TW200938594A - Novel Ru-type sensitizers and method of preparing the same - Google Patents

Abstract

The present invention relates to novel Ru-type dye and a method for preparing the same, more specifically to dye which is be used for a dye-sensitized solar cell to show remarkably improved photoelectric transformation efficiency compared to the existing dye, strengthens bonding force with titanium dioxide, and has excellent Jsc(short circuit photocurrent density) and molar absorption coefficient, thus largely improving the efficiency of solar cell, and a method for preparing the same.

Description

200938594 VI. Description of the Invention: [Technical Field] Field of the Invention The present invention relates to a novel fluorene dye for use in a dye-sensitized solar cell and a process for the preparation thereof. [Prior Art] Background of the Invention ❹ - 10 15 Michael By 1991 Michael of the Lausanne Institute of Technology (EPFL) of the Swiss Confederation

Gratzel et al. have developed dye-sensitized nanoparticle titanium oxide solar cells. There have been a number of studies on this - in terms of dye-sensitized solar cells, the cost of manufacturing solar cells is significantly lower. It may replace the existing amorphous solar cell. And the dye-sensitized solar cell mainly comprises a transition metal oxide which absorbs visible light to generate an electron-hole pair and a transition metal oxide which is generated by the electron. The dyes of solar cells used in the prior art gene dye sensitization include the following compounds.

C00H

*TBA: tetrabutylammonium cation but still need to improve the bonding efficiency with oxide semiconductor particles ★ (short-circuit photocurrent density) and material absorption system turn forward step - 3 20 200938594 good solar cell efficiency and durability . There is therefore a need to develop novel dyes. SUMMARY OF THE INVENTION Technical Problem In order to solve the problems of the foregoing prior art, it is an object of the present invention to provide a dye which exhibits a significantly improved photoelectric conversion efficiency compared to the prior art dye, enhances the bonding force with the oxide semiconductor particles, and It has excellent Jsc (short-circuit photocurrent density) and molar absorption coefficient, which greatly improves the efficiency of solar cells and its preparation method. 10 15 Another object of the present invention is to provide a dye-sensitized photoelectric conversion element comprising the aforementioned dye, which exhibits markedly improved photoelectric conversion efficiency, enhanced bonding force with oxide semiconductor particles, and excellent Jsc (short circuit) Photocurrent density) and molar absorption coefficient, and a solar cell with improved efficiency. Technical Solution In order to achieve the aforementioned object, the present invention provides a quinone type dye represented by the following Chemical Formula 1: [Chemical Formula 1]

200938594 (wherein the ring a may optionally have one or more substituents selected from the group consisting of an i atom, a guanamine, a cyano group, a hydroxyl group, a schlossyl group, a stilbene group, a Ci_3G alkyl group, and a Ci_3G alkoxy group) And X and Y are respectively methyl or one of the following Chemical Formulas 2-1 to 2-14 represents 5 and at least one of X and Y is one of the following Chemical Formulas 2-1 to 2-14 Said: [Chemical Formula 2-1]

[Chemical Formula 2_3]

COOH

5 200938594 [Chemical Formula 2-4] [Chemical Formula 2-5] 5 [Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8] 6 200938594

[Chemical Formula 2-9]

D K1 [Chemical Formula 2-10]

Rj

[Chemical Formula 2-11]

[Chemical Formula 2-12] 7 200938594

5 10 (wherein (*) represents a bond; the ring bl may be selected from a halogen atom, a guanamine, a brewing amine, an aryl group, a thiol group, a nitro group, a stilbene group, a Ci-3G alkyl group, and a Ci-30, as needed. Substituting one or more substituents in the group consisting of alkoxy groups; A is S or hydrazine; and R, R1, R_2 and respectively are chlorine, Ci-15 alkyl, Ci-15 alkoxy, C6 -2Q aryl or C6_2 doped aryl; η is an integer from 1 to 10). The present invention also provides a process for producing a dye represented by the following Chemical Formula 1, comprising the steps of: reacting a compound of the following Chemical Formula 3 with a compound of the following Compound 4, Compound 5, and Compound 6 as follows: [Chemical Formula 3]

5C 8 15 200938594 [RuCl2(p-isopropyltoluene)] 2 [Chemical Formula 4] [Chemical Formula 5]

Nh4ncs (where X, Y, and al are as defined above). The present invention also provides a dye-sensitized photoelectric conversion element comprising oxide semiconductor particles, wherein a compound represented by the above formula 支 is supported on the oxide semiconductor particles. The present invention also provides a dye-sensitized solar cell comprising a dye-sensitized photoelectric conversion element. Excellent effect The novel anthraquinone dye of the present invention exhibits a significant change in the photoelectric conversion efficiency of the prior art dyes to enhance the bonding force with the oxide semiconductor particles, and has excellent Jsc (short-circuit photocurrent density) and molar absorption coefficient. Greatly improve solar cell efficiency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an absorption line diagram using DCSC 1, DCSC 20 2, DCSC 3, DCSC 4, DCSC 8, DCSC 9 according to an embodiment of the present invention and N719 according to a comparative example as a dye. tEmbodiment 3 9 200938594 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will now be explained. The present inventors have found that if the compound represented by Chemical Formula 1 is supported on an oxide semiconductor particle to prepare a dye-sensitized solar cell, the compound 5 is strongly bonded to the oxide semiconductor particles, so that the solar cell exhibits excellent durability and is excellent. The Jsc (short-circuit photocurrent density) and the molar absorption efficiency, thus the dye-sensitized solar cell exhibits excellent efficiency compared to the existing solar cell, thus completing the present invention. The hydrazine dye of the present invention is represented by the following chemical formula: 10 [Chemical Formula 1]

(wherein the ring a can be selected from the group consisting of a functional atom, a guanamine, an aryl group, and a thiol group as needed

And one or more substituents are substituted; and X and Y are each a fluorenyl group or are represented by the following chemical formula 2_U2_14 and at least one of X and Y is by the following chemical formulas 2-1 to 2-14 One of them indicates that at least one of X and Y represents: [Chemical Formula 2-1]

X 200938594

[Chemical Formula 2-2]

/ m [Chemical Formula 2-3] [Chemical Formula 2-4]

€OOH

[Chemical Formula 2-5]

11 200938594 [Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

12 200938594 [Chemical Formula 2-10]

[Chemical Formula 2-13]

13 200938594 (where (*) denotes a bond; the ring bi can be selected from the group consisting of an imine, a amide, a nitrogen, a thiol, a thiol, a thiol, a Ci_3G, and a Cl-3G. Substituting one or more substituents in the group consisting of; A is S or Ο; and R, Rl, R_2 and respectively are nitrogen, Ci-15 alkyl, Ci_i5 alkoxy, 5 C6_2Q aryl or C6.2Q heteroaryl; η is an integer from 1 to 10). Specifically, the oxime dye of the present invention is represented by one of the following Chemical Formulas 1-1 to 1-38: [Chemical Formula 1-1]

Η匕学式1-2]

14 200938594 [Chemical Formula 1-3]

[Chemical Formula 1-4]

5 [Chemical Formula 1-5]

15 200938594 [Chemical Formula 1-6]

[Chemical Formula 1-7]

5 [Chemical Formula 1-8]

16 200938594 [Chemical Formula 1-9]

[Chemical Formula 1-10]

[Chemical Formula 1-11]

17

200938594 [Chemical Formula 1-12] [Chemical Formula 1-13] 5 [Chemical Formula 1-14]

18 200938594

Dropout style 1-15]

[Chemical Formula 1-16]

19 200938594 [Chemical Formula 1-17]

[Chemical Formula 1-18]

5 [Chemical Formula 1-19] 20 200938594

[Chemical Formula 1-20] ❹ [Chemical Formula 1-21]

21 200938594

[Chemical Formula 1-22]

[Chemical Formula 1-23] 22 200938594

[Chemical Formula 1-24]

[Chemical Formula 1-25] 23 200938594

[Chemical Formula 1-26] [Chemical Formula 1-27]

〇 24 200938594

[Chemical Formula 1-28]

[Chemical Formula 1-29] 25 200938594

[Chemical Formula 1-30]

[Chemical Formula 1-31] 26 200938594

[Chemical Formula 1-32]

[Chemical Formula 1-33] 27 200938594

[Chemical Formula 1-34]

[Chemical Formula 1-35] 28 200938594

[Chemical Formula 1-36]

[Chemical Formula 1-37] 29 200938594

[Chemical Formula 1-38]

(wherein A and R are as defined in Chemical Formula 1). The present invention also provides a process for producing a dye represented by the following Chemical Formula 1, comprising the steps of: reacting a compound of the following Chemical Formula 3 with a compound of the following Compound 4, Compound 5, and Compound 6 as follows: [Chemical Formula 3] 30 200938594

[RuC12(p-isopropylisopropylbenzene)] 2 [Chemical Formula 5]

[Chemical Formula 6] nh4ncs (wherein X, Y and al are as defined above). Preferably, the dye of the present invention is produced by one of the methods shown in the following Reaction Formulas 1 to 6: [Reaction formula 1]

R = benzyl, octyl

CC'U

Mi acetic acid ammonium acetate: cyclohexane

31 200938594 [Reaction formula 2]

[Reaction formula 3]

DCSC0 32 200938594 [Reaction 4]

TsQH reflux

2-2·-bipyridyl-4, 4'-dicarboxylic acid HOOC COOH

[Ru (p-isopropyl phenyl) 1) sleep reflow 4 small turns 1 - 60t: reflux 4 hours I, in Dingling (dimlingt)

(In Reaction Scheme 4, R is hydrogen, (^-15 alkyl, C!-15 alkoxy, C6-20 aryl or C6_2G heteroaryl) 5 [Reaction formula 5]

33 200938594 [Reaction 6]

In the above respective reaction formulas, the compound for preparing the starting material of the dye of Chemical Formula 1 can be produced or purchased by a general method. Specifically, dithienothiaphene, trithienothiophene and tetrathienothiophene can be produced by the following preparation of Formula 1-3. And the diphenothithiophene can be prepared in a relatively short reaction time and can be recrystallized without column purification, so that the synthesis is extremely simple (refer to [Chem. Mater. 2007, 19, .4007-4015] and [J. Mater] Chem. 1999, 9, 1719-1725]). 10 [Preparation 1]

34 200938594 [Preparation 2]

Din II A k-kola 哼 THF.-70.C:

NBS

0HC 〇Hc

Br

CHO Br + HS,, C00Et

K2C〇3mT

HO CH3COOH reflux for 12 hours EtOOC

,C00Et

UOH 〇

HOOC

OCH

CU ff backflow for 2 hours

[Preparation 3] 1) LM 2) thiophene bite

H9S

THF. .70-C CHO cm3co〇h reflux for 12 hours ohc^A^cho +

HS^COOR I^CCb

DMF

EtdOC

s^,COOEt

UOH HOOC, .COOH Cu

THF S’ S' porphyrin reflux for 12 hours

The present invention also provides a dye-sensitized photoelectric conversion element in which the dye represented by the above Chemical Formula 1 is supported on an oxide semiconductor particle. The dye-sensitized photoelectric conversion element of the present invention can be used by using a prior art dye. It is prepared by any of the methods of preparing a dye-sensitized photoelectric conversion element for a solar cell. Preferably, the oxide semiconductor film is difficult to form on the substrate using an oxide semiconductor, and the dye of the present invention is supported thereon. The substrate on which the oxide semiconductor film is formed is preferably conductive and commercially available. For example, it is possible to use a conductive metal oxide thin 35 200938594 gold _=2 tin oxide or the like or a metal film such as steel, silver, surface or formed on a transparent polymer such as polyethylidene 5 10 The substrate prepared above. It is preferably one having an electrical conductivity of 〇 ohm or less, more preferably _ ohm or less. As for the oxide semiconductor particles, a metal oxide is preferred. For example, titanium, tin, rhodium, erroneous, marry, indium, ki, sharp, button, hunger oxidation, etc., preferably using titanium, tin, ruthenium, sharp or indium oxide; titanium oxide, oxidized or oxidized material Better to ride with titanium. Oxide semiconductor

The body can be used alone or in combination, or can be applied to a semiconductor surface. The oxide semiconductor particles preferably have an average of M(8) nm and more preferably 1 gangrene: in which there are large and small diameters can be mixed or can be used in multiple layers.

The preparation of the oxide semiconductor film is directly formed on the substrate by spraying the oxide semiconductor particles; using the substrate as an electrode, the electrospray 15 to accumulate a film of the semiconductor particle, or applying on the substrate via a semiconductor particle precursor such as A slurry or a paste of a particle-containing semiconductor particle obtained by hydrolysis of a semiconductor alkoxide or the like, and dried, hardened or sintered. Preferably, the paste is applied to the substrate, in which case the secondary condensed oxide semiconductor particles are dispersed in a dispersion medium to a first particle diameter of 1 to 200 nm to obtain a slurry by a usual method. As the dispersion medium, a medium which can disperse semiconductor particles can be used without limitation. For example, water, an alcohol such as ethanol, a ketone such as acetone, ethyl acetonylacetone, or a smoke such as hexazone can be used and can be used in combination. Water is preferred because water reduces the viscosity of the slurry. Further, a dispersion stabilizer 36 200938594 can be used to stabilize the dispersion of the oxide semiconductor particles. As the dispersion stabilizer, an acid such as acetic acid, hydrochloric acid, nitric acid or the like or acetyl hydrazine, acrylic acid, polyethylene glycol, polyvinyl alcohol or the like can be used. 5 ❹ - 10 15 10 20 The substrate on which the slurry is applied may be sintered at a temperature of 1 Torr or more, preferably 200. (: or above, and the upper limit of the sintering temperature is the melting point (softening point) of the substrate' is usually 900 ° C, preferably 6 〇〇. (: The sintering time is not particularly limited, but preferably within 4 hours. The film thickness on the substrate is from 1 to 200 μm, preferably 丨 5 μm. In the case of sintering, the oxide semiconductor particle film is partially fused, and such fusion does not cause any damage to the present invention. And the 'oxide semiconductor film can be subjected to secondary treatment. For example, the film can be immersed in the carbon semiconductor metal wire, chloride, nitride, sulfide solution, and dried or re-sintered, thereby improving the properties of the film. As the gold oxide, titanium oxide, isopropoxide, second milk reduction, n-dibutyl-diethylene, and alcohol solution can be used. As for the chloride, four titanium carbide can be used. An aqueous solution can be used for vaporizing tin, zinc hydride, etc. The thus obtained oxide semiconducting (tetra) film comprises a method in which an oxide semiconducting dye is present on the oxide semiconducting granule and is limited in its shape. Silk base of conductor film The solution can be properly determined by transferring the solution of the dye to the dye of the above formula 1 or by immersing in the dispersion solvent 2 or fraction f obtained by dispersing the dye. The immersion temperature is from room temperature to / time. 1 minute to 48 hours. As for the solvent for the dissolution of 37 200938594 dye, methanol, ethanol, acetonitrile, dimethyl hydrazine, dimethylformamide, acetone, tert-butanol, etc. may be used. The concentration of the solution is usually 1χ1〇. -6 Μ to 1 Μ, preferably ιχι〇-5μ to lxio·1 Μ. Thus, a dye-sensitized photoelectric conversion element comprising an oxide semiconductor particle in a thin film form can be obtained. The dyes may be used in combination with several dyes. In the case where several dyes are used in combination, only the dyes according to the invention or the dyes according to the invention may be used in combination with other dyes or metal complex dyes. The complex dye is not particularly limited, but it is preferably a ruthenium complex or its fourth salt, phthalocyanine, porphyrin, etc., said 10 in Na. ze.Κ. 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). As for the organic dyes which can be mixed, metal-free phthalocyanine, porphyrin, cyanine, merocyanine, and cedarol can be used. (oxonol), or benzotriene dye, low methyl dye 15 such as W 〇 2 〇〇 2 / 〇 U213 acrylic acid syrup dye, t star dye, azo dye, awake dye, flower dye In the case of using two or more kinds of dyes in combination, the semiconductor film may be sequentially mixed, dissolved, dissolved, and absorbed. When the dye is supported on the oxide semiconductor particle film, in order to prevent the connection between the dyes, it is preferred. It is supported by the inclusion compound in the presence of the inclusion body compound. For the inclusion body compound, bile acid such as deoxycholic acid, deoxydeoxycholic acid, keto deoxycholic acid, cholesteric acid, bile acid can be used. Natto; cholesterol compounds such as cholic acid, polyepoxyethane, etc.; secret, cyclosalazine (calyxarene); polycyclohexane, etc. After the dye is supported, the surface of the semiconductor electrode can be used with amine compounds 38 200938594 4-second-butylpyridine, or having an acid group such as acetic acid, propionic acid, etc. The substrate is treated. The substrate having the dye-supported semiconductor particle film formed thereon can be immersed in an ethanol solution of the amine.

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element. It can be prepared by a conventional method for preparing a solar cell using a photoelectric conversion element of the prior art. The dye-sensitized solar cell may comprise a photoelectric conversion element electrode (negative electrode), wherein the dye represented by the chemical formula is supported on the oxide semiconductor particle, the counter electrode (positive electrode), the redox electrolyte, the hole_transport material Or p-type semiconductors, etc. 10 Preferably, the dye-sensitized solar cell of the present invention is prepared by coating a titanium oxide coating on a transparent conductive substrate; sintering the coated substrate to form a titanium oxide film; Thin _ on it 15

a dye which is immersed in a chemical magic watch* is dissolved in a mixed solution of the towel. Thus, a purely absorbed titanium oxide film electrode has a pair of electrodes formed thereon - a second substrate; a hole passing through the second slab substrate and the pair of electrodes; placing a thermal-polymer film on the pair of electrodes and the dye-absorbing oxidized film and electrically bonding the pair of electrodes and the titanium oxide film An electrode; the electrolyte is injected into the plastic polymer film of the silane and the lyophilized polymer via the Wei hole; and the thermoplastic polymer is sealed. The electro-π 埒掏 埒掏 or p-type semiconductor may be liquid, (9) (gel and gel phase), solid, or the like. The liquefaction reduction electrolyte, the dissolved salt, the electricity, the same value, and the liquid obtained by dissolving the oxygen 1 ^ € η transport material ρ material conductor in the refrigerant and the warm dissolved salt. Condensed form (coagulation and gel phase) 39 200938594 includes a coagulated form obtained by including a redox electrolyte, a dissolved salt, a hole transporting material or a p-type semiconductor in a polymer matrix or a low molecular gelling agent. Solids include redox electrolytes, dissolved salts, hole transport materials, or P-type semiconductors. 5 As for the hole-passing material, an amine derivative or a conductive polymer such as polyacetylene polyaniline, polyseptene or the like may be used, or a material of a discotic liquid crystal phase such as a second type may be used. As the P-type semiconductor, Cul, CuSCN, or the like can be used. It is preferable that the counter electrode 'is a reducing catalytic function having conductivity and a redox electrolyte', for example, by depositing a carbon, a money, a nail, or the like on a glass or a polymer film, or applying a conductive particle. The counter electrode obtained thereon. · As for the redox electrolyte used in the solar cell of the present invention, T* uses an elemental redox electrolyte containing (iv) ions as a counter ion's albating mouth and #素 molecule; a metal redox electrolyte such as a ferrous phase a ferrocyanide or a ferrocene-ferricyanide cation; a metal complex such as a complex complex; an organic redox electrolyte such as a thiol-alkyl disulfide violet pigment, hydrogen brewing, etc. It is preferred to use a dentate redox electrolyte. ❹ ; The dentate molecule contained in the redox electrolyte is preferably a ruthenium molecule. As for the elemental compound containing dentate ions as a counter ion, it is possible to use a functional metal salt such as LiI, bribe, KI, Cai2, Mgi2, Ci^^__, such as Wei Junsi, 破化咪(10), 埃Acridine key or the like can be used 12. When the redox electrolyte is in the form of a solution containing the electrolyte, an electrochemically inert solvent can be used. For example, acetonitrile, carbonic acid extension 40 200938594 propyl ester, ethyl carbonate, 3-methyl 4-indole propionitrile, methoxyacetonitrile, ethylene glycol, propanol, mono-alcohol, diethylene glycol can be used. , butyl vinegar, dimethoxyethane, dimethyl vinegar, 1,3 _ ah, f acid A, 2 - methyl tetrahydrofuran, 3 - methyl ketone - ten final 2, four Azolla, tetrachlorine bitumen, water, etc.; and B5 nitrile, _ propyl vinegar, carbonic acid acetic acid, 3 methoxy propionitrile, ethylene glycol, 3 methoxy can sit -2-_, Or Ding vinegar is better. These solvents may be used singly or in combination. As the gel phase positive electrode, those obtained by including an electrolyte or an electrolyte solution in a polymer matrix or a polymer matrix, or those containing an electrolyte or an electrolyte solution in a powder gelling agent can be used. The concentration of the redox 1 〇 electrolyte is preferably 9 Wt%, and more preferably (1) (4)%. The present invention can be obtained by arranging a light f conversion element (negative electrode) in which a dye is supported on an oxide semiconductor particle on a substrate and a counter electrode (positive electrode) are opposed to each other, and a solution containing a redox electrolyte is filled therein Solar battery. The invention will be described with reference to the following examples, but these examples are intended to be illustrative only, and the scope of the invention is not limited thereto. [Examples] Dye of the dye The quinone dye 20 DCSC 1 (chemical formula 1) and DCSC2 (chemical formula 12) of the present invention were synthesized via the reaction shown in the above Reaction Scheme 1. All the reactions were carried out under argon, and used. The solvent was sodium distilled. As for the starting material 'unpurified aliquot and Aldrich and Strem reagent. Preparation of compound (1) benzyl cyanoacetate (8.4 g, 47.95 mmol) And ammonium acetate (0.709 200938594 g, 9.2 mmol) dissolved in 25 ml of cyclohexane, and slowly added acetic acid (2.5 g, 41.75 mmol) to the mixture. The reaction mixture was stirred for 15 minutes, then 5·methyl- Phenomenon-2-furaldehyde (6.05 g, 47.95 mmol) was added thereto, and the reaction mixture was stirred at ll ° C for 5 hours under nitrogen. After stirring, ammonium acetate (0.709) was added at room temperature 5. The mixture was stirred at ii 〇 ° C for 12 hours, then the organic layer was extracted with 200 ml of ethyl acetate and water and then recrystallized from ethyl acetate. (2) Preparation of compound (2) Compound (2) was prepared by the same method as Compound (1), but using equivalent © 10 Monomolar octyl cyanoacetate in place of cyano-acetic acid benzyl vinegar. (3) Preparation of Compound (3) ", Compound (1) (5 g, 17.6 mmol) and NBS (3.5 g, 19.41 millimoles) was dissolved in 150 ml of tetra-carbonized carbon, then AIBN (〇.H5 g, 0.088 mmol) was added thereto, and the reaction mixture was allowed to act at 8 ° C for 12 hours and 15 hours under nitrogen. The reaction mixture was filtered using a filter paper, the solvent was dried, and then the organic material was extracted with di-methane/water using a separating funnel, and the column was purified (eluent EA: Hx = 1:10) to the isolated compound (2.4 g, 6.61 millimoles) Add 5 ml of P(OEt)3, and the reaction mixture is argonized at 8 Torr under nitrogen for 7 hours. After the flutter, use 250 ml of hexane to remove the starting materials and column. Purified 20 (eluent · MC: acetone = 1:1). (4) Preparation of compound (4) Compound (4) is prepared by the same method as compound (3), but compound (2) is used instead of compound. (1) (5) Preparation of Compound (6) 42 200938594 5 ❹ - 10 15 In the compound (7) (1), gram of grammole and ampule plus (9) gram, ^ mM) THF 20 ML, and compound (3) (〇75 g, 丨8 mmol) were dissolved in 20 mL of THF and slowly added dropwise, then the reaction mixture was stirred at 70 ° C for 12 hours. After the reaction, the solvent was removed and the organic layer was taken to MC. Extraction and separation by recrystallization. (6) Preparation of Compound (7) Compound (7) is produced by the same method as Compound (6), but Compound (4) is used instead of Compound (3). (7) Synthesis of DCSC 1 and DCSC2 Using the prepared compounds 6 and 7, the synthesis method according to Chem. Mater. 2006, 18, 5604-5608 was used to synthesize DCSC 1 (chemical formula 1-1) and DCSC 2 according to the reaction formula 1 (chemical formula 2). Example 2: Synthesis of DCSC 3 (chemical formula u) and DCSC 4 (chemical formula 1-4) using compound 11 and compound 12 or 13 (compound 13 for DCSC 3, compound 12 for DCSC 4), by Chem. Mater · 2006, 18, 5604-5608 'The synthesis method synthesizes DCSC 3 and DCSC 4 according to Reaction Formula 2-1. [Chemical Formula 11]

[Chemical Formula 12] 43 200938594

Cm [Chemical Formula 13]

5 [Reaction formula 2-1]

Example 3: Synthesis of DCSC 9 Hh Compound 1-7) DCSC9 was synthesized according to Reaction Scheme 3. (1) Preparation of Compound (16) Compound (4) (0.3 g, M4 mmol) and CNCH2COOH (0.27 10 g, 3.2 mmol) were dissolved in 25 ml of CH3CN and piperidine (0·5 ml, 0.5 It was added dropwise to the mixture, and then the reaction mixture was refluxed for 5 hours. After completion of the reaction, the compounds were separated by washing three times with 1 mL of CH3CN. (2) Preparation of dye DCSC9 The dye DCSC 9 was synthesized using the synthesis method described in Chem. Mater_ 2006, 44 200938594 18, 5604-5608. Example 4: Synthesis of Dye Compound 1·14Π) Dye Compound 1-14 (1) was synthesized according to the following Reaction Scheme 4-1. [Reaction formula 4-1]

(1) Preparation of 5-(diethylamino) porphin-2-carbaldehyde 5-bromo thiophene-2-methyl (1 ml ' 8.41 mmol) 'diethylamine (2.6 ml, 25.2 mmol) And TsOH (0.048 g, 0.25 mmol) was introduced into the reactor and the reaction mixture was stirred with nitrogen for 24 hours under heating. After stirring, the organic layer was extracted and evaporated with di-methane and water, and then purified by column (eluent E.A: Hx = 1: 2). 1H NMR (CDC13): [ppm] = 0.89 (m, 6H), 3.24 (m, 4H), 6.7 (d, 3JHH = 2.4 Hz, 1H), 7.1 l (d, 3JHH = 2.4Hz, 1H), 9.62 (s, 1H). (2) 5,5,-(lE,l'E)-3,3,-(2,2,-bipyridyl-4,4'-diyl)indole (c_i_) Preparation of ene-3,1-diyl) (Ν, Ν-ethyl phenanthrene-2-amine) 45 200938594 5-(Diethylamino) porphin-2·formaldehyde (〇·44 g, 2·38 millimolar), 2,2,-biacridine-4,4'-diylindole (indenyl)diphosphonic acid tetraethyl ester (0.49 g, 1.13 mmol), and NaH (0_1 The gram of ' 2.48 mmoles was dissolved in 30 mL of THF and the reaction mixture was stirred at reflux under nitrogen for 4 hours. 5 After agitation, the organic layer was extracted with two methane and water and evaporated, then purified by column (eluent E.A). 1H NMR (CDC13): [ppm] = 0.89 (m, 12H), 3.24 (m, 8H), 6.26 (d, 3JHH = 15.4Hz, 2H), ), 6.41 (d, 3JHH = 15.4Hz, 2H), 6.7 (d, 3JHH = 2.4Hz, 2H), 7.01(d, 3JHH = 2.4Hz, 2H), 10 7.31(d, 3JHH= 5.4Hz, 2H), 8.01(s, 2H), 8.31(d, 3JHH = 5.4 Hz, 2H). (3) Preparation of Compound I-I4 (1) Compound 1-14 (1) was synthesized by the synthesis method described in Chem. Mater. 2006, 18, 5604-5608. 15 5,5'_(1E,1' illusion _3,3'<2,2'-bipyridyl-4,4,-diyl) fluorene (prop-1---3,1-diyl) ) bottom (N,N-diethyl porphin-2-amine (〇·26 g, 0.5 mmol), [Ru(p-isopropyltoluene)C12]2 (〇·15 g, 0.25 mmol) Ear), 2,2,-bi-bipyridyl-4,4'-dicarboxylic acid (0.12 g, 0.5 mmol), NH4NCS (0.19 g, 2.5 mmol). Example 5: Dye Compound 1- 14(2) 染料$ Dye Compound 1-14(2) was prepared in the same manner as in Example 3, but the reaction was according to Reaction Scheme 4 (in Reaction Scheme 4, R is a hexyl group). Example 6: Dye Compound 1- 15) The i dye compound 1-15 is prepared according to the reaction formula 5 using the dithiophene 200938594 thiophene prepared by the preparation formula. (1) The synthesized 2-hexyldithieno[2',3'] The porphin (1 gram, 35 65 mM) was dissolved in THF (50 mL) and in _78 it was slowly added with uLi 2 Μ (21 mL). Then the reaction mixture was allowed to run at low temperature for 1 hour. -78 Art in which slowly added trimethyltin chloride 1 Μ (38 ml), the reaction mixture was incubated at low temperature for 1 hour and it was stirred overnight. After 3 minutes, the organic layer was extracted with dioxane and water, evaporated and dried. 1H NMR (CDC13): [ppm] = 〇.4 (s, 9H), 0.88 (m, 3H), 1.29(m, 4H), 1.96(m, 4H), 2.55(m, 2H), 6.62(s, 1H), 6.98(s, 10 1H). (2) 2-Trimethyl (4-hexyldithiophene) And [2,,3,] porphin-2-yl)stannane-(〇_6g' i·34mmol) '4,4'-dibromo-2,2,-bipyridine (0.35g , 1.12 mM) and Pd(PPh3)4 (0_065 g, 0.056 mmol) dissolved in THF (40 mL), and the mixture was refluxed under nitrogen for 8 hr. then the organic layer was extracted with 15 methane and water. , and evaporate, then purify by column (eluent EA:

Hx=l: 2) 〇1H NMR (CDC13): [ppm] = 0.88 (m, 6H), 1.29 (m, 8H), 1.96 (m, 8H), 2.55 (m, 4H), 6.70 (s, 2H) ), 6.98(s, 2H), 7.34(d, 3JHH = 8.8Hz, 2H), 8.18(s, 2H), 8.42(d, 3JHH = 8.8Hz, 2H). 20 (3) The compound synthesized (〇) · 8 g, 1.12 mmol; and [RuC12(p-isopropyltoluene)] 2 (〇.34 g, 0.56 mmol) dissolved in DMF (15 ml), the reaction mixture was viscous at 8 ° C Reflux for 4 hours. Then, 2,2'-bipyridyl-4,4'-dicarboxylic acid (0.27 g, 1.12 mmol) was added, and the reaction mixture was refluxed again at 160 ° C for 4 hours. NH4NCS (0.85 g, 11.2 mmol) and reverse 47 200938594 were added thereto and the mixture was refluxed again at 13 ° C for 4 hours. After the completion of the reaction, the reaction mixture was subjected to vacuum distillation, washed with water and ether, and then filtered to remove the precipitate. The sulphate is dissolved in sterol, and the appropriate TBA 〇H ’ and the sephadex purification (eluent.methanol) are added thereto and then immersed in the chamber and transitioned. The remaining 5 precipitates were washed with water and ether and dried. 1H NMR (CDC13): [ppm] = 〇-88 (m, 6H), 1.29 (m, 8H), 1.96 (m, 8H), 2.55 (m, 4H), 6.70 (s, 2H), 6.98 (s , 2H), 7.34(m, 4H), 8.21(m, 4H), 8.44(m, 4H), 11.4(s, 2H). Example 7: Synthesis of Compound 1-16 ❹ 10 Dye Compound 1-16 The dithienothiophene prepared according to Preparation Scheme 1 was prepared according to Reaction Scheme 6. (1) Preparation of 2-hexyldibenzo[2',3']thiophene 如同 As in Example 4, dithieno[2',3']thiophene (0.37 g, 1.88 mmol) was dissolved in 30 ML was added in THF, and 15 liters (2 mmol) was added thereto at -78 ° C, and then the reaction mixture was stirred for 1 hour. After stirring, 1-bromohexane (0.28 ml, 2 mmol) was added at -78 ° C and the mixture was stirred for an additional hour. After stirring, the organic layer was extracted with dioxane methane and water and evaporated, then purified by column (eluent. M.C.: Hx=l: 2). 1H NMR (CDC13): [ppm] = 0.89 (m, 3H), 1.24 (m, 6H), 20 1.88 (m, 2H), 3.24 (m, 2H), 6.8 (m, 2H), 7.11 (d, 3JHH = 2.4Hz, 1H). (2) Preparation of 2-hexyldiguana[2',3'] porphin _5_furfural 2-hexyl bis-pheno[2',3'] porphin (〇·3g, ι·〇6mmol) dissolved in DMF (10ml) and slowly added P0C13 (〇〇98ml, 丨〇6m48 200938594 Moer)' then the reaction mixture under nitrogen Stir at 80 ° C for 4 hours. After agitation, the organic layer was extracted with two gas and water, evaporated and purified by column (eluent. EA: Hx=l: 2) 1H NMR (CDC13): [ppm] = 0.89 (m, 3H), 1.24(m, 6H), 5 1.88(m, 2H), 3.24(m, 2H), 6.9 (s, 1H), 7.41(s, 1H) 9.61(s, 1H). (3) 5,5'- (lE,1$)-3,3'-(2,2'-linked mouth _4,4'_diyl) 贰(C1-_1_稀-3,1_二基)家(2-hexyl) Preparation of dithieno[2,3,] porphin) 2-hexyl dioxin [2',3'] porphin-5-furfural (0.3 g, 0.97 mmol 10 ears) ' 2,2 '- 咄 咄 -4,4'·diyl fluorene (fluorenylene) tetraethyl bisphosphonate (0.22 g '0.486 mmol) and NaH (0.5 g, 1_2 mmol) dissolved in THF ( 30 ml), the reaction mixture was stirred under nitrogen for 4 hours under reflux. After the transfer, the organic layer was purified by trichloromethane and water extraction and evaporation and purified by column column (eluent. EA) 15 1H R (CDC13): [ppm] = 〇.89 (m, 6H), 1.24(m,12H), 1.88(m,4H), 3.24(m,4H),,6.64(s,2H),), 6.88(d,3JHH = 15.4Hz, 2H), 7.1(s, 2H), 7.29 (d, 3JHH = 15.4 Hz, 2H), 7.31 (d, 3JHH = 5.4 Hz, 2H), 8.01 (s, 2H), 8.31 (d, 3JHH = 5.4 Hz, 2H). (4) Compound 1-16 Preparation 20 Compound 16 was prepared in the same manner as in the synthesis of 1-14 (1) in Example 4. Example 8: 纟·ϋ·料_Sensitized Solar Thunder Pool The solar cell was prepared using a thin titanium dioxide crucible prepared from Dyesol titanium dioxide paste (Australian Waiting Company). The shuttle paste was applied to a ρτ〇 glass substrate, and the glass substrate was pretreated with titanium oxychloride (IV) by a doctor blade method. 49 200938594 The paste on the FTO was sintered at 45 ° C for 30 minutes to form a 13 μm thick titanium dioxide film layer. The sintered film layer was immersed in the dye solution, and DCSC 1 (chemical formula) prepared in Example 1 was dissolved in DMF at a concentration of 0.5 mM' for 24 hours at room temperature. The dye-coated film was immersed in DMF 5 solution for 3 hours to remove unbound dye, and then immersed in an ethanol solution for 3 days to remove DMF. The dye-coated: coated titanium dioxide film is washed with ethanol, and a solar cell is manufactured according to a general solar cell manufacturing method. Wherein the use of 0.05 Μ 12,0.1 M Lil, 〇.6 Μ 1,2-dimethyl-3-hexyl imidazolium iodide and 〇·5 Μ 4-third-butylpyridine in decyloxy 10 propyl A redox electrolyte solution obtained from a nitrile. Examples 9-16 and _1 太阳能 1 solar cells were fabricated in the same manner as in Example 8, but using DCSC 2 (Example 9), DCSC 3 (Example 10), DCSC 4 (Example 11), DCSC 8 (Example 12, respectively) , using chemical formula M6 compound), DCSC 9 (Example 15 I3), Chemical Formula 1-14 (1) Compound (Example 14), Chemical Formula 4 (2) Compound (Example 15), Chemical Formula 1-16 Compound (Example 16) and Ν719 Used as a dye instead of DCSC 1. The photoelectrochemical characteristics, IPCE, absorption spectrum and molar absorption coefficient of the manufactured solar cell were measured, and the results are shown in the figure. The table below shows the absorption peak and the molar absorption coefficient. Table 2 shows Jsc (short-circuit photocurrent density), v〇c (open circuit voltage), FF (fill factor), and photoelectric conversion efficiency (7). The photoelectrochemical properties of the solar cell were determined using a Keithley 236 236 source measurement unit. The measurement unit has a 300 watt xenon lamp equipped with an AM丨5 filter (Oriel) as the light source, 〇.4 χ 〇.4 cm 2 electric 50 200938594 Extreme size and 1 sun (100 mW/cm2) light intensity. Light intensity is controlled using a solar cell. IPCE is measured using a system of PV Measurement Company. The absorption of the dye in the solution and the titanium dioxide film was measured using an HP 8453A diode array spectrophotometer. [Table 1] Dye (£max(l〇4 M^cm'^maxinm) Reference dye ΝΉ9 10260(382) 9810(530) DCSC 1 26700(383) 14130(535) DCSC2 20730(376) 13290(530) DCSC3 34960(441) 22640(533) DCSC4 50070(449) 22500(553) DCSC 8 42150(461) 21350(554) DCSC9 22540(349) 9410(523) As shown in Table 1 and Figure 1, at the entire wavelength, The dyes of the present invention (including Chemical Formula 1-14(1) (Example 14), Chemical Formula 1-14(2) (Example 15), and Chemical Formula 1-16 (Example 16) are not shown) have higher purity than the reference dye N719 The curve indicates a higher molar absorption efficiency and the curve shifts towards a longer wavelength.

10 [Table 2] Dye Jsc (mA/cm2) V〇c(V) FF η(%) Reference dye N719 14.79 687 0.66 6.67 DCSC 1 7.60 626 0.72 3.41 DCSC 2 11.29 630 0.73 5.18 DCSC 3 8.67 618 0.69 3.69 DCSC 4 10.21 654 0.66 4.39 Chemical Formula 1-14 (2) 3.42 565 0.70 1.35 Chemical Formula 1-16 7.02 604 0.72 3.07 As shown in Table 2, the dye of the present invention has a higher curve than N719 at the entire wavelength and has excellent photoelectric conversion efficiency. 51 200938594 Industrial Utilization The novel fluorene dye of the present invention exhibits a significantly improved photoelectric conversion efficiency' to strengthen the bonding force with titanium dioxide and has excellent Jsc (short-circuit photoelectric flow density) and molar absorption coefficient, which greatly improves solar cell efficiency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an absorption line diagram using DCSC 1, DCSC 2, DCSC 3, DCSC 4, DCSC 8, DCSC 9 according to an embodiment of the present invention and N719 according to a comparative example as a dye. [Main component symbol description] (none)

52

Claims (1)

200938594 VII. Patent application scope: 1. An anthraquinone dye represented by the following chemical formula 1: [Chemical Formula 1] X Y ❹ 5 (wherein the ring a may optionally be one or more selected from the group consisting of a halogen atom, a guanamine, a cyano group, a thiol group, a thiol group, a thiol group, a Ci-30 group, and a Ci-30 alkoxy group) Substituent substitution; and X and Y are each methyl or represented by one of the following Chemical Formulas 2-1 to 2-14, and at least one of X and Y is by the following Chemical Formulas 2-1 to 2-14 One of them said: [Chemical Formula 2-1] [Chemical Formula 2-2] 53 200938594 / m [Chemical Formula 2-3] COOH [Chemical Formula 2-4] [Chemical Formula 2-5] [Chemical Formula 2-6] 54 200938594 [Chemical Formula 2-7] [Chemical Formula 2-8] [Chemical Formula 2-9] R* [Chemical Formula 2-10] Ri 55 200938594 R [Chemical Formula 2-12] [Chemical Formula 2-13] Ri η [Chemical Formula 2-14] % η (where (*) represents a bond; ring bl may be selected from a halogen atom as desired], a amine, a guanamine, a cyano group, a thiol group, a nitro group, a fluorenyl group, a c group, and a c group. Substituting one or more substituents in the group consisting of alkoxy groups; eight are s or 0, respectively; and R, R1, and R2AR3 are respectively chlorine, Ci 15 aristocracy, Ci alkoxy, C6 2 fluorenyl or a heteroaryl group; n is an integer from 丨 to )) 2. The quinone dye according to item i of the patent application, wherein the dye is represented by one of the following compounds 1-1 to 1-38: 56 200938594 [Chemical Formula 1-1] [Chemical Formula 1-4] 57 200938594 [Chemical Formula 1-6] 58 200938594 [Chemical Formula 1-8] [Chemical Formula 1-9] 59 5 200938594 [Chemical Formula 1-10] [Chemical Formula 1-11] 60 200938594 HOOC [Chemical Formula 1-12] [Chemical Formula 1-13] 61 200938594 [Chemical Formula 1-14] [Chemical Formula 1-15] 62 200938594 [Chemical Formula 1-16] [Chemical Formula 1-17] 63 200938594 [Chemical Formula 1-18] [Chemical Formula 1-19] 64 200938594 [Chemical Formula 1-20] [Chemical Formula 1-21] 65 200938594 [Chemical Formula 1-22] [Chemical Formula 1-23] 66 200938594 [Chemical Formula 1-25] 67 200938594 [Chemical Formula 1-26] [Chemical Formula 1-27] 68 200938594 [Chemical Formula 1-29] 69 200938594 [Chemical Formula 1-31] 70 200938594 [Chemical Formula 1-32] [Chemical Formula 1-33] 71 200938594 [Chemical Formula 1-34] ❹ [Chemical Formula 1-35] 72 200938594 [Chemical Formula 1-36] [Chemical Formula 1-37] 73 200938594 [Chemical Formula 1-38] (wherein A and R are as defined in Chemical Formula 1). 5 3. A method for producing a dye represented by the following Chemical Formula 1, comprising the steps of: the following chemical formula 3 is sequentially reacted with a compound of the following Chemical Formula 4, Chemical Formula 5, and Chemical Formula 6: [Chemical Formula 3] 74 x200938594 [RuC12 (p-isopropyltoluene)] 2 [Chemical Formula 5] [Numerical Formula 6] nh4ncs (wherein X, Y and al are as defined in the first claim of the patent scope). 10. The method of claim 3, wherein the dye is prepared by one of the following Reaction Formulas 1 to 6: [Reaction Formula 1] Cyclohexane ~ciC COOR mt COOR R=benzyl, octyl Ro<»a SKI Κ*ΒηΟ (7) R = octyl HOOC COOH [RuC12 (p-isopropyltoluene SHJfiCS 75 200938594 [Reaction 2] <r WBS, AIBN ~0<%~*" + (ft Ϊ^ΒβΟ THF 1 n-BnL i 2. DMF .ωι»Ε,!〇 (10) Lib [Reaction formula 3] DCSC$ 76 200938594 [Reaction 4] OHC TsOH reflux 0HQ-trK 2-2' - 吼 吼 -4 4, 4 · - dihydro acid HOOC [Ru (p-iso-two-base) stupid, DS °F, 80 ° C reflux 4 small release 'dimlingt (dimlingt) COQH 160eC Reflux for 4 hours (In Reaction Scheme 4, R is each hydrogen, CM5 alkyl group, CM5 alkoxy group, C6_20 aryl group or C6_2G heteroaryl group) 5 [Reaction formula 5] [Reaction formula 6] 77 200938594 A dye-sensitized photoelectric conversion element comprising a plurality of oxide semiconductor particles, wherein the dye as in the first aspect of the patent application is supported on the oxide semiconductor particles. 5. A dye-sensitized photoelectric conversion element according to claim 5, wherein the dye is supported on the oxide semiconductor particles in the presence of an inclusion compound. 7. The dye-sensitized photoelectric conversion element of claim 5, wherein the oxide semiconductor particles mainly comprise titanium dioxide. 10. The dye-sensitized photoelectric conversion element of claim 5, wherein the semiconductor oxide particles have an average diameter of from 1 to 50 nm. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of claim 5 of the patent application. 10. The dye-sensitized solar cell of claim 9, wherein the dye-sensitized solar cell is prepared by applying a titanium oxide coating to a transparent conductive substrate; Sintering the substrate of the coated layer 78200938594 to form a titanium oxide film; the substrate having the titanium oxide film formed thereon is immersed in the dye represented by the chemical formula 1 dissolved in one of the mixed solutions, thereby forming a dye absorption a titanium oxide film electrode; providing a second glass substrate having a pair of electrodes formed thereon; 5 forming a hole through the second glass substrate and the pair of electrodes; placing a thermoplastic polymer film on the pair of electrodes Interposing the pair of electrodes and the titanium oxide film electrode between the dye-absorbing titanium oxide film electrode and hot pressing; and injecting the electrolyte into the thermoplastic layer between the pair of electrodes and the titanium oxide film electrode via the hole Inside the polymer film; and sealing the thermoplastic, 10-polymer. 〇 79