organic dyes according to the present invention can be manufactured by a manufacturing method comprising the following steps:

(1) the step of making the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out coupling reaction to manufacture the compound of chemical formula 5;

(2) reacting the compound of the chemical formula 5 with BuLi or CF ₃ COOH in an organic solvent to produce a compound of the following chemical formula 6; and

(3) A step in which the compound of chemical formula 6 is subjected to a binding reaction with a compound providing an anchoring group in CH ₃ CN in the presence of piperidine:

[chemical formula 3]

[chemical formula 4]

Y——Sp——Z

[chemical formula 5]

[chemical formula 6]

In the above formula,

X is Br or

Y is *——B(OH) ₂ or *——CHO,

Z is H or

A, Ar ₁ to Ar ₄ , a, b, c, e and Sp are the same as defined above.

In more detail, the compound of chemical formula 5 is produced by first performing a coupling reaction between the compound of chemical formula 3 and the compound of chemical formula 4 above.

时，在t-BuO-K+等催化剂的存在下、在四氢呋喃(THF)等有机溶剂中，与Y为*——CHO的化学式4化合物进行反应而实施。The above-mentioned coupling reaction is preferably carried out as follows: when the substituent X in Chemical Formula 3 is Br, in the presence of a catalyst such as Pd(PPh ₃ ) ₄ and a base such as K ₂ CO ₃ , in the presence of an organic compound such as dimethylformamide (DMF). In a solvent, it is carried out by reacting the compound of chemical formula 4 with Y being *——B(OH) ₂ ; preferably in chemical formula 3, the substituent X is

, in the presence of a catalyst such as t-BuO-K+, in an organic solvent such as tetrahydrofuran (THF), react with a compound of chemical formula 4 whose Y is *——CHO.

In this case, the compounds of Chemical Formulas 3 and 4 used as starting materials can be produced by a usual method or purchased from the market for use. As the compound of the above-mentioned Chemical Formula 3, one of the compounds of the following Chemical Formulas 3-1 to 3-6 is preferably used.

[chemical formula 3-1]

[chemical formula 3-2]

[chemical formula 3-3]

[chemical formula 3-4]

[chemical formula 3-5]

[chemical formula 3-6]

In addition, as the compound of the above-mentioned Chemical Formula 4, any one of the compounds of the following Chemical Formulas 4-1 to 4-3 is preferably used.

[chemical formula 4-1]

[chemical formula 4-2]

[chemical formula 4-3]

Next, the compound of Chemical Formula 5 is reacted with BuLi or CF ₃ COOH in an organic solvent such as DMF to produce a compound of Chemical Formula 6.

时，优选与CF3COOH进行反应。At this time, in the above chemical formula 5, when Z is H, it reacts with BuLi in an organic solvent, and Z is

When, it is preferred to react with CF3COOH.

The organic dye according to the present invention can be produced by subjecting the compound of Chemical Formula 6 obtained as a result to a coupling reaction with an anchoring group-providing compound such as cyanoacetic acid in the presence of piperidine in CH ₃ CN.

Specifically, the organic dye according to the present invention may be produced using the methods described in Reaction Formulas 1 to 10 below, but this is just an example, and the present invention is not limited thereto.

[Reaction 1]

[Reaction 2]

[reaction formula 3]

[Reaction 4]

[Reaction 5]

[Reaction 6]

[Reaction 7]

[Reaction 8]

[reaction formula 9]

[Equation 10]

The organic dye according to the present invention produced by the above-mentioned production method is used as a dye-sensitized photoelectric conversion element for a dye-sensitized solar cell (DSSC), and shows a higher molar absorptivity, Jsc (short-circuit photocurrent density) than conventional dyes. ) and photoelectric conversion efficiency, which can greatly improve the efficiency of solar cells.

Therefore, the present invention provides a dye-sensitized photoelectric conversion element containing the above-mentioned organic dye.

Specifically, the dye-sensitized photoelectric conversion element according to the present invention is characterized by comprising oxide semiconductor fine particles and the aforementioned organic dye supported on the aforementioned oxide semiconductor fine particles.

According to the dye-sensitized photoelectric conversion element of the present invention, in addition to using the above-mentioned organic dyes, it is of course possible to apply a method for producing a dye-sensitized photoelectric conversion element for a solar cell using a common dye. Preferably, the dye-sensitized photoelectric conversion element of the present invention can be A thin film of an oxide semiconductor is produced on a substrate using oxide semiconductor fine particles, and then the organic dye according to the present invention is supported on the thin film.

At this time, as the substrate on which the oxide semiconductor thin film is formed, a substrate having conductivity on the surface is preferable, and a commercially available substrate may be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony can be formed on the surface of transparent polymer materials such as glass, polyethylene terephthalate, and polyethersulfone. thin films, or substrates of metal thin films such as copper, silver, and gold. In this case, the electrical conductivity is generally preferably 1000Ω or less, particularly preferably 100Ω or less.

As the above-mentioned oxide semiconductor fine particles, metal oxides are preferable. As specific examples, oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium, and the like can be used. Among them, oxides of titanium, tin, zinc, niobium, indium, etc. are preferred, titanium oxide, zinc oxide, and tin oxide are more preferred, and titanium oxide is most preferred. The above-mentioned oxide semiconductors may be used alone, or mixed or coated on the surface of a semiconductor.

The particle diameter of the above-mentioned oxide semiconductor fine particles is preferably 1 to 500 nm, more preferably 1 to 100 nm in terms of average particle diameter. In addition, the particles of the oxide semiconductor may be used in a mixture of large-diameter particles and small-diameter particles or in a multi-layered form.

The above-mentioned oxide semiconductor thin film can be produced by the following methods: a method of directly forming a thin film of oxide semiconductor fine particles on a substrate by spraying with a nebulizer, a method of depositing a thin film of semiconductor fine particles with electricity using the substrate as an electrode, or a method of depositing a thin film of semiconductor fine particles. Paddle, or a paste containing fine particles produced by hydrolyzing precursors of semiconductor fine particles such as semiconductor alkoxides, is applied on a substrate, and then dried, cured or fired. Among them, it is preferable to apply the paste to method on the substrate.

In the case of employing the method using the slurry of the above-mentioned semiconductor fine particles, the above-mentioned slurry can be obtained by dispersing secondary aggregated oxide semiconductor fine particles in a dispersion medium by a usual method so that the average primary particle diameter is 1 to 200 nm. get.

As the dispersion medium for dispersing the slurry, as long as it is a dispersion medium capable of dispersing semiconductor fine particles, it can be used without particular limitation. Water, alcohols such as ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used. They are mixed. Among them, water is preferably used as the dispersion medium from the viewpoint of reducing the viscosity change of the slurry. In addition, a dispersion stabilizer may be used for the purpose of stabilizing the dispersed state of the oxide semiconductor fine particles. Specific examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid, and nitric acid, acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

In addition, the firing temperature when firing the slurry-coated substrate is 100° C. or higher, preferably 200° C. or higher, and the upper limit is approximately below the melting point (softening point) of the base material. Usually, the upper limit is 900° C., preferably 600° C. below ℃. In the present invention, the firing time is not particularly limited, but is preferably approximately within 4 hours.

In the present invention, the film thickness of the oxide semiconductor fine particles formed on the substrate is preferably 1 to 200 μm, more preferably 1 to 50 μm. In addition, during firing, a part of the thin film of oxide semiconductor fine particles may be welded, but such welding does not particularly affect the present invention.

A secondary treatment may also be performed on the above-mentioned oxide semiconductor thin film. As an example, in a solution of the same metal alkoxide, chloride, nitride, sulfide, etc. as the semiconductor, the thin film is directly deposited according to different substrates, and then dried or fired again, so that the performance of the semiconductor thin film can be improved. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium tert-butoxide, and n-dibutyldiacetyltin. In this case, an alcohol solution can be used as a solvent. Examples of the aforementioned chlorides include titanium tetrachloride, tin tetrachloride, zinc chloride, and the like. In this case, water can be used as a solvent in an aqueous solution. The oxide semiconductor thin film thus obtained is composed of oxide semiconductor particles.

In the present invention, the method of supporting the dye on the oxide semiconductor fine particles formed in the form of a thin film is not particularly limited, and specific examples include the use of organic dyes represented by the above chemical formulas (I) and (II). A method of immersing the substrate provided with the above-mentioned oxide semiconductor thin film in a solution prepared by dissolving the solvent in which it was dissolved, or in a dispersion liquid prepared by dispersing the above-mentioned organic dye.

The concentration of the organic dye in the above-mentioned solution or dispersion liquid can be appropriately determined according to the dye. The dye concentration is preferably 1×10-6M to 1M, more preferably 1×10-5M to 1×10-1M.

The temperature at the time of deposition is approximately normal temperature to the boiling point of the solvent, and the deposition time is approximately 1 minute to 48 hours.

Specific examples of solvents that can be used for dissolving dyes include methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone, tert-butanol, and the like.

In addition, the organic dye to be carried may be one type, or may be a mixture of multiple types. In the case of mixing, other organic dyes or metal complex dyes may be mixed with the organic dye according to the invention. Examples of metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes or their quaternary salts, phthalocyanines, porphyrins, etc. are preferred, and other organic dyes include metal-free phthalocyanines and porphyrins, Or anthocyanin, merocyanine, oxonol, triphenylmethane series, acrylic dyes disclosed in WO2002/011213 and other methine-based dyes, or xanthene-based, azo-based, anthraquinone-based, perylene-based, etc. The dye (referring to literature [M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J.Am.Chem.Soc., No. 115 vol., pp. 6382 (1993)). In the case of using two or more dyes, the dyes may be sequentially adsorbed on the semiconductor thin film, or may be mixed and dissolved for adsorption.

In addition, in the present invention, when the dye is carried on the thin film of oxide semiconductor fine particles, it is preferable to carry the dye in the presence of an clathrate in order to prevent bonding between the dyes. As the clathrate, cholic acids such as deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, methyl cholate, and sodium cholate, steroid compounds such as polyethylene oxide and cholic acid, crowns, etc., can be used. Ether, cyclodextrin, calixarene, polyethylene oxide, etc.

In addition, after loading the dye, the substrate provided with the thin film of semiconductor fine particles can be treated with an amine compound such as 4-tert-butylpyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of immersing a substrate provided with a dye-carrying semiconductor microparticle thin film in an amine ethanol solution or the like can be used.

In this way, a photoelectric conversion element having oxide semiconductor fine particles in the form of a thin film sensitized with a dye can be obtained.

The present invention provides a dye-sensitized solar cell characterized by comprising the above-mentioned dye-sensitized photoelectric conversion element.

The above-mentioned dye-sensitized solar cell may include a photoelectric conversion element electrode (cathode), a counter electrode (anode), a redox electrolyte, a hole transport material, or a p-type semiconductor in which an organic dye is supported on oxide semiconductor fine particles.

For the above-mentioned dye-sensitized solar cell, a conventional method for producing a solar cell using a photoelectric conversion element can be applied, except that a dye-sensitized photoelectric conversion element using the oxide semiconductor fine particles carrying the above-mentioned organic dye is used. As a specific example, the dye-sensitized solar cell according to the present invention can be manufactured through the following steps: a step of coating a titanium oxide paste on a conductive transparent substrate; firing the substrate coated with the paste to form a titanium oxide thin film. steps; the step of immersing the substrate formed with a titanium oxide film in a mixed solution dissolved with an organic dye to form a titanium oxide film electrode adsorbed with a dye; the step of arranging a second glass substrate formed with a counter electrode on its upper part; forming The step of penetrating the hole (hole) of the second glass substrate and the counter electrode; setting a thermoplastic polymer film between the above-mentioned counter electrode and the above-mentioned titanium oxide film electrode adsorbed with dye, and implementing a hot pressing process, so that the above-mentioned counter electrode and The step of bonding titanium oxide film electrodes; the step of injecting electrolyte into the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; and the step of sealing with the thermoplastic polymer.

The aforementioned redox electrolytes, hole transport materials, p-type semiconductors, and the like can be used in forms such as liquid, solidified (gel and gel), solid, and the like. In the case of using in a liquid state, redox electrolytes, molten salts, hole transport materials, p-type semiconductors, etc. are respectively dissolved in solvents, or room temperature molten salts, etc.; solidified solids (gels and gels) In the case of these, respectively, those containing them in a polymer matrix or a low-molecular-weight gelling agent, etc., etc. are mentioned. When utilizing in the form of a solid, solid redox electrolytes, molten salts, hole transport materials, p-type semiconductors, and the like can be used.

As the hole transport material, known hole transport materials can be used. As specific examples, discotic liquid crystals using conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene, and triphenylene compounds can be used. Phase material. In addition, CuI, CuSCN, or the like can be used as the p-type semiconductor. As the counter electrode, it is preferable to use a counter electrode that has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, a counter electrode obtained by vapor-depositing platinum, carbon, rhodium, ruthenium, or the like on glass or a polymer film, or a counter electrode coated with conductive fine particles can be used.

离子、钴配位化合物等金属配位化合物等的金属氧化还原系电解质、烷基硫醇-烷基二硫化物、紫罗碱染料、氢醌-醌等有机氧化还原系电解质等，优选卤素氧化还原系电解质。作为由卤素化合物-卤素分子组成的卤素氧化还原系电解质中的卤素分子，优选碘分子。另外，作为将卤素离子作为抗衡离子的卤素化合物可以使用LiI、NaI、KI、CaI₂、MgI₂、CuI等卤化金属盐，或者四烷基碘化铵、咪唑碘、比啶碘等卤素的有机铵盐，或者I₂。As the above-mentioned redox electrolyte, a halogen redox electrolyte composed of a halogen compound-halogen molecule using a halogen ion as a counter ion, a ferrocyanide-ferrocyanide or a ferrocene-ferrocene

Metal redox electrolytes such as ions, metal complexes such as cobalt complexes, organic redox electrolytes such as alkylthiol-alkyl disulfides, viologen dyes, hydroquinone-quinone, etc., preferably halogen oxidation Reducing electrolyte. As the halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecule, iodine molecule is preferable. In addition, as a halogen compound using a halogen ion as a counter ion, metal halide salts such as LiI, NaI, KI, CaI ₂ , MgI ₂ , CuI, or tetraalkylammonium iodides, imidazoles, etc., can be used. iodine, pyridine Organic ammonium salts of halogens such as iodine, or I ₂ .

唑烷-2-酮、环丁砜、四氢呋喃、水等，特别优选乙腈、碳酸亚丙酯、碳酸亚乙酯、3-甲氧基丙腈、乙二醇、3-甲氧基-

唑烷-2-酮、丁内酯等。上述溶剂可以使用1种或者混合使用。凝胶状电解质的情况下，可以使用在低聚物和聚合物等基质中含有电解质或电解质溶液的物质，或者在低分子胶凝剂等中同样含有电解质或电解质溶液的物质。氧化还原电解质的浓度优选为0.01至99重量％，更优选为0.1至30重量％。In addition, when the redox electrolyte exists in the form of a solution containing it, an electrochemically inert solvent can be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol , butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-

Oxazolidin-2-one, sulfolane, tetrahydrofuran, water, etc., particularly preferably acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, ethylene glycol, 3-methoxy-

Oxazolidin-2-one, butyrolactone, etc. The above-mentioned solvents may be used alone or in combination. In the case of a gel electrolyte, one containing an electrolyte or an electrolytic solution in a matrix such as an oligomer or a polymer, or one containing an electrolyte or an electrolytic solution in a low-molecular gelling agent or the like can be used. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.

According to the solar cell of the present invention, a photoelectric conversion element (cathode) on which oxide semiconductor fine particles are carried on a substrate is arranged so as to face a photoelectric conversion element (cathode) with a dye, and an electrode (anode) containing a redox electrolyte is filled between them. solution obtained.

Hereinafter, the present invention will be described more specifically based on examples. However, these Examples are only for illustrating the present invention, and the present invention is not limited thereto.

Embodiment 1: the synthesis of chemical formula 8

1) Synthesis of intermediate (8a)

2,7-dibromo-9-phenylacridine (2,7-dibromo-9-phenylacridine), 3',4-dihexyl-2,2'-dithiophen-5-ylboronic acid (3', 4-dihexyl-2, 2′-bithiophen-5-ylboronic acid), Pd(PPh ₃ ) ₄ and 2M K ₂ CO ₃ aqueous solution were mixed in dimethylformamide (DMF), and refluxed for 12 hours. The resulting reaction solution was cooled, water (30 ml) and brine were added, and the organic layer was separated and purified to obtain an intermediate (10a) having the following chemical structural formula.

[Intermediate 8a]

2) Synthesis of intermediate (8b)

The intermediate (8a) produced above was added to an absolute ethanol solution, and n-BuLi was further added under argon. After 3 hours, DMF was added to the resulting reaction product at 0° C. under argon gas, followed by washing with 5% KOH. The resulting reaction solution was dried over magnesium sulfate, and the solvent was removed, followed by purification to obtain an intermediate (8b).

[Intermediate 8b]

3) Synthesis of compound formula 8

The intermediate (8b) produced above and cyanoacetic acid were mixed, followed by vacuum drying. The dried product obtained as a result was added to MeCN and piperidine, and then refluxed for 6 hours. After cooling the resulting reaction solution, the organic layer was removed in vacuo, and the resulting solid product was purified by silica gel chromatography to obtain Compound 8 having the following chemical structural formula.

Elemental Analysis: C, 72.46; H, 6.44; N, 3.78; O, 5.76; S, 11.55)

[chemical formula 8]

Embodiment 2: the synthesis of compound formula 10

1) Synthesis of intermediate (10a)

烷-2-基)噻吩并[3，2-b]噻吩-2-基)-2，3-二氢噻吩[3，4-b][1，4]二

英-5-基硼酸，除此之外，按照与上述实施例1相同的方法实施，得到了下述化学结构式的中间体(10a)。Instead of 3',4-dihexyl-2,2'-dithiophen-5-ylboronic acid use 7-(5-(5,5-dimethyl-1,3-di

Alkyl-2-yl)thieno[3,2-b]thiophen-2-yl)-2,3-dihydrothiophene[3,4-b][1,4]di

In-5-ylboronic acid was carried out in the same manner as in Example 1 above except that, to obtain an intermediate (10a) of the following chemical structural formula.

[Intermediate 10a]

2) Synthesis of intermediate (10b)

In 2) of Example 1 above, the intermediate (10a) produced above was dissolved in tetrahydrofuran (THF), and trifluoroacetic acid and water were added dropwise to the resulting solution, followed by stirring for 4 hours under a nitrogen atmosphere.

After completion of the stirring, the resulting reaction solution was extracted with dichloromethane and water, and the organic layer was evaporated, and purified by column chromatography to obtain an intermediate (10b) of the following chemical structural formula.

[Intermediate 10b]

3) Synthesis of compound formula 10

In 3) of the above-mentioned Example 1, except that the intermediate (10b) was used instead of the intermediate (8b), the same method as the above-mentioned Example 1 was carried out, and the compound of the following chemical structure formula 10 was obtained.

Elemental analysis: C, 61.12; H, 2.72; N, 4.19; O, 12.77; S, 19.20

[chemical formula 10]

Embodiment 3: the synthesis of chemical formula 18

1) Synthesis of intermediate (18a)

烷-2-基)噻吩并[3，2-b]噻吩-2-基)-2，3-二氢噻吩并[3，4-b][1，4]二

英-5-甲醛在叔丁醇钾的存在下、在THF溶剂中进行维蒂希(Wittig)反应，得到了下述化学结构式的中间体(18a)。Tetraethyl(9-phenylacridine-2,7-diyl)bis(methylene)diphosphate and 7-(5-(5,5-dimethyl-1,3-di

Alkyl-2-yl)thieno[3,2-b]thiophen-2-yl)-2,3-dihydrothieno[3,4-b][1,4]di

In-5-carbaldehyde was subjected to Wittig reaction in THF solvent in the presence of potassium tert-butoxide to obtain intermediate (18a) of the following chemical structural formula.

[Intermediate 18a]

2) Synthesis of intermediate (18b)

The intermediate (18b) having the following chemical structural formula was obtained in the same manner as in Example 1 except that the intermediate (18a) produced above was used instead of the intermediate (8a) in Example 1.

[Intermediate 18b]

3) Synthesis of compound formula 18

In the above-mentioned Example 1, except that the intermediate (18b) produced above was used instead of the intermediate (8b), the same method as in Example 1 was carried out, and the compound of the following chemical structure formula 18 was obtained.

Elemental analysis: C, 62.54; H, 3.15; N, 3.98; O, 12.12; S, 18.21

[chemical formula 18]

Embodiment 4: the synthesis of chemical formula 40

In Example 1 above, instead of 2,7-dibromo-9-phenylacridine, 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl )-10-phenylanthracene-9-amine, except that, the same method as in Example 1 was carried out sequentially to obtain the compound of the following chemical structure formula 40.

Elemental analysis: C, 78.00; H, 6.48; N, 2.78; O, 4.24; S, 8.50

[chemical formula 40]

Embodiment 5: the synthesis of compound formula 115

Instead of 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-10-phenylanthracene-9-amine use N-(4-(3,6 -Dibromo-10-phenylanthracene-9-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene- Except for 2-amine, the same method as in the above-mentioned Example 4 was followed to obtain a compound of the following chemical structure formula 115.

Elemental analysis: C, 75.77; H, 4.66; Br, 18.00; N, 1.58

[chemical formula 115]

Embodiment 6: the synthesis of compound formula 42

Instead of 2,7-dibromo-9-phenylacridine use 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-10-phenylanthracene -9-amine, except for this, the same method as in Example 1 was sequentially carried out to obtain the compound of the following chemical structure formula 42.

Elemental analysis: C, 70.31; H, 3.81; N, 3.00; O, 9.14; S, 13.74

[chemical formula 42]

Embodiment 7: the synthesis of compound formula 50

Instead of tetraethyl(9-phenylacridine-2,7-diyl)bis(methylene)diphosphate use tetraethyl(10-(bis(9,9-dimethyl-9H-fluorene- 2-yl) amino)-9-phenylanthracene-2,7-diyl) bis(methylene) diphosphate, except that, according to the method identical with embodiment 3, implement successively, obtain following chemical A compound of structural formula 50.

Elemental analysis: C, 71.00; H, 4.09; N, 2.89; O, 8.80; S, 13.22

[chemical formula 50]

Embodiment 8: the synthesis of compound formula 116

Instead of tetraethyl(10-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-9-phenylanthracene-2,7-diyl)bis(methylene)diphosphoric acid Salt using N-(4-(3,6-dibromo-10-phenylanthracene-9-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9 , 9-Dimethyl-9H-fluoren-2-amine, except that, the same method as the above-mentioned Example 7 was carried out to obtain the compound of the following chemical structure formula 116.

Elemental analysis: C, 72.18; H, 4.15; N, 2.74; O, 8.36; S, 12.57

[chemical formula 116]

Embodiment 9: the synthesis of chemical formula 117

Instead of 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-10-phenylanthracene-9-amine use 2,7-dibromo-9, 9-Dimethyl-10-(4-methoxyphenyl)-9,10-dihydroacridine, except that, according to the method identical with above-mentioned Example 6, obtain the following chemical structure 117 compound.

Elemental analysis: C, 61.06; H, 3.32; N, 3.96; O, 13.56; S, 18.11

[chemical formula 117]

Embodiment 10: the synthesis of compound formula 118

Instead of 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-10-phenylanthracene-9-amine use 3,7-dibromo-10- Except for (4-methoxyphenyl)-10H-phenothiazine, the same method as in the above-mentioned Example 6 was carried out to obtain the compound of the following chemical structure formula 118.

Elemental analysis: C, 58.21; H, 2.78; N, 3.99; O, 13.68; S, 21.33

[chemical formula 118]

Embodiment 11: the synthesis of compound formula 119

Instead of 3,6-dibromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-10-phenylanthracene-9-amine use 3,6-dibromo-9- Except for (4-methoxyphenyl)-9H-carbazole, the same method as in the above-mentioned Example 6 was carried out to obtain the compound of the following chemical structure formula 119.

Elemental analysis: C, 60.04; H, 2.87; N, 4.12; O, 14.11; S, 18.86

[chemical formula 119]

Embodiment 12: the synthesis of chemical formula 120

Instead of tetraethyl(10-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-9-phenylanthracene-2,7-diyl)bis(methylene)diphosphoric acid Salt using tetraethyl(9,9-dimethyl-10-(4-methoxyphenyl)-9,10-dihydroacridin-2,7-diyl) bis(methylene) diphosphate Except for the salt, a compound of the following chemical structural formula 120 was obtained in the same manner as in Example 7.

Elemental analysis: C, 62.40; H, 3.70; N, 3.76; O, 12.90; S, 17.23

[chemical formula 120]

Embodiment 13: the synthesis of chemical formula 121

In Example 6 instead of tetraethyl(10-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-9-phenylanthracene-2,7-diyl)bis( methyl) diphosphate and use tetraethyl(10-(4-methoxyphenyl)-10H-phenothiazine-3,7-diyl) bis(methylene) diphosphate, in addition , according to the same method as in the above-mentioned Example 6 to obtain the compound of the following chemical structure formula 121.

Elemental analysis: C, 59.71; H, 3.19; N, 3.80; O, 13.02; S, 20.29

[chemical formula 121]

Embodiment 14: the synthesis of chemical formula 122

Instead of tetraethyl(10-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-9-phenylanthracene-2,7-diyl)bis(methylene)diphosphoric acid The salt used was tetraethyl(9-(4-methoxyphenyl)-9H-carbazole-3,6-diyl)bis(methylene)diphosphate, except that The same method was carried out to obtain the compound of the following chemical structure formula 122.

Elemental analysis: C, 61.49; H, 3.28; N, 3.91; O, 13.40; S, 17.91

[chemical formula 122]

Fabrication of dye-sensitized solar cells

In order to evaluate the current-voltage characteristics of the dyes according to the invention, dye-sensitized solar cells were fabricated with a 13+10 μm TiO2 transparent layer.

0.04M的I₂、0.025M的LiI、0.05M的硫氰酸胍和0.28M的叔丁基吡啶而成的电解质注入到电池中来制造染料敏化太阳能电池。染料敏化太阳能电池的光电池性能是利用1000W氙光源来测定，并将其结果示于下述表1。In detail, the washed FTO (Pilkington, 8Ωsq-1) glass substrate was immersed in a 40 mM TiCl4 aqueous solution. A TiO2 paste (Solaronix, 13nm anatase) was screen printed to produce a first TiO2 layer of 13 μm thickness, and for light scattering a second TiO2 layer of 10 μm thickness was fabricated using other pastes (CCIC, HWP-400) layer. After the prepared TiO2 electrode was immersed in the solution of the dye according to the present invention (the compounds produced in the above-mentioned Examples 1-14 were respectively dissolved at 0.3 mM in ethanol containing 10 mM 3a, 7a-dihydroxy-5b-cholic acid) , placed at room temperature for 18 hours. A counter electrode was produced by coating a H2PtCl6 solution (containing 2 mg of Pt in 1 mL of ethanol) on an FTO substrate. Next, dissolve 0.6M 3-hexyl-1,2-dimethylimidazolium iodide in acetonitrile

An electrolyte composed of 0.04M I ₂ , 0.025M LiI, 0.05M guanidine thiocyanate and 0.28M t-butylpyridine was injected into the battery to manufacture a dye-sensitized solar cell. The photovoltaic performance of the dye-sensitized solar cell was measured using a 1000W xenon light source, and the results are shown in Table 1 below.

Table 1

Distinguish Efficiency (η) (%) Distinguish Efficiency (η) (%) Example 1 4.2 Example 8 4.8 Example 2 4.4 Example 9 4.3 Example 3 4.6 Example 10 5.2 Example 4 5.0 Example 11 4.4 Example 5 4.8 Example 12 4.4 Example 6 5.4 Example 13 5.6 Example 7 5.5 Example 14 4.5

As shown in Table 1 above, the dyes of the present invention exhibit excellent efficiency.

Although the present invention has been described using the specific embodiments above, within the scope of the present invention, those skilled in the art can make various modifications and changes to the present invention.

Industrial Utilization Possibility

The dye compound of the present invention is used in dye-sensitized solar cells (DSSC) to show higher molar absorptivity, Jsc (short-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of solar cells.

Claims (9)

1. the dye-sensitized photoelectric conversion device by following Chemical formula 1 or 2 expressions is used organic dye:

Chemical formula 1

Chemical formula 2

In the said formula,

A is C or N, but A is when being N, and b and c are 0,

B is O, S, CR ¹R ²Or NR ³, at this moment, R ¹To R ³Be hydrogen or C1-12 alkyl independently of one another,

Ar ₁To Ar ₅Independently of one another for replacing or non-substituted C ₆-C ₅₀Aryl,

At this moment, A ₁To Ar ₃Can be interconnection and form ring,

A is 0 or 1,

B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,

D is 0 or 1,

E is 0 or 1,

Be selected from the group of forming by

Sp independently of one another for be selected from by

In the group of forming more than a kind, this moment, L was selected from by O, S, CR independently of one another ⁶R ⁷, SiR ⁸R ⁹And NR ¹⁰In the group of forming, R4 and R5 are selected from by hydrogen, replacement or non-substituted C independently of one another _1-12Alkyl, replacement or non-substituted C _6-30Aryl and replacement or non-substituted C _6-20In the group that heteroaryl is formed, or can interconnect and form ring, R ⁶To R ¹⁰Be hydrogen or replacement or non-substituted C independently of one another _1-12Alkyl, n are 1 to 10 integer.

2. organic dye according to claim 1 is characterized in that,

A is C or N, but when A was N, b and c were 0,

B is S or CR ¹R ², this moment R ¹And R ²Be hydrogen or methyl independently of one another,

Ar ₁To Ar ⁵Be C independently of one another ₆-C ₅₀Aryl or by alkyl or the substituted C of alkoxyl group ₆-C ₅₀Aryl,

A is 0 or 1,

B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,

D is 0 or 1,

E is 0 or 1,

An is

Sp selected

the group consisting of.

3. organic dye according to claim 1 is characterized in that, said organic dye is selected from the compound of following chemical formula 7 to 122 expressions:

Chemical formula 7

Chemical formula 8

Chemical formula 9

Chemical formula 10

Chemical formula 11

Chemical formula 12

Chemical formula 13

Chemical formula 14

Chemical formula 15

Chemical formula 16

Chemical formula 17

Chemical formula 18

Chemical formula 19

Chemical formula 20

Chemical formula 21

Chemical formula 22

Chemical formula 23

Chemical formula 24

Chemical formula 25

Chemical formula 26

Chemical formula 27

Chemical formula 28

Chemical formula 29

Chemical formula 30

Chemical formula 31

Chemical formula 32

Chemical formula 33

Chemical formula 34

Chemical formula 35

Chemical formula 36

Chemical formula 37

Chemical formula 38

Chemical formula 39

Chemical formula 40

Chemical formula 41

Chemical formula 42

Chemical formula 43

Chemical formula 44

Chemical formula 45

Chemical formula 46

Chemical formula 47

Chemical formula 48

Chemical formula 49

Chemical formula 50

Chemical formula 51

Chemical formula 52

Chemical formula 53

Chemical formula 54

Chemical formula 55

Chemical formula 56

Chemical formula 57

Chemical formula 58

Chemical formula 59

Chemical formula 60

Chemical formula 61

Chemical formula 62

Chemical formula 63

Chemical formula 64

Chemical formula 65

Chemical formula 66

Chemical formula 67

Chemical formula 68

Chemical formula 69

Chemical formula 70

Chemical formula 71

Chemical formula 72

Chemical formula 73

Chemical formula 74

Chemical formula 75

Chemical formula 76

Chemical formula 77

Chemical formula 78

Chemical formula 79

Chemical formula 80

Chemical formula 81

Chemical formula 82

Chemical formula 83

Chemical formula 84

Chemical formula 85

Chemical formula 86

Chemical formula 87

Chemical formula 88

Chemical formula 89

Chemical formula 90

Chemical formula 91

Chemical formula 92

Chemical formula 93

Chemical formula 94

Chemical formula 95

Chemical formula 96

Chemical formula 97

Chemical formula 98

Chemical formula 99

Chemical formula 1 00

Chemical formula 1 01

Chemical formula 1 02

Chemical formula 1 03

Chemical formula 1 04

Chemical formula 1 05

Chemical formula 1 06

Chemical formula 1 07

Chemical formula 1 08

Chemical formula 1 09

Chemical formula 1 10

Chemical formula 1 11

Chemical formula 1 12

Chemical formula 1 13

Chemical formula 1 14

Chemical formula 1 15

Chemical formula 1 16

Chemical formula 1 17

Chemical formula 1 18

Chemical formula 1 19

Chemical formula 1 20

Chemical formula 1 21

Chemical formula 1 22

4. the described dye-sensitized photoelectric conversion device of claim 1 comprises with the method for manufacture of organic dye:

(1) make the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out the step that linked reaction is come the compound of manufacturing chemistry formula 5;

(2) compound that makes said chemical formula 5 in organic solvent with BuLi or CF ₃COOH reacts the step of the compound of making following chemical formula 6; And

(3) compound that makes said chemical formula 6 is at CH ₃In the presence of piperidines, carry out the step of association reaction among the CN with the compound that anchoring group is provided,

Chemical formula 3

Chemical formula 4

Y——Sp——Z

Chemical formula 5

Chemical formula 6

In the said formula,

X is Br or

Y is *---B (OH) ₂Or *---CHO,

Z is H or

A, Af1 to Ar4, a, b, c, e and Sp are identical with the definition in the claim 1.

5. a dye-sensitized photoelectric conversion device contains the oxide semiconductor particulate and supports in the described organic dye of the claim 1 of said oxide semiconductor particulate.

6. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said organic dye is in the presence of inclusion compound, to support in the oxide semiconductor particulate.

7. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said oxide semiconductor particulate contains titanium oxide.

8. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said oxide semiconductor particulate has 1 to 500nm median size.

9. a dye sensitization solar battery is characterized in that, comprises that the described dye-sensitized photoelectric conversion device of claim 5 is as electrode.