KR20120042450A - Squaraine dye for dye sensitized solar cell - Google Patents

Abstract

PURPOSE: A squaraine-based dye for dye-sensitized solar battery is provided to collect orthochromatic film light to 780 nm by introducing indole group and pyrrole group, and to have improved short circuit photocurrent density(Jsc), photoelectricity conversion efficiency(η) relative to existing organic pigment, and excellent long time stability. CONSTITUTION: A squaraine-based dye is in chemical formula 1. In chemical formula 1, D is one compound of compounds in chemical formula 2-1, 2-2 and 2-3. In chemical formula 2-1, 2-2 and 2-3, R1 is a compound selected from hydrogen, a C1-6 alkyl group, a C1-6 alkoxy, alkoxyaryl, and a compound in chemical formula 2-4. R2 is C1-5 alkyl group. X is S or O, Y is O or CH2, and K is an integer of 0 or 1. In chemical formula 3, R3 is a C1-6 alkyl group, l and n is an integer of 0-2, and m is an integer of 0 or 1.

Description

Squaraine dye for dye-sensitized solar cell {Squaraine dye for dye sensitized solar cell}

The present invention relates to a squaraine-based dye for a dye-sensitized solar cell, a manufacturing method thereof, a photoelectric conversion element containing a squaraine-based dye, and a solar cell provided with the photoelectric conversion element, and more particularly, to a photovoltaic cell of a dye-sensitized solar cell. To provide a new organic dye for dye-sensitized solar cells to increase the conversion efficiency.

A solar cell refers to a battery in which an internal semiconductor absorbs light and flows current using a photovoltaic effect in which electrons and holes are generated. Conventionally, as a semiconductor of a solar cell, a semiconductor having a diode form by n-p junction of an inorganic material such as silicon or gallium arsenide (GaAs) has been mainly used. However, the inorganic semiconductor has a high energy conversion efficiency and high manufacturing cost, and thus the utilization of the inorganic semiconductor was not sufficient. In order to overcome the problems of the inorganic semiconductor as described above, a technique for replacing the inorganic semiconductor with an organic dye has been proposed.

In general, dyes have a color mainly by absorbing light in the visible light band, and solar cells using the same are called redox (redox), in which organic dyes are separated into electrons and holes and then recombined when they absorb light. ) To generate a current through the reaction. This type of solar cell is called a dye-sensitized solar cell.

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. Unlike conventional silicon solar cells, dye-sensitized solar cells are composed of dye molecules capable of absorbing visible light and generating electron-hole pairs, and photovoltaic solar cells composed mainly of transition metal oxides that transfer generated electrons. It is a battery. As a dye used in dye-sensitized solar cells, ruthenium metal complexes having high photovoltaic conversion efficiency have been widely used, but this ruthenium metal complex has a disadvantage of being too expensive.

Recently, organic dyes containing no metals, which exhibit excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intramolecular charge-transfer (CT) absorption, can replace expensive ruthenium metal complexes. It has been found that it can be used as a battery dye, and research on organic dyes lacking metal has been focused. Organic dyes generally have the structure of electron donor-electron acceptor residues linked by π-binding units. In most organic dyes, amine derivatives act as electron donors, 2-cyanoacrylic acid or rhodanine residues act as electron acceptors, and these two sites are linked to π-binding systems such as metain units or thiophene chains. Is connected by.

In general, structural changes in amine units, which are electron donors, result in changes in electronic properties, for example, absorption spectra shifted towards blue, and by varying π-bond lengths, the absorption spectra and redox potential. Can be adjusted.

However, most of the organic dyes known to date show lower conversion efficiency and lower driving stability compared to ruthenium metal complex dyes, due to the aggregation of dyes on the semiconductor surface and the formation of unstable radical species during the redox reaction cycle. lost. Therefore, efforts to develop new dyes having improved molar absorption coefficient and high photoelectric conversion efficiency compared to existing organic dye compounds by changing the type of electron donor and acceptor or the π-bond length have been continued.

Accordingly, the present inventors have made intensive efforts to develop a solar cell module that can solve the above-described problems in the prior art, and have completed the present invention.

An object of the present invention is to provide a squaraine-based dye for dye-sensitized solar cells and a method for producing the same.

Another object of the present invention is to provide a dye-sensitized photoelectric conversion element and a dye-sensitized solar cell having excellent photoelectric conversion efficiency (η), short circuit photocurrent density (J _sc ), and long-term stability using the dye.

According to one aspect of the invention, there is provided a squaraine-based dye represented by the formula (1).

[Formula 1]

(In Chemical Formula 1, D is any one of compounds represented by Chemical Formulas 2-1 to 2-3, and A is a compound represented by -COOH or Chemical Formula 3 below.)

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

(In Chemical Formulas 2-1 to 2-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)

[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)

(3)

(In Formula 3, R ₃ is a C1-C6 alkyl group, l and n are integers of 0 to 2, m is an integer of 0 or 1.)

According to an embodiment of the present invention, D may be a compound represented by Chemical Formula 2-1.

According to an embodiment of the present invention, A may be -COOH.

According to an embodiment of the present invention, the dye may be a compound represented by the following Chemical Formula 1-1a.

[Formula 1-1a]

According to an embodiment of the present invention, the dye may be a compound represented by the following Chemical Formula 1-1b.

[Formula 1-1b]

According to another aspect of the invention, the compound represented by the following formula (4) is reacted with 1-methyl-2- (trimethylstannyl) -1H-pyrrole (1-methyl-2- (trimethylstannyl) A first step of preparing a compound represented by Formula 5;

[Formula 4]

[Chemical Formula 5]

A second step of preparing a compound represented by Chemical Formula 6 by reacting the compound represented by Chemical Formula 5 with squarylium chloride (squarilyum choride);

[Formula 6]

The compound represented by Formula 6 is 5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium (5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium) and Reacting to prepare a compound represented by Formula 7;

[Formula 7]

(In the above formulas 4 to 7, wherein R ₄ is one of the compounds represented by the formula 8-1 to 8-3.)

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

(In Formulas 8-1 to 8-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)

[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)

Provided is a method for producing a squaraine-based dye comprising a.

According to an embodiment of the present invention, in the preparation method, R ₄ may be a compound represented by Chemical Formula 8-1.

According to an embodiment of the present invention, in the manufacturing method, R ₁ may be characterized in that hydrogen.

According to an embodiment of the present invention, in the preparation method, R ₁ may be a hexyloxy group (OC ₆ H ₁₃ ).

According to still another aspect of the present invention, a dye-sensitized photoelectric conversion device may be provided, including oxide semiconductor fine particles supported by the squaraine-based dye.

According to an embodiment of the present invention, the oxide semiconductor fine particles may be characterized in that the TiO ₂ .

According to another aspect of the present invention, a dye-sensitized solar cell having the dye-sensitized photoelectric conversion element may be provided.

Squalane-based dyes of the present invention can collect the color of light up to 780 nm by introducing indole groups (indole) and pyrrole groups, improved short-circuit photocurrent density (J _sc ), than conventional organic dyes, Photoelectric conversion efficiency? And excellent long-term stability.

1 is an absorption and emission spectrum of the ethanol solution of the dye 1-1a (JK 216) and dye 1-1b (JK 217) prepared in Examples 1 and 2.
FIG. 2 is a schematic diagram showing isodensity surface plots of HOMO and LUMO calculated by DFT / TDDFT calculation of Dye 1-1a (JK 216) prepared in Example 1. FIG.
FIG. 3 is a schematic diagram showing isodensity surface plots of HOMO and LUMO calculated by DFT / TDDFT calculation of Dye 1-1b (JK 217) prepared in Example 2. FIG.
4 is a photocurrent action spectrum of the solar cell of Example 3. FIG.
FIG. 5 shows the short-circuit photocurrent density measured over time while maintaining the DSSC prepared in Example 3 (using electrolyte B) at 60 ° C. under visible-light soaking (AM 15G, 100 mW cm ⁻² ) for 1000 hours. J _sc ), open voltage (V _oc ), fill factor (FF) and photoelectric conversion efficiency (η).

Squalane-based dyes for dye-sensitized solar cells according to the present invention is a compound represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1, D is any one of compounds represented by Chemical Formulas 2-1 to 2-3, and A is a compound represented by -COOH or Chemical Formula 3 below.)

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

(In Chemical Formulas 2-1 to 2-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)

[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)

 (3)

(In Formula 3, R ₃ is a C1-C6 alkyl group, l and n are integers of 0 to 2, m is an integer of 0 or 1.)

In the present invention, the D may act as an electron donor and the A may act as an electron acceptor.

Preferably, in Formula 1, D may be a compound represented by Formula 2-1.

Preferably, in Formula 1, A may be -COOH.

More preferably, the dye may be a compound represented by the following Chemical Formula 1-1a or 1-1b.

[Formula 1-1a]

[Formula 1-1b]

The method for producing a squaraine-based dye for solar cells according to the present invention includes the reaction of the first to third steps described in detail below.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

Squalane-based dye production method of the present invention specifically comprises the following steps.

Representation of the first step to the third step can be represented by the following reaction scheme 1. The compound represented by the following Chemical Formula 4 is reacted with 1-methyl-2- (trimethylstannyl) -1H-pyrrole (1-methyl-2- (trimethylstnnyl) -1H-pyrrole) to prepare a compound represented by the following Chemical Formula 5 The first step to do;

[Formula 4]

[Chemical Formula 5]

A second step of preparing a compound represented by Chemical Formula 6 by reacting the compound represented by Chemical Formula 5 with squarylium chloride;

[Formula 6]

The compound represented by Formula 6 is 5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium (5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium) and Reacting to prepare a compound represented by Formula 7;

[Formula 7]

(In the above formulas 4 to 7, wherein R ₄ is one of the compounds represented by the formula 8-1 to 8-3.)

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

(In Formulas 8-1 to 8-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)

[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)

Representation of the first step to the third step can be represented by the following reaction scheme 1.

Scheme 1

(In Reaction Scheme 1, R ₃ is one of the compounds represented by Formulas 8-1 to 8-3, and A is -COOH or the compound represented by Formula 3.)

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

(In Formulas 8-1 to 8-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)

[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)

The present invention also 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 a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used. The formed thing 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 1? It is preferable that it is 500 nm, More preferably, it is 1? 100 nm is preferred. 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 apply | coating the paste containing microparticles | fine-particles obtained by hydrolyzing a precursor on a board | substrate, it can manufacture by the method of drying, hardening, or baking, etc., The method of apply | coating a paste on a board | substrate is preferable. In this method, the slurry has an average primary particle size of 1? It can obtain by disperse | distributing to 200 nm.

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.

In the present invention, the thickness of the thin film on the substrate is 1? 200 micrometers is suitable, Preferably it is 1? 50 μm. 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. As an 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 alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopro epoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. Examples of the chloride include titanium tetrachloride, tin tetrachloride, zinc chloride and the like, 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 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 × 10 ^-6 M? 1 M is suitable, preferably 1 × 10 ⁻⁵ M? It may be 1 × 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 used by mixing two or more 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, 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, steroid compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and callix 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 device electrode (cathode) and a counter electrode supporting the dye represented by Formula 1 on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.

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.

Examples of the redox electrolyte used in the solar cell of the present invention include a halogen redox electrolyte containing halogen ions as a counter ion and a halogen redox electrolyte composed of halogen molecules, metal complexes such as ferrocyanate, ferrocene-ferricinium ions, and cobalt complexes. Organic redox electrolytes such as metal redox electrolytes, alkylthiol-alkyldisulfides, viologen dyes, hydroquinone-quinones, and the like, and halogen redox 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-methoxypropionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferred. 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 Examples. However, these Examples are only for illustrating the present invention, and the scope of the present invention will not be construed as being limited by these Examples.

Analysis method

All reactions were performed under argon atmosphere and the solvent was distilled off with suitable reagents purchased from Sigma-Aldrich, TCI and Organics. ¹ H spectra and ¹³ C spectra were measured with a Varian Mercury 600 spectrometer. Elemental analysis was performed with a Carlo Elba instrument CHNS-OEA 1108 analyzer, and mass spectra were measured with a JEOL JMS-SX102A instrument. Absorption and photolumonescence spectra were measured with a Perkin-Elmer Lambda 2S UV-visible spectrometer and a Perkins LS fluorescence spectrometer, respectively.

In the embodiment of the present invention was prepared squaraine-based dye in the same manner as in Scheme 2.

Scheme 2

Example  1: 1-1a (dye JK  216 Preparation

1-1. N- (9,9-dimethyl-9H- Fluorene -2-yl) -9,9-dimethyl-N- (4- (5- (1- methyl -1H-pyrrole-2-yl) thiophen-2-yl) Phenyl ) -9H- Fluorene -2- Amine ( 5-1a )of  Produce

N- (4- (5-bromothiophen-2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-flu under nitrogen atmosphere Of oren-2-amine (0.4 g, 0.62 mmol), 1-methyl-2- (trimethylstannyl) -1H-pyrrole (0.17 g, 0.74 mmol) and Pd (PPh ₃ ) ₄ (0.072 g, 0.062 mmol) The mixture was placed in dry toluene (40 ml) and refluxed for 2 days. After cooling to room temperature, the solution was evaporated. The residue was dissolved in methylene chloride and washed twice with distilled water. The organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and separated by silica gel chromatography (eluent, CH ₂ Cl ₂ : hexane = 1: 4) to give the title compound 5-1a .

Melting Point : 113 ℃

MS : m / z 637 [M +]

¹ H NMR ( CDCl ₃ ) : δ 7.65 (d, 2H, ³ J = 7.8 Hz), 7.61 (d, 2H, ³ J = 8.4 Hz), 7.51 (d, 2H, ³ J = 8.4 Hz),, 7.36 (d, 2H, ³ J = 7.2 Hz), 7.32 (t, 2H), 7.28 to 7.23 (m, 4H), 7.20 (d, 1H, ³ J = 3.6 Hz), 7.18 (d, 2H, ³ J = 9.0 Hz), 7.11 (dd, 2H, ³ J = 7.2 Hz), 6.97 (d, 1H, ³ J = 4.2 Hz), 6.71 (m, 1H), 6.36 (m, 1H), 6.17 (m, 1H) , 3.77 (s, 3 H), 1.40 (s, 12 H).

¹³ C NMR ( CDCl ₃ ) : δ 155.3, 153.7, 147.4, 147.2, 139.1, 134.5, 133.8, 128.8, 128.5, 127.5, 127.2, 126.7, 126.5, 125.8, 124.4, 124.1, 123.4, 122.7, 122.6, 120.8, 119.6 , 118.8, 110.5, 108.1, 47.0, 35.6, 27.2.

Theoretical for C ₄₅ H ₃₈ N ₂ S : C, 84.60; H, 6.00. Found : C, 84.35; H, 6.11.

1-2. 3- (5- (5- (4- ( Bis (9,9-dimethyl-9H-fluoren-2-yl) amino ) Phenyl ) Thiophene -2-yl) -1- methyl -1H-pyrrole-2-yl) -4- Hydroxycyclobut -3-yen-1,2- Dion 6-1a )of  Produce

Squarylium chloride (0.047 g, 0.31 mmol) was added to the compound 5-1a in dry Et ₂ O (20 ml), and the mixed solution turned dark yellow and a red precipitate formed. The mixture was stirred at room temperature for 1 hour. The mixture was concentrated to a volume of about 20 ml and then the red precipitate was filtered off with a filter and washed with hexane in the filter, whereupon the emichloride turned to the corresponding emisquaraine. The red precipitate was dissolved in 20 ml of acetone and 0.2 ml of NEt ₃ . After stirring for 6 hours at room temperature, the solvent was removed. The residue was dissolved in methylene chloride and washed twice with distilled water. The organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and separated by silica gel chromatography (eluent, CH ₂ Cl ₂ : methanol = 10: 1) to give the title compound 6-1a .

Melting Point : 153 ℃

MS : m / z 734 [M < + >].

¹ H NMR ( DMSO - d ₆ ) : δ 7.76 (d, 2H, ³ J = 8.4 Hz), 7.74 (d, 2H, ³ J = 8.4 Hz), 7.61 (d, 2H, ³ J = 7.8 Hz), 7.50 (d, 2H, ³ J = 7.2 Hz), 7.45 (d, 1H, ³ J = 4.2 Hz), 7.33 to 7.26 (m, 7H), 7.11 (d, 2H, ³ J = 8.4 Hz), 7.05 ( d, 2H, ³ J = 8.4 Hz), 6.90 (d, 1H, ³ J = 4.2 Hz), 6.45 (d, 1H, ³ J = 4.2 Hz), 4.16 (s, 3H), 1.37 (s, 12H) .

¹³ C NMR ( DMSO - d ₆ ) : δ 194.3, 192.2, 191.1, 155.4, 153.7, 147.5, 147.2, 143.1, 138.7, 135.8, 129.6, 129.2, 128.4, 127.8, 126.7, 126.1, 125.4, 124.4, 124.0, 123.7 , 122.1, 121.6, 121.1, 120.4, 118.8, 111.1, 109.1, 47.2, 35.5, 27.2.

Theoretical for C ₄₉ H ₃₈ N ₂ O ₃ S : C, 80.08; H, 5.21. Found : C, 80.65; H, 5.11.

1-3. (E) -2- (5- (5- (4- ( Bis (9,9-dimethyl-9H-fluoren-2-yl) amino ) Phenyl ) Thiophen-2-yl) -1- methyl -1H-pyrrole-2-yl) -4-((5- Carboxy -3,3-dimethyl-1- Octyl -3H- Indolium -2-yl) methylene) -3- Oxocyclobut -One- Enolate ( 1-1a )of  Produce

Compound 6-1a (0.1 g 0.13 mmol) and 5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium (0.06 g 0.13 mmol) were added to a mixture of 30 ml of benzene and 30 ml of butanol. Melted. The mixture was refluxed for 18 hours with Dean-Stark apparatus. The solvent was partially removed until the product precipitated, and silica gel chromatography (eluent, CH ₂ Cl ₂ : methanol = 10: 1) gave the title compound 1-1a .

Melting Point : 178 ℃

MS : m / z 1031 [M < + >].

¹ H NMR ( DMSO - d ₆ ) : δ 8.14 (s, 1H), 8.04 (d, 1H, ³ J = 8.4 Hz), 7.72 (m, 3H), 7.67 (d, 2H, ³ J = 8.4 Hz) , 7.62 (d, 2H, ³ J = 8.4 Hz), 7.59 (d, 1H, ³ J = 3.6 Hz), 7.56 (d, 1H, ³ J = 3.6 Hz), 7.52 (d, 2H, ³ J = 7.2 Hz), 7.49 (d, 1H, ³ J = 4.2 Hz), 7.35 to 7.27 (m, 6H), 7.12 (d, 2H, ³ J = 8.4 Hz), 7.05 (d, 2H, ³ J = 7.8 Hz) , 6.85 (d, 1H, ³ J = 4.2 Hz), 6.11 (s, 1H), 4.36 (s, 3H), 4.27 (m, 2H), 1.76 (s, 6H), 1.51 (m, 2H), 1.39 (s, 12H), 1.34-1.20 (m, 10H), 0.84 (m, 3H).

¹³ C NMR ( DMSO - d ₆ ) : δ 197.7, 193.9, 181.5, 162.1, 159.1, 158.3, 155.9, 151.7, 148.1, 147.8, 146.6, 145.9, 144.2, 140.3, 139.6, 137.9, 135.4, 134.6, 131.8, 129.9 , 129.6, 128.4, 128.1, 127.6, 125.0, 123.9, 122.1, 121.6, 121.0, 120.7, 119.0, 117.7, 113.1, 110.0, 109.5, 108.1, 54.9, 47.5, 35.7, 33.7, 31.3, 28.9, 27.1, 26.7, 26.0 , 25.1, 22.0, 20.8, 13.9.

Theoretical for C ₆₉ H ₆₅ N ₃ O ₄ S : C, 80.28; H, 6. 35; N, 4.07. Found : C, 79.99; H, 6. 41; N, 4.11.

Example  2: 1-1b (dye JK  217)

2-1. 7- ( Hexyloxy ) -N- (7- ( Hexyloxy ) -9,9-dimethyl-9H- Fluorene 2-yl) -9,9- Dimethyl -N- (4- (5- (1- methyl -1H-pyrrole-2-yl) thiophen-2-yl) Phenyl ) -9H- Fluorene 2-amine ( 5-1b Manufacturing

N- (4- (5-bromothiophen-2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluorene-2 N- (4- (5-bromothiophen-2-yl) phenyl) -7- (hexyloxy) -N- (7- (hexyloxy) -9,9-dimethyl-9H-flu instead of an amine The title compound 5-1b was obtained by the same method as 1-1 of Example 1 using oren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine (0.4 g, 0.48 mmol). .

Melting Point : 96 ℃

MS : m / z 838 [M < + >].

¹ H NMR ( CDCl ₃ ) : δ 7.54 (d, 2H, ³ J = 8.4 Hz), 7.50 (d, 2H, ³ J = 8.4 Hz), 7.48 (d, 2H, ³ J = 9.0 Hz), 7.20 ( s, 2H), 7.19 (d, 1H, ³ J = 4.2 Hz), 7.16 (d, 2H, ³ J = 9.0 Hz), 7.07 (dd, 2H, ³ J = 7.8 Hz), 6.97 (d, 1H, ³ J = 4.2 Hz), 6.93 (s, 2H), 6.86 (dd, 2H, ³ J = 7.8 Hz), 6.70 (m, 1H), 6.36 (m, 1H), 6.17 (m, 1H), 4.01 ( t, 4H), 3.77 (s, 3H), 1.84 (m, 4H), 1.49 (m, 4H), 1.39 (s, 12H), 1.36 (m, 8H), 0.91 (t, 6H).

¹³ C NMR ( CDCl ₃ ) : δ 158.9, 155.6, 154.8, 147.7, 146.2, 134.6, 131.9, 128.0, 126.4, 125.8, 124.3, 123.6, 123.1, 122.5, 122.1, 120.3, 119.8, 119.0, 117.7, 113.1, 110.0 , 109.5, 108.1, 68.5, 47.0, 35.5, 31.8, 29.6, 27.3, 26.0, 22.8, 14.2.

Theoretical for C ₅₇ H ₆₂ N ₂ O ₂ S : C, 81.85; H, 7.45. Found : C, 81.99; H, 7.31.

2-2. 3- (5- (5- (4- ( Vis (7- ( Hexyloxy ) -9,9-dimethyl-9H- Fluorene -2- days) amino) Phenyl ) Thiophen-2-yl) -1- methyl -1H-pyrrole-2-yl) -4- Hydroxycyclobut -3-yen-1,2- Dion 6-1b Manufacturing

The title compound 6-1b was obtained in the same manner as in Example 1-2, using the 5-1b compound instead of the 5-1a compound of Example 1.

Melting Point : 139 ℃

MS : m / z 934 [M < + >].

¹ H NMR ( DMSO - d ₆ ) : δ 7.63 (d, 2H, ³ J = 8.4 Hz), 7.61 (d, 2H, ³ J = 8.4 Hz), 7.58 (d, 2H, ³ J = 7.8 Hz), 7.42 (d, 1H, ³ J = 4.2 Hz), 7.24 (m, 2H), 7.09 (s, 2H), 7.05 (d, 2H, ³ J = 8.4 Hz), 7.00 (d, 2H, ³ J = 8.4 Hz), 6.90 (d, 1H, ³ J = 4.2 Hz), 6.87 (d, 2H, ³ J = 8.4 Hz), 6.44 (d, 1H, ³ J = 4.2 Hz), 4.16 (s, 3H), 3.99 (t, 4H), 1.72 (m, 4H), 1.45 (m, 4H), 1.34 (s, 12H), 1.31 (m, 8H), 0.88 (t, 6H).

¹³ C NMR ( DMSO - d ₆ ) : δ 193.1, 192,5, 191.4, 159.2, 157.4, 157.1, 149.7, 148.8, 136.1, 135.8, 130.7, 128.9, 127.1, 126.3, 124.6, 124.2, 123.6, 122.8, 120.6 , 120.1, 119.4, 118.3, 113.9 111.2, 110.2, 109.2, 68.4, 47.2, 35.8, 31.9, 28.9, 27.5, 26.1, 22.4, 14.3.

Theoretical for C ₆₁ H ₆₂ N ₂ O ₅ S : C, 78.34; H, 6.68. Found: C, 78.01; H, 6.49.

2-3. (E) -2- (5- (5- (4- ( Vis (7- Hexyloxy ) -9,9-dimethyl-9H- Fluorene -2-yl) amino) Phenyl ) Thiophen-2-yl) -1- methyl -1H-pyrrole-2-yl) -4-((5- Carboxy -3,3-dimethyl-1- Octyl -3H-indolium-2-yl) methylene) -3- Oxocyclobut -One- Enolate  ( 1-1b Manufacture).

The title compound 1-1b was obtained by the same method as the Example 1-3, using 6-1b (0.1g 0.08 mmol) compound instead of 6-1a compound of Example 1.

Melting Point : 162 ℃

MS : m / z 1231 [M < + >].

¹ H NMR ( DMSO - d ₆ ) : δ 8.13 (s, 1H), 8.01 (d, 1H, ³ J = 7.2 Hz), 7.65 to 7.62 (m, 7H), 7.59 (m, 1H), 7.54 (m , 1H), 7.47 (d, 1H, ³ J = 4.2 Hz), 7.26 (s, 2H), 7.10 (s, 2H), 7.06 (d, 2H, ³ J = 7.8 Hz), 7.02 (d, 2H, ³ J = 7.8 Hz), 6.88 (d, 2H, ³ J = 9 Hz), 6.85 (d, 1H, ³ J = 4.2 Hz), 6.09 (s, 1H), 4.35 (s, 3H), 4.29 (m , 2H), 4.00 (t, 4H), 1.75 (m, 8H), 1.73 (s, 6H), 1.44 (m, 10H), 1.35 (s, 12H), 1.34-1.23 (m, 10H), 0.89 ( t, 6H), 0.82 (t, 3H).

¹³ C NMR ( DMSO - d ₆ ) : δ 199.1, 195,5, 189.5, 177.3, 171.1, 162.6, 160.8, 159.7, 159.4, 154.3, 149.9, 148.1, 146.3, 145.9, 144.3, 137.1, 136.2, 135.1, 134.3 , 133.6, 128.9, 128.3, 127.2, 126.8, 124.1, 123.7, 123.1, 122.5, 121.5, 121.1, 120.4, 118.1, 114.2, 113.1, 111.8, 110.5, 109.3, 68.4, 54.7, 47.5, 46.1, 35.9, 35.6, 33.2 , 31.9, 31.7, 28.8, 28.1, 27.5, 27.2, 26.1, 25.8, 25.2, 24.8, 22.5, 22.1, 20.1, 13.7, 13.3.

Theoretical for C ₈₁ H ₈₉ N ₃ O ₆ S : C, 78.92; H, 7. 28; N, 3.41. Found : C, 78.77; H, 7. 21; N, 3.29.

Example  3: Manufacture of Dye-Sensitized Solar Cell

FTO glass plates (Pilkington TEC Glass-TEC 8, 2.3 mm thick Solar) were washed in an ultrasonic bath for 30 minutes using a surfactant and then washed with water and ethanol. The FTO glass plate was immersed in an aqueous 40 mM TiCl ₄ solution at 70 ° C. for 30 minutes and then washed with water and ethanol. The transparent nanocrystalline layer on the FTO glass plate was printed on a TiO ₂ paste (Soalronix, Ti-Nanoxide T / SP) using a doctor blade and then dried at 25 ° C. for 2 hours. The TiO ₂ electrode was gradually heated under air flow at 325 ° C. for 5 minutes, at 375 ° C. for 5 minutes, at 450 ° C. for 5 minutes and at 500 ° C. for 15 minutes. The TiO ₂ electrode was further immersed in an aqueous 40 mM TiCl ₄ solution at 30 ° C. for 30 minutes and sintered at 500 ° C. for 30 minutes. The TiO ₂ electrode was then immersed in 1-1a and 1-1b (0.1 mM in ethanol containing 3a, 7a-hydroxy-5b-cholic acid (Cheno)) prepared in Examples 1 and 2 for 24 hours at room temperature. After washing with water, acetone and 0.1M aqueous hydrochloric acid solution in an ultrasonic bath. The counter electrode was prepared by coating a droplet of H ₂ PtCl ₆ solution (2 g of platinum in 1 ml of ethanol) on an FTO plate and heat-treating at 400 ° C. for 15 minutes. Place a hot melt film (Surlyn) as a spacer between the dye-adsorbed TiO2 electrode and the platinum-electrode, and heat it to 80 ° C to assemble a sealed sandwich cell, and then hot melt film and cover glass (0.1 mm thick). The solar cell was manufactured by sealing the hole with).

At this time, two electrolytes (electrolytes A and B) were used for the solar cell. Electrolyte A is 0.6 M 1,2-dimethyl-3-propylimidazolium iodine, 0.05 M iodine, 0.1 M lithium iodide, 0.1 M tert-butylpyridine dissolved in acetonitrile, and electrolyte B is DMII / 1-ethyl-3-methylimidazolium iodine / 1-ethyl-3-methylimidazolium tetracyanoborate / I ₂ / N-butylbenzimidazole / GNCS (molar ratio: 12/12/16 / 1.67 / 3.33 / 0.67).

Test Example  : In the example  Measurement of physical properties of manufactured dyes and batteries

The photoelectrochemical properties, IPCE index, absorbance spectrum, and molar extinction coefficient of the solar cell manufactured in the above example were measured and shown in FIGS. 1, 4, 5, and Table 1.

dyes λ _abs ^a / nm
(ε / M ^-1 cm ^-1 ) E _redox ^b / V E _{0 -0} ^c / V E _LUMO ^d / V J _sc (mAcm ^-2 ) V _oc
(V) FF η ^e
(%) 1-1a
( JK  216) 365 (27,800),
669 (93,400) 1.00 1.72 -0.72 13.92 0.61 0.74 6.29 1-1b
( JK  217) 367 (28,900),
672 (77,900) 0.92 1.68 -0.76 13.73 0.58 0.70 5.54

a: absorption spectrum measured in tetrahydrofuran (THF) solution

b: redox potential versus Fc / Fc ⁺ of a dye on TiO ₂ measured in CH ₃ CN with 0.1 M (nC ₄ H ₉ ) ₄ NPF ₆ at a scan rate of 50 mVs ^-1 (E _ox is the oxidation potential)

c: voltage crossing point between absorption spectrum and emission spectrum in tetrahydrofuran (THF) solution

d: value calculated by E _{ox -} E _{0 -0}

e: Performance of DSSC measured over 0.175 cm ² working area

Electrolyte: 0.6 M DMPImI, 0.05 I ₂ , 0.1 M LiI and 0.1 M TBP dissolved in acetonitrile

1 is an absorption and emission spectrum of the ethanol solution of the dyes 1-1a and 1-1b prepared in Examples 1 and 2. As shown in Figure 1, the absorption spectra of dyes 1-1a are at 669 nm (ε = 93,400 M cm ^-1 ) and 365 nm (ε = 27,800 M cm ^-1 ) due to the π-π ^* transition of the conjugated system. Two maximum absorption bands are shown, and the absorption spectra of dyes 1-1b show two maximum absorption bands at 672 nm (ε = 77,900 M cm ⁻¹ ) and 367 nm (ε = 28,900 M cm ⁻¹ ). When dyes 1-1a and 1-1b were excited in the π-π ^* band, they exhibited strong emission peaks at 764 nm and 788 nm, respectively, and the E _{0 -0} transition energy was measured to be 1.72 and 1.68, respectively. .

Cyclic voltammograms of Dye 1-1a and Dye 1-1b showed semi-reversible oxidation at 1.00 V and 0.92 V, respectively, compared to NHE. These dyes 1-1a and 1-1b are high oxidation potential of the dye I ^- is associated with that drive the oxidation-reduction pair (~ 0.5V) of the regenerated dye-fast ^- / I _3. The excited state oxidation potentials (E ^* _ox ) of 1-1a and 1-1b were -0.72 V and -0.76 V, respectively, compared to NHE, which was more negative than the conduction band of TiO ₂ (conduction band of TiO ₂₎ . : -0.5 V).

DFT / TDDFT calculations were performed to obtain the root cause of electron absorption of the dyes 1-1a and 1-1b prepared in Examples 1 and 2. 2 and 3 show isodensity surface plots of HOMO and LUMO calculated by DFT / TDDFT calculation of dyes 1-1a and 1-1b, respectively.

Figure 4 shows the photocurrent action spectrum of the solar cell in Example 3. The solar cells prepared using dye 1-1a exceeded 50% in the 465 nm to 750 nm spectral range, exhibiting a maximum incident photoelectric conversion efficiency (IPCE) of 60% at 503 nm, and 13.92 mA cm ^{−. The short-circuit} photocurrent density (J _sc ) of 2, the open voltage (V _oc ) of 0.61V, the filling rate (FF) of 0.72, and the conversion efficiency (η) of 6.29% were shown (under AM 1.5 stimulus light illumination). In addition, the low incident intensity (0.12 sun) of the solar cell manufactured using the dye 1-1a showed a power conversion efficiency of 6.73%.

Figure 5 shows the short-circuit photocurrent density (J _sc ), open voltage (V) of the solar cell prepared in Example 3 using electrode B under visible light soaking (AM 15G, 100 mW cm ⁻² ) at 60 ° C. _oc ), filling rate ( ff ), and the change of the photoelectric conversion efficiency ((eta)) were measured and shown with time (▲: 1-1a, ▼: 1-1b). At this time, a 420 nm cut-off filter was placed on the cell surface during illumination. As can be seen in FIG. 5, the cells comprising the dyes 1-1a and 1-1b combined with the ionic liquid electrolyte showed excellent long-term stability in the accelerated light soaking test at 60 ° C. The initial efficiency of the solar cell including the dye 1-1a was 2.24%, and the efficiency increased slightly to 2.50% after 1000 hours of light soaking at 60 ° C. In addition, although the open-circuit voltage (V _oc) of the cell containing the dye 1-1a at 60 ℃ after light soak for 1000 hours is reduced to 96 mV in the rotation stage photocurrent density (J _sc) is 4.39 mA cm ^-2 6.11 mA cm ^- Increased to ² to compensate for the loss of open voltage.

As can be seen from the above results, the squaraine-based near-infrared dye of the present invention exhibits excellent short-circuit photocurrent density (J _sc ), photoelectric conversion efficiency (η) and long-term stability, and can greatly improve the efficiency of solar cells. This property makes it possible to use for solar windows such as green houses or BIPV.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

Squalane-based dyes represented by the formula (1).
[Formula 1]

(In Chemical Formula 1, D is any one of compounds represented by Chemical Formulas 2-1 to 2-3, and A is a compound represented by -COOH or Chemical Formula 3 below.)
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

(In Chemical Formulas 2-1 to 2-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)
[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)
(3)

(In Formula 3, R ₃ is a C1-C6 alkyl group, l and n are integers of 0 to 2, m is an integer of 0 or 1.)
The method of claim 1,
D is a squaraine-based dye, characterized in that the compound represented by the formula (2-1).
The method of claim 1,
A is -COOH squaraine-based dyes, characterized in that.
The method of claim 1,
Squalane-based dye, characterized in that the dye is a compound represented by the formula (1-1a).
[Formula 1-1a]

The method of claim 1,
Squalane-based dye, characterized in that the dye is a compound represented by the formula (1-1b).
[Formula 1-1b]

The compound represented by the following formula (4) is reacted with 1-methyl-2- (trimethylstannyl) -1H-pyrrole (1-methyl-2- (trimethylstannyl) -1H-pyrrole) to prepare a compound represented by the following formula (5). The first step to do;
[Chemical Formula 4]

[Chemical Formula 5]

A second step of preparing a compound represented by Chemical Formula 6 by reacting the compound represented by Chemical Formula 5 with squarylium chloride;
[Formula 6]

The compound represented by Formula 6 is 5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium (5-carboxy-2,3,3-trimethyl-1-octyl-3H-indolium) and Reacting to prepare a compound represented by Formula 7;
[Formula 7]

(In the above formulas 4 to 7, wherein R ₄ is one of the compounds represented by the formula 8-1 to 8-3.)
[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

(In Formulas 8-1 to 8-3, R ₁ is _one of hydrogen, a C1-C6 alkyl group, a C1-C6 alkoxy group, an alkoxyaryl group, or a compound represented by the following Formula 2-4.)
[Formula 2-4]

(In the above formula 2-4, R ₂ is a C1-C5 alkyl group, X is S or O, Y is O or CH ₂ , K is an integer of 0 or 1.)
Method for producing a squaraine-based dye comprising a.
The method of claim 6,
R ₄ is a method for producing a squaraine dye, characterized in that the compound represented by the formula (8-1).
The method of claim 6,
The R ₁ is a method for producing a squaraine dye, characterized in that hydrogen.
The method of claim 6,
Wherein R ₁ is a hexyloxy group (-OC ₆ H ₁₃ ) characterized in that the manufacturing method of squaraine-based dyes.
A dye-sensitized photoelectric conversion element comprising oxide semiconductor fine particles supported by the squaraine-based dye according to any one of claims 1 to 5.
The method of claim 10,
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles are TiO ₂ .
A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device according to claim 11.

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