KR20100128096A - Novel ruthenium-based dye and preparation thereof - Google Patents

Abstract

PURPOSE: A ruthenium-based dye and a manufacturing method thereof are provided to enhance the coherence force of the dye with titanium dioxide and to improve photo-electricity conversion efficiency. CONSTITUTION: A ruthenium-based dye is marked with chemical formula 1. In chemical formula 1, a1 ring is capable of having more than one substituent selected from the group consisting of halogen, amide, cyano, hydroxyl, nitro, C1~C20 alkyl, C1~C20 alkoxy, and acyl. X and Y are selected from the group consisting of functional groups marked with chemical formula 1-a, 1-b, 1-c, and 1-d.

Description

Novel ruthenium-based dyes and preparation method thereof {NOVEL RUTHENIUM-BASED DYE AND PREPARATION THEREOF}

The present invention relates to a novel ruthenium-based dye used in dye-sensitized solar cells (DSSC) and a method for producing the same.

Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.

Typical dyes used in dye-sensitized solar cells include the following compounds.

* TBA: tetrabutylammonium cation

However, it is still required to increase the efficiency and durability of the solar cell by increasing the binding force with the oxide semiconductor fine particles, the photoelectric conversion efficiency, the J _sc (short circuit photocurrent density) and the molar extinction coefficient compared to the above dyes. There is a need for research.

Therefore, the present invention exhibits significantly improved photoelectric conversion efficiency than conventional ruthenium-based dyes, enhances the bonding force with oxide semiconductor fine particles, and has excellent J _sc (single-circuit photocurrent density) and molar extinction coefficient to greatly increase the efficiency of solar cells. It is an object to provide a dye which can be improved and a method for producing the same.

In addition, the present invention exhibits a remarkably improved photovoltaic conversion efficiency including the dye, enhanced binding force with oxide semiconductor fine particles, dye-sensitized photoelectric conversion device excellent in J _sc (short circuit photocurrent density) and molar absorption coefficient, and efficiency It is an object to provide a significantly improved dye-sensitized solar cell.

In order to achieve the above object, the present invention provides a ruthenium-based dye represented by the following formula (1):

[Formula 1]

Where

the a1 ring may have one or more substituents, the substituents may be halogen, amide, cyano, hydroxy, nitro, C _1-20 alkyl, C _1-20 alkoxy or acyl,

,

,

또는

이다 (*부분이 결합부분이며, R₁ 내지 R₁₀은 각각 독립적으로 수소, 할로겐, 아민, 히드록시, C_1-12 알킬, C_1-12 알콕시, C_6-20 아릴 또는 C_6-20 헤테로아릴이다).X and Y are each independently

,

,

or

(* Moiety is a bonding moiety, R ₁ to R ₁₀ are each independently hydrogen, halogen, amine, hydroxy, C _1-12 alkyl, C _1-12 alkoxy, C _6-20 aryl or C _6-20 hetero Aryl).

In another aspect, the present invention provides a method for preparing a dye represented by the formula (1a) characterized in that the compound of the formula (2) is sequentially reacted with the compound of the formula (3), (5), (6) and (7).

[Formula 1a]

[Formula 2]

(3)

[Chemical Formula 5]

[Ru ( p -cymene) Cl ₂ ] ₂

[Formula 6]

[Formula 7]

NH ₄ SCN

In another aspect, the present invention provides a method for preparing a dye represented by the formula (1b) characterized in that the compound of the formula (8) is sequentially reacted with the compound of the formula (9), (11), (5), (6) and (7).

[Chemical Formula 1b]

[Formula 8]

[Formula 9]

SnMe ₃ Cl

[Formula 11]

[Chemical Formula 5]

[Ru ( p -cymene) Cl ₂ ] ₂

[Formula 6]

[Formula 7]

NH ₄ SCN

In another aspect, the present invention provides a method for preparing a dye represented by the formula (1c) characterized in that the compound of formula 13 is sequentially reacted with triisopropyl borate, the compound of formula 11, formula 5, formula 6 and formula 7.

[Formula 1c]

[Formula 13]

[Formula 11]

[Chemical Formula 5]

[Ru ( p -cymene) Cl ₂ ] ₂

[Formula 6]

[Formula 7]

NH ₄ SCN

In another aspect, the present invention provides a method for preparing a dye represented by the formula (1d) characterized in that the compound of formula 13 is sequentially reacted with a compound of dimethylformamide, formula 17, formula 5, formula 6 and formula 7.

≪ RTI ID = 0.0 &

[Formula 13]

[Formula 17]

[Chemical Formula 5]

[Ru ( p -cymene) Cl ₂ ] ₂

[Formula 6]

[Formula 7]

NH ₄ SCN

In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by the formula (1).

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

The novel ruthenium-based dye of the present invention exhibits significantly improved photoelectric conversion efficiency than conventional dyes, enhances the binding force with titanium dioxide, and improves the efficiency of the solar cell due to excellent J _sc (short circuit photocurrent density) and molar extinction coefficient. It can greatly improve.

The present inventors, when manufacturing a dye-sensitized solar cell by supporting the compound represented by the formula (1) in the oxide semiconductor fine particles, it is strongly bonded to the oxide semiconductor fine particles and excellent in durability, photoelectric conversion efficiency, J _sc (short circuit photocurrent density) and mol It was confirmed that the higher the extinction coefficient than the existing dye-sensitized solar cells exhibited higher efficiency and completed the present invention.

Ruthenium-based dyes of the present invention may preferably be represented by any of the following structures:

In another aspect, the present invention provides a method for producing a dye represented by the formula (1a), the dye represented by the formula (1a) is sequentially reacted with a compound of the formula (2) and a compound of the formula (3), (5), (6) Specifically, (1) the compound of Chemical Formula 2 is prepared by mixing and refluxing the compound of Chemical Formula 2 with a compound of Chemical Formula 3 in an organic solvent (eg, tetrahydrofuran (THF)) in the presence of NaH, and refluxing. (2) It may be prepared by reacting a compound of formula 4 with a compound of formula 5 in an organic solvent (e.g., dimethylformamide (DMF)) and subsequently reacting with a compound of formula 6 and 7 in succession ( See Scheme 1 below).

Scheme 1

In another aspect, the present invention provides a method for producing a dye represented by the formula (1b), the dye represented by the formula (1b) is a compound of the formula (8) to the formula (9), (11), (5), (6) and (7) It is prepared by sequentially reacting, specifically, (1) the compound of formula (10) by reacting the compound of formula (8) with the compound of formula (9) in the presence of n-BuLi in an organic solvent (e.g. tetrahydrofuran (THF)) (2) reacting a compound of Formula 10 with a compound of Formula 11 in the presence of Pd (PPh ₃ ) ₄ in an organic solvent (eg toluene) to prepare a compound of Formula 12, (3) It can be prepared by reacting a compound of with a compound of the formula (5) in an organic solvent (eg dimethylformamide (DMF)) and subsequently reacting with the compound of formula 6 and 7 in sequence (See Scheme 2).

Scheme 2

In another aspect, the present invention provides a method for producing the dye represented by the formula (1c) and 1d, the dye represented by the formula (1c) is a compound of formula 13 to triisopropyl borate, formula 11, formula 5, formula 6 and formula It is prepared by sequentially reacting with a compound of, specifically (1) by reacting the compound of formula 13 with triisopropyl borate in the presence of n-BuLi in an organic solvent (e.g. tetrahydrofuran (THF)) To prepare a compound of (2) and (2) reacting a compound of formula 14 with a compound of formula 11 in the presence of Pd (PPh ₃ ) ₄ in an organic solvent to prepare a compound of formula 15, (3) Prepared by reacting with a compound represented by the following Chemical Formula 5 in an organic solvent (e.g., dimethylformamide (DMF)) and subsequently reacting with the compound represented by the following Chemical Formulas 6 and 7 It may be;

The dye represented by Formula 1d is prepared by sequentially reacting a compound of Formula 13 with a compound of dimethylformamide, Formula 17, Formula 5, Formula 6, and Formula 7. Specifically, (1) Reaction with dimethylformamide in the presence of hydrochloric acid in an organic solvent (eg tetrahydrofuran (THF)) to prepare a compound of formula (16), and (2) the compound of formula 16 in the presence of K ₂ CO ₃ in an organic solvent A compound of formula 18 is prepared by reacting with a compound of formula 17, and (3) the compound of formula 18 is reacted with a compound of formula 5 in an organic solvent (eg, dimethylformamide (DMF)), and subsequently, And by reacting sequentially with the compound of 7 (see Scheme 3 below).

Scheme 3

In Schemes 1 to 3, 1,1,7,7-tetramethylzulolidine, which is the basis of compounds used as starting materials for the preparation of the dyes of Formulas 1a, 1b, 1c and 1d, is represented by the following Scheme 4 and Can be prepared together. In this case, the reaction scheme takes a relatively short time, and the π-electron of phenyl is increased by the electron donor of gluolidine with the help of nitrogen-covalent pair of electrons and two neighboring hexagonal compounds of juliolidine. Make a significant contribution (see Tetrahedron Letters 44 (2003) 145 and Adv. Funct. Mater. 2007, 17, 93).

Scheme 4

In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for solar cells using a conventional dye, of course, preferably the present invention The dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.

In this invention, it is preferable that the surface is electroconductive as a board | substrate which provides the thin film of an oxide semiconductor, and what is marketed can also be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on the surface of glass or transparent polymer materials such as polyethylene terephthalate or polyethersulfone, or metal thin films such as steel, silver, and gold What formed this can be used. In this case, the conductivity is preferably 1000 Ω or less, particularly preferably 100 Ω or less.

As the fine particles of the oxide semiconductor, a metal oxide is preferable. As specific examples, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, among these, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferred. The oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.

The particle diameter of the fine particles of the oxide semiconductor is preferably 1 to 500 nm, more preferably 1 to 100 nm as the average particle diameter. In addition, the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.

The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide. After applying the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate, it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferred. In the case of this method, a slurry can be obtained by disperse | distributing the oxide semiconductor microparticles | fine-particles which are secondary aggregated so that an average primary particle diameter may be 1-200 nm in a dispersion medium by a conventional method.

The dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols such as water and ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used, and these can be mixed and used. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. Specific examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid and nitric acid, or acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

The substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below ℃. In the present invention, the firing time is not particularly limited, but is generally within 4 hours.

It is preferable that the thickness of the thin film on a board | substrate in this invention is 1-200 micrometers, Preferably it is 1-50 micrometers. Although some thin layers of oxide semiconductor fine particles are welded when firing, such welding is not particularly troubled for the present invention.

In addition, the oxide semiconductor thin film may be subjected to secondary treatment. For example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride, or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example by dispersing a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was provided in the obtained dispersion liquid is mentioned. The concentration in the solution or dispersion can be appropriately determined by the dye. The deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours. Specific examples of the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like. The dye concentration of the solution is usually 1 x 10 ^-6 M to 1 M is suitable, preferably 1 x 10 ^-5 M to 1 x 10 ^-1 M. In this way, the photoelectric conversion element of this invention which has oxide semiconductor microparticles | fine-particles on the thin film sensitized with dye can be obtained.

The dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, another dye or a metal complex dye can be mixed with the dye of this invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferable, and organic dyes used for mixing include metal-free phthalocyanine, porphyrin, cyanine, merocyanine, Methine dyes such as oxonol, triphenylmethane, and acrylic acid dyes as shown in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene-based dyes (MK Nazeeruddin, A). .Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., Vol. 115, p . 6382 (1993). ). In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.

In the present invention, when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the dyes from bonding. Examples of the inclusion compound include carboxylic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, methyl ester of cholate, and sodium cholate, steroidal compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix arene, Polyethylene oxide and the like can be used.

After the dye is supported, the semiconductor electrode surface can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.

In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion electrode (cathode) and a charge in which the dye represented by Chemical Formula 1 is supported on the oxide semiconductor fine particles. It may be composed of an electrode (anode), a redox electrolyte, a hole transport material, or a p-type semiconductor.

Preferably, one example of a specific method of manufacturing a dye-sensitized solar cell of the present invention is the step of coating a titanium oxide paste on a conductive transparent substrate, baking the substrate coated with a paste to form a titanium oxide thin film, titanium oxide thin film Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon. Forming a hole penetrating a glass substrate and a counter electrode, placing a thermoplastic polymer film between the counter electrode and the dye-adsorbed titanium oxide film electrode, and performing a heat compression process to perform the counter electrode and titanium oxide. Bonding a film electrode to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; Implanting be and can be prepared through the step of sealing the thermoplastic polymer.

Redox electrolytes, hole transport materials, p-type semiconductors, and the like may be in the form of liquids, coagulants (gels and gels), solids, and the like. As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and at room temperature, dissolved salts, etc., in the case of coagulation bodies (gels and gels), these are polymer matrices or low molecular gelling agents. What was contained in etc. can be mentioned, respectively. As the solid, a redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.

Examples of the hole transport material include an amine derivative, a conductive polymer such as polyacetylene, polyaniline, and polythiophene, and an object using a discotech liquid crystal phase such as triphenylene-based compound. Moreover, CuI, CuSCN, etc. can be used as a p-type semiconductor. It is preferable that the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.

As the redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen redox-based electrolytes are preferable. As a halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecules, an iodine molecule is preferable. As a halogen compound having a halogen ion as a large ion, halogenated metal salts such as LiI, NaI, KI, CaI ₂ , MgI ₂ and CuI, or organic ammonium salts of halogens such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, Or I ₂ can be used.

In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of a gel positive electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent 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.

In the solar cell of the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is carried on an oxide semiconductor fine particle on a substrate so as to face it, and a solution containing a redox electrolyte is filled therebetween. Can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Synthesis of Dyes

All reactions were run in an argon atmosphere and the solvent was distilled off with a suitable reagent purchased from Sigma-Adrich. ¹ H NMR spectra were measured on a Varian Mercury 300 spectrometer. Absorbance spectra were measured with a Perkin-Elmer Lambda 2S UV-visible spectrometer.

Example 1 Preparation of a Compound of Formula 1a

(1-1) A compound of formula 2 (1.5 g, 5.83 mmol), a compound of formula 3 (1.26 g, 2.77 mmol) and potassium tert-butoxide (0.66 g, 5.83 mmol) were dissolved in 30 ml of THF, followed by nitrogen gas. Stir at room temperature for 4 hours. The organic layer was extracted with methylene chloride and water, and then distilled and column chromatographed (eluent-E.A: Hx = 1: 2) to synthesize a compound of Chemical Formula 4.

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.77 (m, 8H), 3.18 (m, 8H), 6.75 (d, ³ J _HH = 16 Hz, 2H), 6.98 (d, ³ J _HH = 16 Hz, 2H), 7.30 (s, 4H), 7.60 (s, 2H), 8.63 (d, ³ J _HH = 5.2 Hz, 2H), 8.71 (d, ³ J _HH = 5.2 Hz, 2H) .

(1-2) The synthesized compound of formula 4 (0.83g, 1.19mmol) and compound of formula 5 (0.36g, 0.598mmol) were dissolved in 15ml of DMF, and then blocked at light under nitrogen gas at 180 ° C for 4 hours. Stirred. After stirring, the compound of formula 6 (0.29 g, 1.19 mmol) was added dropwise and stirred at 160 ° C. for 4 hours. Finally, the compound of formula 7 (0.45 g, 5.98 mmol) was added dropwise and stirred at 140 ° C. for 4 hours. Purification is described in Chem. Mater. 2006, 18, 5604-5608 to prepare a compound of formula 1a (see Scheme 1 below).

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.77 (m, 8H), 3.18 (m, 8H), 6.75 (d, ³ J _HH = 16 Hz, 2H), 6.98 (d, ³ J _HH = 16 Hz, 2H), 7.29 (s, 4H), 7.60 (s, 2H), 7.65 (s, 2H), 8.60 (m, 4H), 8.70 (m, 4H), 12.84 (s, 2H) .

Scheme 1

Example 2 Preparation of a Compound of Formula 1b

(2-1) 1,1,7,7-tetramethylzulolidine (1.0 g, 4.36 mmol) was dissolved in 30 ml of THF, and n-BuLi (2M, 2.5 ml) was slowly added dropwise at -78 ° C, followed by nitrogen. Stirred under gaseous state for 1 hour. After stirring, the compound of formula 9 (1M, 5ml) was slowly added dropwise under -78 ° C, and then stirred for 1 hour under nitrogen gas, followed by further stirring at room temperature for 30 minutes. The organic layer was extracted with methylene chloride and water and distilled to obtain an oily compound. Compound (0.32 g, 1.34 mmol) and Pd (PPh ₃ ) ₄ (0.12 g, 0.1 mmol) were added thereto, dissolved in toluene (40 ml), and stirred under reflux for 8 hours under nitrogen gas. The organic layer was extracted with methylene chloride and water, and then distilled and column chromatographed (eluent-EA: Hx = 1: 2) to synthesize a compound of Chemical Formula 12.

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.77 (m, 8H), 3.18 (m, 8H), 7.30 (s, 4H), 7.58 (s, 2H), 8.61 (d , ³ J _HH = 5.2 Hz, 2H), 8.73 (d, ³ J _HH = 5.2 Hz, 2H).

(2-2) The synthesized compound of formula 12 (0.61g, 0.998mmol) and compound of formula 5 (0.3g, 0.49mmol) were dissolved in DMF (15ml), and then 180 minutes for 4 hours while blocking light under nitrogen gas. Stir at ° C. After stirring, the compound of formula 6 (0.24 g, 0.98 mmol) was added dropwise, followed by stirring at 160 ° C. for 4 hours. Finally, the compound of formula 7 (0.47 g, 4.9 mmol) was added dropwise and stirred at 140 ° C. for 4 hours. Purification is described in Chem. Mater. 2006, 18, 5604-5608 to prepare a compound of formula 1b (see Scheme 2 below).

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.77 (m, 8H), 3.18 (m, 8H), 7.31 (s, 4H), 7.60 (s, 2H), 7.65 (s , 2H), 8.60 (m, 4H), 8.70 (m, 4H), 12.80 (s, 2H).

Scheme 2

Example 3 Preparation of a Compound of Formula 1d

(3-1) After dissolving the compound of Formula 12 (0.74 g, 1.8 mmol) in 20 ml of THF, n-BuLi (2M, 1.08 ml) was slowly added dropwise at -78 ° C and stirred for 1 hour under nitrogen gas. After stirring, DMF (0.2ml, 2.6mmol) was slowly added dropwise under -78 ° C, stirred for 1 hour under nitrogen gas, and further stirred at room temperature for 30 minutes. The organic layer was extracted with methylene chloride and water, and then distilled and column chromatographed (eluent-E.A: Hx = 1: 2) to synthesize a compound of Chemical Formula 16.

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 12H), 1.78 (m, 4H), 3.20 (m, 4H), 6.75 (d, ³ J _HH = 16 Hz, 1H), 6.98 (d, ³ J _HH = 16 Hz, 1H), 7.28 (s, 2H), 7.39 (d, d, ³ J _HH = 10.4 Hz, 2H), 7.61 (d, ³ J _HH = 10.4 Hz, 2H), 9.81 (s, 1H).

(3-2) A compound of formula 16 (0.69 g, 1.89 mmol), a compound of formula 17 (0.29 g, 0.63 mmol) and potassium tert-butoxide (0.21 g, 1.89 mmol) were dissolved in 30 ml of THF, and then in a nitrogen gas state. Stir at room temperature for 4 hours. After stirring, the organic layer was extracted with methylene chloride and water, and then distilled and column chromatographed (eluent-E.A: Hx = 1: 2) to synthesize a compound of Chemical Formula 18.

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.78 (m, 8H), 3.20 (m, 8H), 6.72 (m, 2H), 6.96 (m, 2H), 7.31 (s , 4H), 7.39 (d, ³ J _HH = 10.4 Hz, 4H), 7.61 (m, 6H), 8.63 (d, ³ J _HH = 5.2 Hz, 2H), 8.71 (d, ³ J _HH = 5.2 Hz, 2H).

(3-3) The synthesized compound of formula 18 (0.27g, 0.314mmol) and compound of formula 5 (0.092g, 0.149mmol) were dissolved in 15ml of DMF and then blocked at light under nitrogen gas at 180 ° C for 4 hours. Stirred. After stirring, the compound of formula 6 (0.076g, 0.314mmol) was added dropwise and stirred at 160 ° C for 4 hours. Finally, the compound of Chemical Formula 7 (0.14 g, 1.49 mmol) was added dropwise and stirred at 140 ° C. for 4 hours. Purification is described in Chem. Mater. 2006, 18, 5604-5608 to prepare a compound of formula 1d (see Scheme 3 below).

¹ H NMR (CDCl ₃ ): [ppm] = 1.48 (s, 24H), 1.80 (m, 8H), 3.24 (m, 8H), 6.72 (m, 2H), 6.96 (m, 2H), 7.31 (s , 4H), 7.41 (d, ³ J _HH = 10.4 Hz, 4H), 7.58 (m, 6H), 7.65 (s, 2H), 8.60 (m, 4H), 8.73 (m, 4H), 12.78 (s, 2H)

Scheme 3

Example 4 Measurement of Physical Properties of Prepared Dyes

The absorption spectra of the dye compounds 1a, 1b and 1d of the present invention prepared in Examples 1 to 3 are shown in Tables 1 and 2, and FIGS. 1 and 2. As Comparative Compounds 1 and 2, conventionally known compounds having the following structures were used.

     <Comparative Compound 1> <Comparative Compound 2>

TABLE 1

TABLE 2

λ _max Absorbance ε density Compound 1b 304nm 3.304 6.60 × 10 ⁴ L / mol * cm 5 × 10 ^-5 M Compound 1b 390 nm 2.166 4.33 × 10 ⁴ L / mol * cm 5 × 10 ^-5 M Compound 1b 544 nm 0.788 1.57 × 10 ⁴ L / mol * cm 5 × 10 ^-5 M Compound 1d 318nm 1.48 4.93 × 10 ⁴ L / mol * cm 3 × 10 ^-5 M Compound 1d 362nm 1.2 4.00 × 10 ⁴ L / mol * cm 3 × 10 ^-5 M Compound 1d 548nm 0.628 2.09 × 10 ⁴ L / mol * cm 3 × 10 ^-5 M

As can be seen from the results of Table 1-2 and FIGS. 1-2, the dye compounds of the present invention prepared in Examples 1 to 3 exhibit much higher absorbance than Comparative Compounds 1 and 2, thereby greatly improving the efficiency of the solar cell. It is expected to.

Example 5 Preparation and Measurement of Dye-Sensitized Solar Cell

In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was prepared using an 8 μm or 12 μm TiO ₂ transparent layer (Compounds 1a and 1b were 12 μm and Compound 1d was 8 μm). A TiO ₂ paste (Solaronix, 13 nm paste) was screen printed to produce an 8 μm thick TiO ₂ transparent layer. This TiO ₂ film was treated with 40 mM TiCl ₄ solution and dried at 500 ° C. for 30 minutes. After the treated film was cooled to 60 ° C., each of the dye compounds 1a, 1b and 1d of the present invention prepared in Examples 1 to 3 was impregnated in a dimethylformamide solution. As a reference, an ethanol solution of N719 was used. A sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 μm thick) as a spacer between the dye-adsorbed TiO ₂ electrode and the platinum-electrode. As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI ₂ , 0.025 M GSCn and 0.28 M tert -butylpyridine was dissolved in acetonitrile.

N719 used as a reference compound is a ruthenium-based catalyst used in conventional dye-sensitized solar cells and has a structure as follows.

Without using a mask and using a mask, the photoelectrochemical characteristics of the solar cells prepared using the dye compounds 1a, 1b and 1d of the present invention, respectively, are shown in FIGS. 3 to 5 and Table 3 below. Indicated. The photoelectrochemical characteristics of the solar cell were measured using a Keithley M 236 source measuring device, and a 300 W Xe lamp equipped with an AM 1.5 filter (Oriel) was used as the light source, and the electrode size was 0.4 × 0.4 cm ² . The intensity was 1 sun (100 mW / cm ² ). Light intensity was adjusted using a Si solar cell.

[Table 3]

V _oc (V) J _sc (mA / cm ² ) FF (%) Light conversion efficiency (%) Compound 1a 0.6143 2.442 75.97 1.14 Compound 1a
(Mask) 0.6118 2.166 73.38 0.97 Compound 1b 0.7033 3.324 75.45 1.76 Compound 1b
(Mask) 0.6913 2.375 72.97 1.2 Compound 1d 0.6969 3.406 74.86 1.78 Compound 1d
(Mask) 0.7034 2.702 77.86 1.48 Reference compound 0.7555 10.139 73.07 5.6

In Table 3, J _sc represents a short-circuit photocurrent density, V _oc represents an open circuit photovoltage, and FF represents a fill factor.

1 is an absorption spectrum of the dye compound 1a of the present invention prepared in Example 1, and Comparative Compounds 1 and 2,

2 is an absorption spectrum of the dye compounds 1a, 1b and 1d of the present invention prepared in Examples 1 to 3,

3 to 5 are photocurrent-voltage curves (under AM 1.5 radiation) of solar cells prepared using the dye compounds 1a, 1b and 1d of the present invention prepared in Examples 1 to 3, respectively.

Claims (12)

Ruthenium-based dyes represented by Formula 1 below: [Formula 1]

Where the a1 ring may have one or more substituents, the substituents may be halogen, amide, cyano, hydroxy, nitro, C _1-20 alkyl, C _1-20 alkoxy or acyl, X and Y are each independently

,

,

or

(* Moiety is a bonding moiety, R ₁ to R ₁₀ are each independently hydrogen, halogen, amine, hydroxy, C _1-12 alkyl, C _1-12 alkoxy, C _6-20 aryl or C _6-20 hetero Aryl). The method of claim 1, A ruthenium-based dye, wherein the dye is represented by one of the following structures:

Comprising sequentially reacting a compound of Formula 2 with a compound of Formula 3, Formula 5, Formula 6 and Formula 7, To prepare a dye represented by the formula (1a): [Formula 1a]

[Formula 2]

(3)

[Chemical Formula 5] [Ru ( p -cymene) Cl ₂ ] ₂ [Formula 6]

[Formula 7] NH ₄ SCN Comprising sequentially reacting a compound of Formula 8 with a compound of Formula 9, Formula 11, Formula 5, Formula 6, and Formula 7, To prepare a dye represented by the formula (1b): [Chemical Formula 1b]

[Formula 8]

[Formula 9] SnMe ₃ Cl [Formula 11]

[Chemical Formula 5] [Ru ( p -cymene) Cl ₂ ] ₂ [Formula 6]

[Formula 7] NH ₄ SCN Comprising sequentially reacting a compound of Formula 13 with a compound of Triisopropylborate, Formula 11, Formula 5, Formula 6, and Formula 7, Preparation method of the dye represented by the formula (1c): [Formula 1c]

[Formula 13]

[Formula 11]

[Chemical Formula 5] [Ru ( p -cymene) Cl ₂ ] ₂ [Formula 6]

[Formula 7] NH ₄ SCN Comprising sequentially reacting a compound of Formula 13 with a compound of dimethylformamide, Formula 17, Formula 5, Formula 6, and Formula 7, Preparation method of the dye represented by the formula (1d): &Lt; RTI ID = 0.0 &

[Formula 13]

[Formula 17]

[Chemical Formula 5] [Ru ( p -cymene) Cl ₂ ] ₂ [Formula 6]

[Formula 7] NH ₄ SCN A dye-sensitized photoelectric conversion device comprising oxide semiconductor fine particles carrying the ruthenium-based dye of claim 1. The method of claim 7, wherein A dye-sensitized photoelectric conversion device characterized in that a ruthenium-based dye is supported on the oxide semiconductor fine particles in the presence of an inclusion compound. The method of claim 7, wherein Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide as an essential component. The method of claim 7, wherein Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles have an average particle diameter of 1 to 500 nm. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device of claim 7 as an electrode. The method of claim 11, Wherein the dye-sensitized solar cell, coating a titanium oxide paste on a conductive transparent substrate, baking the paste-coated substrate to form a titanium oxide thin film, the dye represented by the formula (1) is dissolved in a substrate formed with a titanium oxide thin film Impregnating the mixed solution to form a titanium oxide film electrode on which dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon, a hole penetrating through the second glass substrate and the counter electrode. Forming a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode to which the dye is adsorbed, and performing a heat compression process to bond the counter electrode and the titanium oxide film electrode to each other; Injecting an electrolyte into the thermoplastic polymer film between the pole and the titanium oxide film electrode, and the thermoplastic polymer The dye-sensitized solar cell, characterized in that is produced through the step of sealing.

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