KR101940491B1 - A NOBLE Ru-TYPE SENSITIZERS AND METHOD FOR PREPARING OF IT - Google Patents

Abstract

The present invention relates to a novel ruthenium (Ru) -based dye and a method for producing the same, and more particularly, to a dye-sensitized solar cell which exhibits remarkably improved photoelectric conversion efficiency , Titanium dioxide and a dye capable of enhancing the efficiency of a solar cell due to its excellent short circuit photocurrent density (Jsc) and molar extinction coefficient, and a method for producing the dye.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel ruthenium-based dye and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a novel ruthenium-based dye used as a dye in a dye-sensitized solar cell and a method for producing the same.

Much research has been done in this area since the development of dye-sensitized nanoparticle titanium dioxide solar cells by Michael Gratzel of the Swiss National Lozan Institute for Technology (EPFL) in 1991. Dye-sensitized solar cells have the potential to replace existing amorphous silicon solar cells because they have a significantly lower manufacturing cost than conventional silicon solar cells. Unlike silicon solar cells, dye-sensitized solar cells absorb visible light, - a dye molecule capable of forming a hole pair, and a transition metal oxide that transfers generated electrons as main constituent materials.

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

* TBA: tetrabutylammonium cation

However, it is still required to improve the efficiency and durability of the solar cell by increasing the bonding strength with the oxide semiconductor fine particles, photoelectric conversion efficiency, short circuit photocurrent density (Jsc) and molar extinction coefficient as compared with the above dyes. Research is needed.

In order to solve the problems of the prior art as described above, the present invention provides a dye-sensitized solar cell which exhibits remarkably improved photoelectric conversion efficiency than conventional dyes, enhances bonding strength with oxide semiconductor particles, has excellent short circuit photocurrent density (Jsc) And to provide a dye capable of greatly improving the efficiency of a solar cell and a method for producing the same.

The present invention also provides a dye-sensitized photoelectric conversion device which exhibits remarkably improved photoelectric conversion efficiency including the dye, has enhanced bonding force with oxide semiconductor particles, has a short circuit photocurrent density (Jsc) and a molar absorptivity coefficient, And to provide a solar cell.

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

[Chemical Formula 1]

In Formula 1, Me is Ru or Os, each of the a1 rings independently has no substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, , A C _1-30 alkyl group or a C _1-30 alkoxy group, Y is hydrogen, Na, or tert-butyl alcohol (TBA)

X ₁ and X ₂ are each independently methyl or a compound represented by the following general formula (2), at least one of X ₁ and X ₂ is a compound represented by the general formula (2)

(2)

,

,

및

로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, Se, Si 및 NR₅로 이루어진 군으로부터 선택되고, R₁ 내지 R₄는 각각 독립적으로 수소, 치환 또는 비치환된 C_1-12 알킬, 치환 또는 비치환된 C_6-30 아릴 및 치환 또는 비치환된 C_6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R₅는 수소 또는 치환 또는 비치환된 C_1-30 알킬이고, n은 1 내지 10의 정수이며,In the formula (2), A represents

,

,

And

, Wherein each X is independently selected from the group consisting of O, S, Se, Si and NR ₅ , R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C _{1 - 12} alkyl, substituted or unsubstituted C _6-30 aryl, and substituted or unsubstituted selected from the group consisting of unsubstituted C _6-20 aryl or heteroaryl, or connected to each other may form a ring, R ₅ is hydrogen or Substituted or unsubstituted C _1-30 alkyl, n is an integer of 1 to 10,

B is a compound represented by the following formula (3) or a compound represented by the following formula (4)

(3)

[Chemical Formula 4]

In Formula 3, Ar ₁ , Ar _2, and Ar ₃ are each independently selected from the group consisting of substituted or unsubstituted C _6-50 aryl, substituted or unsubstituted C _6-20 heteroaryl, And * is a bonding moiety. In the formula (4), R ₆ and R ₇ are each independently substituted or unsubstituted C _1-30 alkyl, and * is a bonding moiety.

The present invention also provides a process for preparing a dye represented by the general formula (1), wherein the compound of the general formula (5) is sequentially reacted with the compounds of the general formulas (6), (7) and (8)

[Chemical Formula 5]

[Chemical Formula 6]

[RuCl ₂ ( p -cymene)] ₂

(7)

[Chemical Formula 8]

NH ₄ NCS

In Formulas 5, 6, 7 and 8, X ₁ , X ₂ , and a ₁ are as defined above.

Further, the present invention provides a dye-sensitized photoelectric conversion device comprising oxide semiconductor microparticles carried by a compound represented by the formula (1).

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

The novel ruthenium-based dye of the present invention exhibits remarkably improved photoelectric conversion efficiency compared to conventional dyes, enhances bonding force with oxide semiconductor fine particles, has excellent short circuit photocurrent density (Jsc) and molar absorptivity, Can greatly improve.

1 is an absorption spectrum of the dye compound of the present invention and N719 prepared in Example 1,
FIG. 2 is a graph of a short-circuit photocurrent density (Jsc) measured with a dye-sensitized solar cell manufactured using the dye compound of the present invention prepared in Example 1,
3 is a graph of a short-circuit photocurrent density (Jsc) measured with a dye-sensitized solar cell manufactured using a N719 dye compound.

Hereinafter, the present invention will be described in detail.

The present inventors have found that when a dye sensitized solar cell is produced by supporting a compound represented by the formula (1) on oxide semiconductor fine particles, the dye-sensitized solar cell is strongly bonded to oxide semiconductor fine particles and is excellent in durability and has excellent photoelectric conversion efficiency, short circuit photocurrent density (Jsc) And thus the efficiency of the dye-sensitized solar cell was higher than that of the conventional dye-sensitized solar cell. Thus, the present invention was completed.

The dye of the present invention is characterized by being represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Me is Ru or Os, each of the a1 rings independently has no substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, , A C _1-30 alkyl group or a C _1-30 alkoxy group, Y is hydrogen, Na, or tert-butyl alcohol (TBA)

X ₁ and X ₂ are each independently methyl or a compound represented by the following general formula (2), at least one of X ₁ and X ₂ is a compound represented by the general formula (2)

(2)

,

,

및

로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, Se, Si 및 NR₅로 이루어진 군으로부터 선택되고, R₁ 내지 R₄는 각각 독립적으로 수소, 치환 또는 비치환된 C_1-12 알킬, 치환 또는 비치환된 C_6-30 아릴 및 치환 또는 비치환된 C_6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R₅는 수소 또는 치환 또는 비치환된 C_1-30 알킬이고, n은 1 내지 10의 정수이며,In the formula (2), A represents

,

,

And

, Wherein each X is independently selected from the group consisting of O, S, Se, Si and NR ₅ , R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C _{1 - 12} alkyl, substituted or unsubstituted C _6-30 aryl, and substituted or unsubstituted selected from the group consisting of unsubstituted C _6-20 aryl or heteroaryl, or connected to each other may form a ring, R ₅ is hydrogen or Substituted or unsubstituted C _1-30 alkyl, n is an integer of 1 to 10,

B is a compound represented by the following formula (3) or a compound represented by the following formula (4)

(3)

[Chemical Formula 4]

In Formula 3, Ar ₁ , Ar _2, and Ar ₃ are each independently selected from the group consisting of substituted or unsubstituted C _6-50 aryl, substituted or unsubstituted C _6-20 heteroaryl, And * is a linking moiety, wherein R ₆ and R ₇ are each independently substituted or unsubstituted C _1-30 alkyl, * is a linking moiety, preferably R ₆ and R ₇ is a C _5-10 alkyl, including C _5-10 alkyl or sulfur.

Preferably, the dye represented by the formula (1) is one of the compounds represented by the following formulas (1-1) to (1-48).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Chemical Formula 1-25]

[Chemical Formula 1-26]

[Chemical Formula 1-27]

[Chemical Formula 1-28]

[Chemical Formula 1-29]

[Chemical Formula 1-30]

[Chemical Formula 1-31]

(1-32)

[Chemical Formula 1-33]

[Chemical Formula 1-34]

[Chemical Formula 1-35]

[Chemical Formula 1-36]

[Chemical Formula 1-37]

[Chemical Formula 1-38]

[Chemical Formula 1-39]

[Chemical Formula 1-40]

[Chemical Formula 1-41]

[Chemical Formula 1-42]

[Chemical Formula 1-43]

[Chemical Formula 1-44]

[Chemical Formula 1-45]

[Chemical Formula 1-46]

[Chemical Formula 1-47]

[Chemical Formula 1-48]

The present invention also provides a process for preparing a dye represented by the general formula (1), wherein the compound of the general formula (5) is sequentially reacted with the compounds of the general formulas (6), (7) and (8)

[Chemical Formula 5]

[Chemical Formula 6]

[RuCl ₂ ( p -cymene)] ₂

(7)

[Chemical Formula 8]

NH ₄ NCS

In Formulas 5, 6, 7 and 8, X ₁ , X ₂ , and a ₁ are as defined above.

In the present invention, the compounds used as starting materials in the preparation of the dyes of formula (1) can be prepared or purchased by conventional methods.

Further, the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye-sensitized photoelectric conversion element is characterized in that the dye represented by Formula 1 is supported on the oxide semiconductor fine particles. The dye-sensitized photoelectric conversion device according to the present invention can be applied not only to the dye represented by the formula (1), but also to the dye-sensitized photoelectric conversion device for solar cells using conventional dyes. The dye-sensitized photoelectric conversion element of the present invention may be produced by preparing an oxide semiconductor thin film on a substrate using oxide semiconductor fine particles, and then carrying the dye of the present invention on the thin film.

In the present invention, as the substrate on which the thin film of the oxide semiconductor is provided, the surface of the substrate is preferably conductive, and a commercially available substrate may be used. As a concrete example, a conductive metal oxide such as indium, fluorine, and antimony coated on the surface of a glass or a polymeric material having transparency such as polyethylene terephthalate or polyethersulfone, or a metal thin film of steel, silver, Can be used. In this case, the conductivity is usually preferably 1000 Ω or less, and 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 may be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, and among them, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferable. The oxide semiconductor may be used singly, or it may be mixed or coated on the surface of a semiconductor.

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

The oxide semiconductor thin film may be formed by a method of forming oxide semiconductor fine particles directly on a substrate by spraying spray or the like, a method of electrically depositing a semiconductor fine particle thin film using the substrate as an electrode, a method of depositing semiconductor fine particles such as slurry of semiconductor fine particles or semiconductor alkoxide A paste containing fine particles which can be obtained by hydrolyzing a precursor is coated on a substrate, followed by drying, curing or firing, or a method of applying a paste onto a substrate. In the case of this method, the slurry can be obtained by dispersing the oxide semiconductor microparticles that are secondarily agglomerated by a conventional method so that the average primary particle diameter becomes 1 to 200 nm in the dispersion medium.

The dispersion medium for dispersing the slurry is not particularly limited as long as it can disperse the semiconductor fine particles. The dispersion medium may be an alcohol such as water or ethanol, a ketone such as acetone or acetyl acetone, or a hydrocarbon such as hexane. And it is preferable that water is used among them in view of reducing viscosity change of the slurry. Further, a dispersion stabilizer may be used for the purpose of stabilizing the dispersion 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, and acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

The substrate to which the slurry has been applied can be fired. The firing temperature is not lower than 100 占 폚, preferably not lower than 200 占 폚, and the upper limit is generally not higher than the melting point (softening point) Lt; / RTI > The firing time in the present invention is not particularly limited, but is preferably within four hours.

In the present invention, the thickness of the thin film on the substrate is preferably 1-200 占 퐉, and preferably 1-50 占 퐉. When firing is performed, a thin layer of the oxide semiconductor fine particles is partially deposited, but such deposition is not particularly troublesome for the present invention.

Further, the oxide semiconductor thin film may be subjected to a secondary treatment. For example, the performance of a semiconductor thin film may be improved by dipping a thin film directly on a solution of an alkoxide, chloride, nitrogen, sulfide or the like of the same metal as the semiconductor, and drying or re-firing the substrate. Examples of the metal alkoxide include titanium ethoxide, titanium is isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin and the like, and alcohol solutions thereof can be used. Examples of the chloride include titanium tetrachloride, tin tetrachloride, and zinc chloride, and an aqueous solution thereof can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

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. Specific examples thereof include a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving the dye, And the substrate provided with the oxide semiconductor thin film is immersed in the obtained dispersion. The concentration in the solution or dispersion can be suitably determined by the dye. The immersion time is generally from room temperature to the boiling point of the solvent, and the immersion time is from 1 minute to 48 hours. Specific examples of the solvent that can be used for dissolving the dye include methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone, and t-butanol. The dye concentration of the solution is usually 1 × 10 ^-6 M ^-1 M, preferably 1 × 10 ^-5 M ^-1 × 10 ^-1 M. Thus, the photoelectric conversion element of the present invention having oxide semiconductor fine particles in the form of a thin film formed by increasing or decreasing the dye can be obtained.

The dyes represented by the formula (1) to be carried in the present invention may be either one kind or a mixture of several kinds. In case of mixing, only the dye of the present invention can be used, and other dyes or metal complex dyes can be mixed. Examples of the metal complex dyes which can be mixed include, but are not limited to, MKNazeeruddin, A. Kay, I. Radicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzel, J. Am . Chem. Soc., Vol. 115, p. 6382 (1993). Ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin and the like are preferable. Examples of the organic dyes to be mixed include phthalocyanine, porphyrin, cyanine, merocyanine, Dyes such as phenanthrene, norbornene, triphenylmethane, and acrylic acid dyes shown in WO2002 / 011213; dyes such as xanthene, azo, anthraquinone and perylene dyes. In the case of using two or more kinds of dyes, the dye may be successively adsorbed to the semiconductor thin film, or may be mixed and dissolved to be adsorbed.

In the present invention, when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to carry the dye in the presence of the adsorbing compound in order to prevent bonding of the dyes to each other. Examples of the above-mentioned inclusion compound include: Colecular compounds such as deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester and sodium cholate; steroid compounds such as polyethylene oxide and cholic acid; crown ethers, cyclodextrin, Polyethylene oxide and the like can be used.

After the dye is supported, the surface of the semiconductor electrode can be treated with an amine compound such as 4-t-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 semiconductor fine particle thin film having a dye supported thereon in an ethanol solution of amine can be used.

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element, wherein the dye-sensitized solar cell using the dye-sensitized photoelectric conversion element using the dye- In addition, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion element may be applied. For example, a photoelectric conversion element electrode (cathode) in which the dye represented by Chemical Formula 1 is supported on the oxide semiconductor fine particles, (Anode), a redox electrolyte, a hole transporting material, or a p-type semiconductor.

Preferably, the method of manufacturing the dye-sensitized solar cell of the present invention includes coating a titanium oxide paste on a conductive transparent substrate, firing a paste-coated substrate to form a titanium oxide thin film, A step of impregnating the formed substrate with a mixed solution in which the dye represented by the general formula (1) is dissolved to form a dye-adsorbed titanium oxide film electrode, a step of providing a second glass substrate on which a counter electrode is formed, Forming a hole through the substrate and the counter electrode, placing a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode on which the dye is adsorbed, and performing a hot pressing process to form the counter electrode and the titanium oxide film Bonding the electrode to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole, A step of injecting an electrolyte, and a step of sealing the thermoplastic polymer.

Examples of the redox electrolyte, the hole transporting material, and the p-type semiconductor include liquid, coagulated (gel and gel), solid and the like. Examples of the liquid phase include redox electrolytes, dissolution salts, hole transport materials, and p-type semiconductors dissolved in a solvent, and at room temperature dissolution salts. In the case of coagulated solids (gel and gel), these are dissolved in a polymer matrix or a low- And the like, and the like. Solids such as redox electrolytes, soluble salts, hole transport materials, p-type semiconductors and the like can be used.

As the hole transporting material, conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene, and articles using a discotic liquid crystal phase such as a triphenylene compound can be used. As the p-type semiconductor, CuI, CuSCN and the like can be used. It is preferable that the counter electrode has conductivity and acts catalytically on the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium or the like may be deposited on a glass or polymer film, or coated with conductive fine particles.

Examples of the redox electrolyte used in the solar cell of the present invention include halogen redox electrolytes composed of halogen compounds and halogen molecules having halogen ions as counter ions, A metal oxide red-based electrolyte such as a metal complex of an alkali metal, an alkyl thiol-alkyl disulfide, a viologen dye, an organic redox electrolyte such as a hydroquinone-quinone, and a halogen redox electrolyte. The halogen molecule in the halogen redox electrolyte composed of a halogen compound-halogen molecule is preferably an iodine molecule. In addition, the halogen compound to a halogen ion as a counter ion LiI, NaI, KI, CaI _2, MgI _2, a halogenated metal salt such as CuI, or tetra-alkyl ammonium iodine, imidazolium iodine, the organic ammonium salt of halogen such as flutes Stadium iodine, Or I ₂ can be used.

When the redox electrolyte is formed in the form of a solution containing it, electrochemically inactive ones can be used as the solvent. Specific examples thereof include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylolactone, dimethoxyethane, dimethyl carbonate, Dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran and water. Particularly, acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butylolactone and the like are preferable. These solvents may be used alone or in combination. In the case of a gel-type positive electrolyte, an electrolyte or an electrolyte solution may be contained in a matrix such as an oligomer and a polymer, or an electrolyte or an electrolyte solution may be used in the same manner as a whole molecular gelling agent. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.

The solar cell of the present invention is characterized in that a counter electrode (anode) is disposed so as to face a photoelectric conversion element (cathode) carrying a dye on the oxide semiconductor fine particles on a substrate and a solution containing the 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]

The reaction involved in the synthesis of the dye proceeded in an argon atmosphere, and the solvent was distilled with a suitable reagent purchased from Sigma-Aldrich.

Example 1 Synthesis of dye

The ruthenium-based dye compound 4 was prepared according to the reaction shown in Reaction Scheme 1 described below.

[Reaction Scheme 1]

(1) Preparation of Compound (1)

N-Butyllithium (56.06 ml, 2.5 M in Hexane, 140 mmol) was slowly added dropwise at -78 ° C, and 30 g of 3,4-dibromo-2,2'-bipyridine (20 g, 63.70 mmol) After stirring for a minute, DMF (10.24 g, 140.14 mmol) was added and stirred at 25 DEG C for 6 hours under a nitrogen gas atmosphere. After stirring, ether was extracted with 300 ml of water. The organic layer was extracted with water and recrystallized under chloroform / methanol (1/10).

(2) Preparation of Compound 2

Thieno [3,2-b] thiophene (10 g, 71.31 mmol) was dissolved in 200 ml of THF, n-Butyllithium (28.52 ml 2.5 M in Hexane, 71.31 mmol) was slowly added dropwise at -78 ° C, 9-bromoheptadecane (22.77 g, 71.31 mmol) was added, and the mixture was stirred at 25 DEG C for 6 hours under a nitrogen gas atmosphere. After stirring, the reaction mixture was extracted with 200 ml of chloroform. The organic layer was extracted with water and purified by column chromatography (chloroform / hexane = 1: 1) followed by recrystallization under chloroform / methanol (1/20).

(3) Preparation of Compound 3

Thiophene (26.77 g, 70.69 mmol) and trimethylamine (0.42 mmol) were added to a solution of 2,2'-bipyridine-4,4'-dicarbaldehyde (15 g, 70.69 mmol) g, 7.07 mmol) were dissolved in 100 ml of acetic anhydride and stirred under reflux. After stirring, the mixture was extracted with chloroform (300 ml). The organic layer was extracted with water and recrystallized under chloroform / methanol (1/10).

(4) Preparation of Compound 4

Compound No. 5 was synthesized according to the synthesis method of the existing literature (Chem. Mater. 2006, 18, 5604-5608) using the compound 3 prepared above, as shown in Scheme 1.

Example 2 Synthesis of dye

The ruthenium-based dye compound 7 was prepared according to the reaction shown in Reaction Scheme 2 described below.

[Reaction Scheme 2]

(1) Preparation of Compound 5

Compound 5 was synthesized by using Thiophene instead of Thieno [3,2-b] thiophene in the preparation of Compound 2 of Example 1 above.

(2) Preparation of Compound 6

Compound 6 was synthesized by using Compound 5 instead of 2- (heptadecan-9-yl) thieno [3,2-b] thiophene in the process for producing Compound 3 of Example 1. [

(3) Preparation of Compound 7

The compound 4 was synthesized in the same manner as in Example 1, except that Compound 6 was used instead of Compound 3.

Example 3 Synthesis of dye

The ruthenium-based dye compound 10 was prepared according to the reaction shown in Reaction Scheme 3 described below.

[Reaction Scheme 3]

(1) Preparation of Compound 8-1

Compound 8-1 was synthesized by using Compound 8 instead of Thieno [3,2-b] thiophene in the preparation of Compound 2 of Example 1 above.

(2) Preparation of Compound 9

Compound 9 was synthesized by using Compound 8-1 instead of 2- (heptadecan-9-yl) thieno [3,2-b] thiophene in the process for producing Compound 3 of Example 1. [

(3) Preparation of Compound 10

The compound 4 was synthesized in the same manner as in Example 1, except that Compound 3 was used instead of Compound 3.

Example 4: Measurement of physical properties of the prepared dye

The absorption spectra of the dye compounds of the present invention prepared in Example 1 are shown in Table 1 and FIG. As a comparative dye, N719, which is used as a dye of a conventional dye-sensitized solar cell, was used.

λ _max
(nm) ε
(M ^-1 cm ^-1 ) λ _edge
(nm) HOMO
(eV) LUMO
(eV) Example 1 609 11700 840 -5.55 -3.95 N719 515 14000 731 -5.50 -3.80

As can be seen from the results of Table 1 and FIG. 1, the dye compound of the present invention prepared in Example 1 exhibits much higher absorbance than the comparative dye, and is expected to improve the efficiency of the solar cell.

Although not shown in Table 1, the dye compounds of the present invention prepared in Examples 2 and 3 exhibited the same absorbance as those of the dye compounds prepared in Example 1 above.

Example 5: Preparation of dye-sensitized solar cell and measurement of physical properties

In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using a TiO ₂ transparent layer with different thicknesses as shown in Table 2 and Figs. 2 to 3 below. And a TiO ₂ paste (Solaronix, 13 nm paste) was screen-printed to prepare a TiO ₂ transparent layer. The TiO ₂ film was treated with a 40 mM TiCl ₄ solution and dried at 500 ° C for 30 minutes. After the treated film was cooled to 60 캜, the dye compound of the present invention prepared in Example 1 was impregnated in a dimethylformamide solution. An ethanol solution of N719 was used as a reference. The sealed sandwich cell was assembled by placing a hot melt film (Surlyn 1702, 25 탆 thick) as a spacer between the dye-adsorbed TiO ₂ electrode and the platinum-counter electrode and heating. As the electrolyte solution, 0.6 M 3-hexyl-1,2-dimethylimidazolium iodide, 0.04 MI ₂ , 0.025 M GSCn and 0.28 M tert -butylpyridine dissolved in acetonitrile were used. Scattering layer and AR coating were not applied.

The photoelectrochemical characteristics of the solar cell prepared using the dye compound of the present invention and N719 were measured and shown in FIG. 2 (Examples 1 to 3) and Table 2 below. The photoelectrochemical properties of the solar cell were measured using a Keithley M 236 source measuring apparatus. A 300 W Xe lamp equipped with an AM 1.5 filter (Oriel) was used as the light source. The electrode size was 0.4 × 0.4 cm ² , The intensity was 1 sun (100 mW / cm ² ). The intensity of light was adjusted using Si solar cell.

V _oc (V) J _sc (mA / cm ² ) FF (%) 侶 (%) Area (cm ² ) Thickness (um) N719 0.866 6.83 76.64 4.53 0.162 3.93 0.818 11.12 74.31 6.76 0.165 7.58 0.801 12.74 73.21 7.47 0.187 11.81 Example 1 0.800 11.03 73.86 6.52 0.177 3.92 0.757 14.63 73.10 8.10 0.163 7.92 0.747 15.81 73.07 8.64 0.193 12.17

In Table 2, J _sc represents a short-circuit photocurrent density, V _oc represents an open circuit photovoltage, and FF represents a fill factor.

As shown in Table 2 and FIG. 2 to FIG. 3, it was confirmed that the dye compound of the present invention exhibited a very high photoelectric conversion efficiency as compared with N719, and the dye compounds prepared in Examples 2 and 3 are also shown in Table 2 However, the photoelectric conversion efficiency was equivalent to that of Example 1, indicating that it could be used as a dye compound of a dye-sensitized solar cell.

Claims (7)

A dye represented by the following formula (1):
[Chemical Formula 1]

In Formula 1, Me is Ru or Os,
a1 rings each independently have a substituent or may have one or more substituents, the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, an acyl group, C _1-30 alkyl, or C _{1- Lt; / RTI} > alkoxy group,
Y is hydrogen, Na, or tert-butyl alcohol (TBA)
X ₁ and X ₂ are each a group represented by the following formula (2)
(2)

In the formula (2), A represents

,

And

Wherein each X is independently selected from the group consisting of O, S, Se, Si and NR ₅ , R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C _1-12 Alkyl, substituted or unsubstituted C _6-30 aryl and substituted or unsubstituted C _6-20 heteroaryl, or may be connected to each other to form a ring, and R ₅ is hydrogen or substituted or unsubstituted hwandoen is C _1-30 alkyl, n is an integer from 1 to 10,
B is a group represented by the following formula (4)
[Chemical Formula 4]

In Formula 4, R ₆ and R ₇ are each independently substituted or unsubstituted C _1-30 alkyl, and * is a bonding moiety. The method according to claim 1,
The dye is a ruthenium (Ru) -based dye which is one of the compounds represented by the following formulas:
[Chemical Formula 1-25]

[Chemical Formula 1-27]

[Chemical Formula 1-29]

[Chemical Formula 1-31]

[Chemical Formula 1-33]

[Chemical Formula 1-35]

[Chemical Formula 1-37]

[Chemical Formula 1-39]

[Chemical Formula 1-41]

A process for preparing a dye represented by the following formula (1), wherein the compound represented by the following formula (5) is sequentially reacted with a compound represented by the following formula (6), (7)
[Chemical Formula 5]

[Chemical Formula 6]
[RuCl ₂ ( p -cymene)] ₂
(7)

[Chemical Formula 8]
NH ₄ NCS
X ₁ , X ₂ , and a ₁ in the above formulas (5), (6), (7) and (8) are as defined in claim 1. A dye-sensitized photoelectric conversion element comprising oxide semiconductor microparticles carried by a dye according to any one of claims 1 to 5. 5. The method of claim 4,
Wherein said dye-sensitized photoelectric conversion element is a dye-sensitized photoelectric conversion element in which a dye is supported on oxide semiconductor microparticles in the presence of an inclusion compound. 5. The method of claim 4,
Wherein the oxide semiconductor fine particles include titanium dioxide having an average particle size of 1-500 nm as an essential component. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element according to claim 4.

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