WO2009096702A2 - Novel organic dye and method for preparing same - Google Patents

Abstract

The present invention relates to a novel organic dye and a method for preparing same. The dye compound of the present invention is used in a dye-sensitized solar cell (DSSC), and improves molar absorptivity, short circuit photocurrent density (Jsc) and photoelectric converting efficiency which significantly enhances the efficiency of the solar cell. The novel organic dye and preparation method therefor according to the present invention allows for refining the process without requiring an expensive column and remarkably reduces costs for dye synthesis.

Description

Novel organic dyes and preparation methods thereof

The present invention relates to a novel dye and a method for manufacturing the same, and more particularly, the molar absorption coefficient, J _sc (single-circuit photocurrent density), which is used in dye-sensitized solar cells (DSSC), is improved compared to conventional dyes. The present invention relates to a novel dye and a method for producing the same, which greatly improve the efficiency of a solar cell by displaying photovoltaic conversion efficiency and can be purified without using an expensive column, thereby significantly lowering the cost of dye synthesis.

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

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 absorption efficiency, redox reaction stability, and intramolecular charge-transfer (CT) -based 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 a 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, the structural change of the amine unit, which is an electron donor, results in a change in the electronic properties, for example, an absorption spectrum shifted toward blue, and by changing the π-bond length, the absorption spectrum 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.

In order to solve the problems of the prior art as described above, the present invention exhibits an improved molar absorption coefficient, J _sc (short circuit photocurrent density) and photovoltaic conversion efficiency than the conventional dyes, which can greatly improve the efficiency of solar cells. And it aims to provide a manufacturing method thereof.

In addition, an object of the present invention is to provide a dye-sensitized photoelectric conversion device having a significantly improved photovoltaic conversion efficiency including the dye, excellent molar absorption coefficient and J _sc (single-circuit photocurrent density), and a solar cell with remarkably improved efficiency. .

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

[Formula 1]

In the formula of Formula 1,

R ₁ is a C ₁ to C ₂₀ alkyl group, C ₆ to C ₃₀ aryl group, heteroaryl group or acyl group,

_{R 2, R 3, R 4} , R 5, R 6, R 7, R 8 and R ₉ are each independently hydrogen, C alkyl group of ₁ ~ C _10, a halide group, an alkoxy group of C ₁ ~ C _10, O A real group, a C ₆ -C ₃₀ aryl group or heteroaryl group,

Ar is a compound containing at least one compound having a heteroatom of a C ₆ ~ C ₃₀ aryl group, a C ₄ ~ C ₃₀ heteroaryl group or an aryl amino group,

Y is hydrogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, halogen atom, amide group, cyano group, hydroxyl group, nitro group or acyl group,

m "is an integer from 1 to 4,

n is an integer from 1 to 7,

A is

,

or

to be

(And in formula of the A, X is hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group or an acyl group, R ₁₀ and R ₁₁ are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group or C ₁ ~ C ₂₀ alkoxy group, m, m 'is an integer of 1 to 4).

In another aspect, the present invention provides a method for producing an acridine dye represented by the formula (1) characterized in that the compound of formula (2) is reacted with the formulas (3) and (4).

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, R _1, R _2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , Ar, Y, m ", n, and A are the same as defined in Formula 1 above. And H ₁ and H ₂ are each independently halogen.

 The present invention provides a chromone dye represented by the following formula (5).

[Formula 5]

In Chemical Formula 5,

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, an alkyl group of C ₁ to C ₂₀ , an acyl group, an aryl group of C ₆ to C ₃₀ , a heteroaryl group, a halide group or Nitrile group,

Y is

or

ego,

Z is a cyclic compound having a heteroatom of an aryl group, heteroaryl group or aryl amino group of C ₅ to C ₃₀ , preferably

,

or

And at least one kind, and when two or more kinds are included, they may be directly connected or connected with an ethylene group therebetween (wherein X is a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, or an acyl group). , A C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group, m is an integer of 0 to 4, n is an integer of 1 to 7),

Ar ₁ is a C ₁ to C ₅₀ alkyl group, C ₁ to C ₅₀ alkoxy group, C ₆ to C ₅₀ aryl group, heteroaryl group or aryl amine group.

In another aspect, the present invention provides a method for producing a chromone dye represented by the formula (5) characterized in that the compound of formula (6) is reacted with the formulas (7) and (8).

[Formula 6]

[Formula 7]

[Formula 8]

Y

In Formulas 6 to 8, Ar _1, Z, and Y are as defined in Formula 5, and H ₁ is halogen.

The present invention also provides a dye-sensitized photoelectric conversion device including the oxide semiconductor fine particles carrying the dye represented by the formula (1) or (5).

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element as an electrode.

The novel dyes of the present invention exhibit improved molar absorption coefficient, J _sc (short circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, which greatly improves the efficiency of solar cells and enables purification without using expensive columns. The cost of dye synthesis can be significantly lowered.

Figure 1 shows an IV curve of the dye prepared in Example 1 which is an embodiment of the present invention,

Figure 2 shows the IV curve of the dye prepared in Example 2 which is an embodiment of the present invention,

Figure 3 shows the IV curve of the dye prepared in Example 4 which is an embodiment of the present invention,

Figure 4 shows the UV absorbance of the dye prepared in Example 4 which is an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The acridine-based dye of the present invention has a specific aliphatic compound as an electron donor, has a thiophene unit or a thienothiophene unit at an intermediate linking portion, and is represented by the following Chemical Formula 1.

[Formula 1]

In the formula of Formula 1,

R ₁ is a C ₁ to C ₂₀ alkyl group, C ₆ to C ₃₀ aryl group, heteroaryl group or acyl group,

R _2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently hydrogen, C ₁ -C ₁₀ alkyl group, halide group, C ₁ -C ₁₀ alkoxy group, a A real group, a C ₆ -C ₃₀ aryl group or heteroaryl group,

Ar is a compound containing at least one compound having a heteroatom of a C ₆ ~ C ₃₀ aryl group, C ₄ ~ C ₃₀ heteroaryl group or aryl amino group,

Y is hydrogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, halogen atom, amide group, cyano group, hydroxyl group, nitro group or acyl group,

m "is an integer from 1 to 4,

n is an integer from 1 to 7,

A is

,

or

to be

(And in formula of the A, X is hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group or an acyl group, R ₁₀ and R ₁₁ are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group or C ₁ ~ C ₂₀ alkoxy group, m, m 'is an integer of 1 to 4).

It is preferable that -Ar (Y _{m "} ) _n -A of Formula 1 is one of the following compounds.

,

,

,

,

,

,

,

,

, or

In the above, A is as defined above.

Preferably, the acridine-based dye represented by Formula 1 is preferably a compound of Formulas 1-1 to 1-8.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

The acridine-based dye represented by Chemical Formula 1 may be prepared by reacting a compound of Chemical Formula 2 with Chemical Formulas 3 and 4.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, R _1, R _2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , Ar, Y, m ", n, and A are the same as defined in Formula 1 above. And H ₁ and H ₂ are each independently halogen.

Preferably, the acridine-based dye represented by Formula 1 may be prepared through any one of Schemes 1 to 3 below.

Scheme 1

Scheme 2

Scheme 3

The chromone dye of the present invention includes a chromone compound by introducing a chromone compound, a specific aliphatic compound as an electron donor, a thiophene unit or a thienothiophene unit at an intermediate linking portion, and a cyanoacrylic acid as an electron acceptor. , It is represented by the following formula (5).

[Formula 5]

In Chemical Formula 5,

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, an alkyl group of C ₁ to C ₂₀ , an acyl group, an aryl group of C ₆ to C ₃₀ , a heteroaryl group, a halide group or Nitrile group,

Y is

or

ego,

Z is a cyclic compound having a heteroatom of an aryl group, heteroaryl group or aryl amino group of C ₅ to C ₃₀ , preferably

,

or

And at least one kind, and when two or more kinds are included, they may be directly connected or connected with an ethylene group therebetween (wherein X is a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, or an acyl group). , A C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group, m is an integer of 0 to 4, n is an integer of 1 to 7),

Ar ₁ is a C ₁ to C ₅₀ alkyl group, C ₁ to C ₅₀ alkoxy group, C ₆ to C ₅₀ aryl group, heteroaryl group or aryl amine group.

Preferably, Ar ₁ -Z of Formula 5 is

, ,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

or

to be.

Also, preferably Ar ₁ of Formula 5 is

,

,

,

,

,

or

to be.

The chromone dye represented by Formula 5 is preferably a compound of Formulas 5-1 to 5-8.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

As described above, the chromone dye of the present invention represented by Chemical Formula 5 may be prepared by reacting a compound of Chemical Formula 6 with Chemical Formulas 7 and 8.

[Formula 6]

[Formula 7]

[Formula 8]

Y

In the general formula 6 to 8 Ar _{1, Z,} Y are as defined in Formula 5, H ₁ is a halogen.

Preferably, the method for preparing the chromone dye is preferably prepared including the process of Scheme 4 or 5.

Scheme 4

Scheme 5

In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) or (5) 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) or (5) of the conventional method of manufacturing a dye-sensitized photoelectric conversion device for a solar cell using a dye can be applied, of course, preferably In the dye-sensitized photoelectric conversion device of the present invention, it is preferable that a thin film of oxide semiconductor is produced on a substrate using oxide semiconductor fine particles, and then the dye of the present invention is supported 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.

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

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

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

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

In the present invention, the thickness of the thin film on the substrate is suitably 1-200 μm, preferably 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. For example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropyl epoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, a specific example, a solution obtained by dissolving a dye represented by the formula (1) or (5) with a solvent that can dissolve, or dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was installed in the dispersion liquid obtained by disperse | distributing 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-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 suitably 1 × 10 ^-6-1 M, preferably 1 × 10 ^-5-1 × 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) or (5) supported in the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, another dye or a metal complex dye can be mixed with the dye of this invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin and the like are preferable, and organic dyes used for mixing are metal-free phthalocyanine, porphyrin or 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. .Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., Vol. 115, p . 6382 (1993). ). In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.

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

After supporting the dye, the surface of the semiconductor electrode 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 addition, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element, the dye-sensitized photoelectric conversion element using the oxide semiconductor fine particles carrying the dye represented by the formula (1) or (5) In addition to using the conventional methods for manufacturing a solar cell using a conventional photoelectric conversion element can be applied, of course, a specific example of the photoelectric conversion element electrode supporting the dye represented by the formula (1) or (5) on the oxide semiconductor fine particles (Cathode), counter electrode (anode), redox electrolyte, hole transport material or p-type semiconductor and the like.

Preferably, one example of a specific method of manufacturing a dye-sensitized solar cell of the present invention is the step of coating a titanium oxide paste on a conductive transparent substrate, baking the substrate coated with a paste to form a titanium oxide thin film, titanium oxide thin film Impregnating the formed substrate into a mixed solution in which the dye represented by Formula 1 or Formula 5 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and having a second glass substrate having a counter electrode formed thereon. Forming a hole through the second glass 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; Bonding a pole and a titanium oxide film electrode, and thermoplasticizing between the counter electrode and the titanium oxide film electrode through the hole It can be prepared through the step of injecting an electrolyte into the polymer film and the step of sealing the thermoplastic polymer.

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

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

As the redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen redox-based electrolytes are preferable. As a halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecules, an iodine molecule is preferable. 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; Organic ammonium salts of halogen such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine; Or you can use the I _2.

In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of a gel positive electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01-99% by weight, more preferably 0.1-30% 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, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

The dye was synthesized through the procedure of Scheme 1.

 (One). Preparation of Compound (3) in Scheme 1

 Compound (6) 10-butyl-9- (3 ', 4-dihexyl-2,2'-bithiophen-5-yl) -10,10a-dihydroacridine (1.5 g, 2.63 mmol) dissolved in THF (40 ml) After n-BuLi (1.57 ml, 3.15 mmol) was slowly added dropwise and stirred under nitrogen gas for 1 hour, and then triisopropylborate (0.72 ml, 3.15 mmol) was added thereto, followed by low temperature stirring at -78 ℃ nitrogen for 1 hour at 0 ° C. HCl 2 M (5 ml) was added thereto, followed by further stirring for 30 minutes.

After stirring, the organic layer was extracted with Methylenechloride and water, dried through evaporation and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 2.32 (br, s, 2H), 3.69 (m , 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.72 (s, 1H), 7.11 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8 Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H).

 (2). Preparation of Compound (4)

 Compound (3) 5 '-(10-butyl-10,10a-dihydroacridin-9-yl) -3,4'-dihexyl-2,2'-bithiophen-5-ylboronic acid (2.94 g, 4.8 mmol), 2- (5- bromothieno [3,2-b] thiophen-2-yl) -5,5-dimethyl-1,3-dioxane (1.6 g, 4.8 mmol), tetrakis- (tripheneylphos-phine) palladium (0) (0.27 g, 0.24 mmol) Potassium carbonate (1.99 g, 14.4 mmol) was added thereto, dissolved in THF (60 ml), and stirred under reflux for 12 hours under nitrogen gas.

After stirring, the organic layer was extracted with Methylenechloride and water, dried through evaporation and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.80 (s, 6H), 0.88 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H) ), 3.64 (d, 3JHH = 10.8 Hz, 2H), 3.69 (m, 4H), 3.76 (d, 3JHH = 10.8 Hz, 2H), 3.86 (m, 2H), 5.02 (s, 1H), 5.68 (s , 1H), 6.72 (s, 1H), 7.11 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H).

 (3). Preparation of Compound (5)

Compound (4 ) 10-butyl-9- (5 '-(5- (5,5-dimethyl-1,3-dioxan-2-yl) thieno [3,2-b] thiophen-2-yl)- 3 ', 4-dihexyl-2,2'-bithiophen-5-yl) -10,10a-dihydroacridine (2.28 g, 2.78 mmol) dissolved in THF (30 ml) and then trifluoroacetic acid (10 ml), Water (1 ml ) Was added dropwise and stirred for 4 hours under a nitrogen atmosphere.

After stirring, the organic layer was extracted with Methylenechloride and water, and then evaporated and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H) , 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.72 (s, 1H), 7.12 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8 Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H), 10.28 (s, 1H).

 (4). Preparation of the Final Dye

 Compound (5) 5- (5 '-(10-butyl-10,10a-dihydroacridin-9-yl) -3,4'-dihexyl-2,2'-bithiophen-5-yl) thieno [3,2] -b] thiophene-2-carbaldehyde (0.4 g, 0.73 mmol), Cyanoacetic acid (0.074 g, 0.87 mmol) and Piperidine (0.19 ml, 1.9 mmol) were dissolved in Acetonitrile (30 ml) and stirred under reflux for 4 hours. .

After stirring, the organic layer was extracted with Methylenechloride and water, dried through evaporation and column purified. (Eluent. EA: MeOH = 1: 5) 1H NMR (CDCl ₃ ): [ppm] = 1H NMR (CDCl3 ): [ppm] = 0.88 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 ( m, 4H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.72 (s, 1H), 7.12 (s, 1H), 7.82 (m, 2H), 8.42 (m , 2H), 8.62 (d, 3JHH = 8 Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H), 11.28 (s, 1H).

Example 2

The dye was synthesized through the process of Scheme 2.

 (One). Preparation of Compound (6) in Scheme 2

 Compound 9- (5-bromo-3-hexylthiophen-2-yl) -10-butyl-10,10a-dihydroacridine (2.03 g, 4.2 mmol), 3-hexylthiophen-2-ylboronic acid (0.89 g, 4.2 mmol), Tetrakis- (tripheneylp-hosphine) palladium (0) (0.24 g, 0.21 mmol) was added Potassium carbonate (1.71 g, 12.6 mmol), dissolved in THF (40 ml), and stirred under reflux for 12 hours under nitrogen gas.

After stirring, the organic layer was extracted with Methylenechloride and water, and then evaporated and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H) , 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.72 (s, 1H), 6.94 (d, 3JHH = 2.4Hz, 1H), 7.09 (d, 3JHH = 2.4Hz, 1H), 7.82 (m, 2H), 8.42 (m, 2H ), 8.62 (d, 3JHH = 8 Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H).

 (2). Preparation of Compound (7)

 Compound (6) 10-butyl-9- (3 ', 4-dihexyl-2,2'-bithiophen-5-yl) -10,10a-dihydroacridine (1.5 g, 2.63 mmol) in THF (40 ml) After melting, n-BuLi (1.57 ml, 3.15 mmol) was slowly added dropwise and stirred for 1 hour under nitrogen gas, followed by DMF (0.24 ml, 3.15 mmol), followed by low temperature stirring at -78 ° C. for 1 hour at 0 ° C. The mixture was further stirred for 30 minutes.

After stirring, the organic layer was extracted with Methylenechloride and water, dried through evaporation and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.86 (m, 2H) ), 5.02 (s, 1H), 6.72 (s, 1H), 7.11 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 ( d, 3JHH = 9.2 Hz, 2H), 10.24 (s, 1H).

 (3). Preparation of the Final Dye

 Compound (7) 5 '-(10-butyl-10,10a-dihydroacridin-9-yl) -3,4'-dihexyl-2,2'-bithiophene-5-carbaldehyde (1.02 g, 1.7 mmol), Cyanoacetic Acid (0.17 g, 2.04 mmol) and Piperidine (0.44 ml, 4.44 mmol) were dissolved in Acetonitrile (40 ml) and stirred under reflux for 4 hours.

After stirring, the organic layer was extracted with Methylenechloride and water and evaporated, followed by column purification. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H) , 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.73 (s, 1H), 7.12 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 (d, 3 JHH = 9.2 Hz, 2H), 11.24 (s, 1H).

Example 3

The dye was synthesized through the process of Scheme 3.

 (One). Preparation of Compound (9) in Scheme 3

9- (5-bromo-3-hexylthiophen-2-yl) -10-butyl-10,10'-dihydroacridine (2.15 g, 4.8 mmol) and 2- (5-bromothieno) as the compound (3) of Example 1 [3,2-b] thiophen-2-yl) -5,5-dimethyl-1,3-dioxane (1.6 g, 4.8 mmol), tetrakis- (tripheneylphos-phine) palladium (0) (0.27 g, 0.24 mmol ) Potassium carbonate (1.99 g, 14.4 mmol) was added thereto, dissolved in THF (60 ml), and stirred under reflux for 12 hours under nitrogen gas.

After stirring, the organic layer was extracted with Methylenechloride and water, dried through evaporation and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.80 (s, 6H), 0.88 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.64 (d, 3JHH = 10.8 Hz, 2H), 3.69 (m, 4H), 3.76 (d, 3 JHH = 10.8 Hz, 2H), 3.86 (m, 2H), 5.02 (s, 1H), 5.68 (s, 1H), 6.70 (s , 1H), 6.96 (s, 1H), 7.08 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H).

 (2). Preparation of Compound (10)

 The compound (9) 10-butyl-9- (5- (5- (5,5-dimethyl-1,3-dioxan-2-yl) thieno [3,2-b] thiophen-2-yl) -3-hexylthiophen-2- After dissolving yl) -10,10a-dihydroacridine (1.2 g, 1.83 mmol) in THF (40 ml), Trifluoroacetic acid (10 ml) and Water (1 ml) were added dropwise and stirred under nitrogen atmosphere for 4 hours.

After stirring, the organic layer was extracted with Methylenechloride and water, and then evaporated and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H) , 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.70 (s, 1H), 6.96 (s, 1H), 7.08 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H), (s, 10.24).

 (3). Preparation of the Final Dye

 Compound (10) 5- (5- (10-butyl-10,10a-dihydroacridin-9-yl) -4-hexylthiophen-2-yl) thieno [3,2-b] thiophene-2-carbaldehyde (0.8 g , 1.4 mmol), Cyanoacetic acid (0.14 g, 1.68 mmol) and Piperidine (0.36 ml, 3.7 mmol) were dissolved in Acetonitrile (30 ml) and stirred under reflux for 4 hours.

After stirring, the organic layer was extracted with Methylenechloride and water, and then evaporated and column purified. (Eluent. EA: MeOH = 5: 1) 1H NMR (CDCl ₃ ): [ppm] = 0.88 (m, 3H) , 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m, 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.70 (s, 1H), 6.96 (s, 1H), 7.08 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, 3JHH = 8Hz, 2H), 8.81 (d, 3JHH = 9.2 Hz, 2H), (s, 11.25).

Example 4

The dye was synthesized through the procedure of Scheme 4.

 (1) Preparation of Compound (1) in Scheme 4

(4-Bromo-phenyl) -bis- (9,9-dimethyl-9H-fluoren-2-yl) -amine (0.98 g, 1.76 mmol), 3-hexylthiophen-2-yl-boronic acid ( 0.37 g, 1.76 mmol), tetrakis- (triphenylphosphine) palladium (0) (0.1 g, 0.088 mmol) and potassium carbonate (0.73 g, 5.28 mmol) were added and dissolved in DMF (40 mL). It was stirred under reflux for 12 hours.

After stirring, the organic layer was extracted with methylene chloride and water, evaporated and purified by column. (Eluent.M.C: Hx = 1: 5)-> methylene chloride: hexane = 1: 5

¹ H NMR (CDCl ₃ ): [ppm] = 0.89 (m, 3H), 1.29 (m, 4H), 1.52 (m, 4H), 2.52 (m, 2H), 1.47 (s, 12H), 6.7 (d , ³ J _HH = 2.4 Hz, 1H), 6.91 (d, ³ J _HH = 2.4 Hz, 1H), 7.09 (m, 4H), 7.31 (m, 4H), 7.38 (m, 4H), 7.58 (d, ³ J _HH = 11.6 Hz, 2H), 7.62. (M, 4H).

(2) Preparation of Compound (2) in Scheme 4

N- (9,9-dimethyl-9H-fluoren-2-yl) -N- (4- (3-hexylthiophen-2-yl) phenyl) -9,9-dimethyl prepared in (1) above. -9H-fluorene-2-amine (2.08 g, 3.2 mmol) and NBS (0.69 g, 3.87 mmol) were dissolved in THF (30 mL) and stirred under nitrogen atmosphere for 4 hours.

After stirring, the organic layer was extracted with methylene chloride and water, evaporated and purified by column (eluent. M.C: Hx = 1: 5).

¹ H NMR (CDCl ³ ): [ppm] = 0.89 (m, 3H), 1.29 (m, 4H), 1.47 (s, 12H), 1.52 (m, 4H), 2.52 (m, 2H), 6.93 (s , 1H), 7.09 (m, 4H), 7.31 (m, 4H), 7.38 (m, 4H), 7.58 (d, 3JHH = 11.6 Hz, 2H), 7.62. (M, 4H)

(3) Preparation of Compound (3) in Scheme 4

N- (4- (5-bromo-3-hexylthiophen-2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl)-produced in the above (2) 9,9-dimethyl-9H-fluoren-2-amine (1.53 g, 2.11 mmol), 3-hexylthiophen-2-yl-boronic acid (0.45 g, 2.11 mmol), tetrakis- (triphenylphosphine Palladium (0) (0.12 g, 0.1 mmol) and potassium carbonate (0.87 g, 6.33 mmol) were added thereto, dissolved in THF (40 mL), and the mixture was stirred under reflux for 12 hours under nitrogen gas.

After stirring, the organic layer was extracted with methylene chloride and water, evaporated and purified by column (eluent. M.C: Hx = 1: 5).

¹ H NMR (CDCl ³ ): [ppm] = 0.89 (m, 6H), 1.29 (m, 8H), 1.47 (s, 12H), 1.52 (m, 8H), 2.52 (m, 4H), 6.82 (s , 1H), 6.94 (d, 3JHH = 2.4 Hz, 1H), 7.09 (m, 5H), 7.31 (m, 4H), 7.38 (m, 4H), 7.58 (d, 3JHH = 11.6 Hz, 2H), 7.62 . (m, 4H)

(4) Preparation of Compound (4) in Scheme 4

In the same manner as in (2), N- (4- (5'-bromo-3 ', 4-dihexyl-2,2'-bithiophen-5-yl) phenyl) -N- (9,9- Dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine was prepared and purified, and then the N- (4- (5'-bromo-3 ', 4 -Dihexyl-2,2'-bithiophen-5-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluorene-2 -Amine (1.2 g, 1.34 mmol) was dissolved in THF (40 mL). Then, n-butyllithium (0.8 mL, 1.6 mmol) was slowly added dropwise at −78 ° C., stirred at low temperature under nitrogen gas for 1 hour, and then triisopropylborate (0.37 mL, 1.6 mmol) was added thereto. After stirring under nitrogen at −78 ° C. for an hour, the mixture was further stirred at 0 ° C. for 30 minutes. 1 M hydrochloric acid (3 ml) was added dropwise and stirred for 1 hour, followed by extracting the organic layer with methylene chloride and water, evaporating and purifying the column (eluent. EA: MeOH = 5: 1).

¹ H NMR (CDCl ³ ): [ppm] = 0.89 (m, 6H), 1.29 (m, 8H), 1.47 (s, 12H), 1.52 (m, 8H), 2.07 (br, s, 2H), 2.52 (m, 4H), 6.82 (s, 1H), 7.09 (m, 5H), 7.31 (m, 4H), 7.38 (m, 4H), 7.58 (d, 3JHH = 11.6 Hz, 2H), 7.62. (m , 4)

(5) Preparation of Compound (5) in Scheme 4

5 '-(4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -3,4'-dihexyl-2,2'-bite prepared in the above (4) Offen-5-yl-boronic acid (1.02 g, 1.19 mmol), 6-bromo-4H-chromen-4-one (0.267 g, 1.19 mmol), tetrakis- (triphenylphosphine) palladium (0 ) (0.068 g, 0.06 mmol) and potassium carbonate (0.49 g, 3.57 mmol) were dissolved in THF (30 mL), and the mixture was stirred under reflux for 12 hours under nitrogen gas.

After stirring, the organic layer was extracted using methylene chloride and water, evaporated and purified by column (eluent. M.C: Hx = 1: 2).

(6) Preparation of Compound (6) in Scheme 4

6- (5 '-(4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -3,4'-dihexyl-2 prepared in (5) above; 2'-bithiophen-5-yl) -4H-chromen-4-one (0.8 g, 0.84 mmol), cyanoacetic acid (0.84 g, 1 mmol) and piperidine (0.21 mL, 2.2 mmol) It was dissolved in nitrile (30 mL) and stirred under reflux for 4 hours.

After stirring, the organic layer was extracted with methylene chloride and water, evaporated, and purified by column (eluent. EA: MeOH = 5: 1).

Example 5

The dye was synthesized through the process of Scheme 5.

 (1) Preparation of Compound (7) in Scheme 5

Dissolve 10-butylacridin-9 (10H) -one (1.72 g, 6.84 mmol) in THF (50 mL) and slowly add dropwise 2 M n-butyllithium (4.1 mL, 8.2 mmol) at -78 ° C. After stirring under nitrogen gas for 1 hour, 2-bromo-3-hexylthiophene (2.03 g, 8.2 mmol) was added thereto, stirred for 1 hour under nitrogen at -78 ° C, and further stirred at 0 ° C for 30 minutes. Stirred.

After stirring, put the chloride (II) (1.55 g, 8.2 mmol) dissolved in 2 M hydrochloric acid (5 ml), stir at room temperature for 1 hour, and then extract the organic layer using methylene chloride and water. After evaporation the column was purified (eluent. MeOH: EA = 1: 5).

¹ H NMR (CDCl ₃ ): [ppm] = 1.05 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m , 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.51 (s, 1H), 6.98 (m, 2H), 7.94 (d, ³ J _HH = 10.8 Hz, 2H), 8.41 (d, ³ J _HH = 12.4 Hz, 2H), 8.59 (m, 4H).

 (2) Preparation of Compound (8) in Scheme 5

10-butyl-9- (3-hexylthiopan-2-yl) -10,10a-dihydroacridine (1.78 g, 4.41 mmol) and NBS (0.94 g, 5.29 mmol) prepared in (1) above. Was dissolved in THF (40 mL) and stirred under nitrogen gas at room temperature for 4 hours. Then, the organic layer was extracted with methylene chloride and water, evaporated and column purified (eluent. MeOH: EA = 1: 5).

¹ H NMR (CDCl ₃ ): [ppm] = 1.05 (m, 3H), 1.24 (m, 5H), 1.67 (m, 2H), 1.72 (m, 2H), 1.80 (m, 2H), 1.91 (m) , 2H), 3.69 (m, 4H), 3.86 (m, 2H), 5.02 (s, 1H), 6.96 (s, 1H), 7.82 (m, 2H), 8.42 (m, 2H), 8.62 (d, ³ J _HH = 8 Hz, 2H), 8.81 (d, ³ J _HH = 9.2 Hz, 2H)

 (3) Preparation of Compound (9) in Scheme 5

9- (5-bromo-3-hexylthiophen-2-yl) -10-butyl-10,10a-dihydroacridine (1.52 g, 3.15 mmol) prepared in the above (2) was treated with THF (40 ML), and n-butyllithium (1.89 mL, 3.78 mmol) was slowly added dropwise at -78 ° C and stirred under nitrogen gas for 1 hour. Triisopropyl borate (0.87 mL, 3.78 mmol) was added thereto, and the mixture was stirred for 1 hour under a nitrogen state of −78 ° C., followed by further stirring at 0 ° C. for 30 minutes. 1M hydrochloric acid (4 mL) was added dropwise and stirred for 1 hour, followed by extracting and evaporating the organic layer using methylene chloride and water (eluent. EA: MeOH = 5: 1).

 (4) Preparation of Compound (10) in Scheme 5

5- (10-Butyl-10,10a-dihydroacridin-9-yl) -4-hexylthiophen-2-yl-boronic acid (1.02 g, 2.27 mmol) prepared in (3) above, 6 Bromo-4H-chromen-4-one (0.51 g, 2.27 mmol), tetrakis- (triphenylphosphine) palladium (0) (0.13 g, 0.11 mmol) and potassium carbonate (0.94 g, 6.81 mmol) After dissolving in THF (40 mL) and refluxed under nitrogen gas for 12 hours and stirred.

After stirring, the organic layer was extracted using methylene chloride and water, evaporated and purified by column (eluent. EA: MeOH = 5: 1).

 (5) Preparation of Compound (11) in Scheme 5

6- (5- (10-butyl-10,10a-dihydroacridin-9-yl) -4-hexylthiophen-2-yl) -4H-chromen-4- prepared in the above (4) Warm (0.8 g, 1.46 mmol), cyanoacetic acid (0.15 g, 1.76 mmol) and piperidine (0.38 mL, 3.87 mmol) were dissolved in acetonitrile (40 mL) and stirred under reflux for 4 hours.

After stirring, the organic layer was extracted using methylene chloride and water, evaporated and purified by column (eluent. EA: MeOH = 5: 1).

 Example 6 Manufacture of Dye-Sensitized Solar Cell

In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using a 13 + 10 μm TiO ₂ transparent layer. The washed FTO (Pilkington, 8 μsq ⁻¹ ) glass substrate was impregnated in 40 mM TiCl ₄ aqueous solution. TiO ₂ paste (Solaronix, 13 nm anatase) was screen printed to produce a 13 μm thick first TiO ₂ layer, and another 10 μm thick TiO ₂ scattering layer with another paste (CCIC, HWP-400) for light scattering Was prepared. This TiO ₂ electrode was impregnated with a solution of each of the dye compounds of the present invention prepared in Example 1-5 (0.3 mM dye in 10 mM 3a, 7a-dihydroxy-5b-cholic acid containing ethanol) and at room temperature It was left for 18 hours.

The counter electrode was prepared by coating a H ₂ PtCl ₆ solution (2 mg Pt in 1 mL ethanol) on an FTO substrate. Then, an electrolyte in which 0.6M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04MI ₂ , 0.025M LiI, 0.05M guanidium thiocyanate and 0.28M tert -butylpyridine was dissolved in acetonitrile was obtained. Was injected into a dye-sensitized solar cell.

Example 7

The physical properties of the solar cell manufactured in Example 6 were measured and shown in Table 1 and FIGS. 1 to 4.

Table 1

	Voc (V)	Isc (I)	Jsc (mA / cm 2 )	Fill Factor (%)	Test device area (cm 2 )	efficiency (%)
Example 1	0.53	4.35	1.61	77.41	0.27	0.66
Example 2	0.66	9.86	3.65	77.21	0.27	1.78
Example 4	0.54	2.54	9.61	71.50	0.264	3.71

1 to 3 show IV curves of the dyes prepared in Examples 1, 2 and 4, respectively, and FIG. 4 shows UV absorbance of the dyes prepared in Example 4.

As can be seen from the above results, the novel dye of the present invention exhibits excellent molar absorption coefficient, J _sc (short circuit photocurrent density) and photoelectric conversion efficiency, and thus can be usefully used as a dye for solar cells, without using expensive columns. Purification is possible, which can significantly lower the cost of dye synthesis.

The novel dyes of the present invention exhibit improved molar absorption coefficient, J _sc (short circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, which greatly improves the efficiency of solar cells and enables purification without using expensive columns. The cost of dye synthesis can be significantly lowered.

Claims (17)

1. Acridine-based dyes represented by Formula 1 below:

   [Formula 1]

   

   In the formula of Formula 1,

   R ₁ is a C ₁ to C ₂₀ alkyl group, C ₆ to C ₃₀ aryl group, heteroaryl group or acyl group,

   R _2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently hydrogen, C ₁ -C ₁₀ alkyl group, halide group, C ₁ -C ₁₀ alkoxy group, a A real group, a C ₆ -C ₃₀ aryl group or heteroaryl group,

   Ar is a compound comprising C ₆ ~ C ₃₀ aryl group, C ₄ ~ C over a ₃₀ heteroaryl group, or a compound having a hetero atom (heteroatom) of the aryl group of one kind,

   Y is hydrogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, halogen atom, amide group, cyano group, hydroxyl group, nitro group or acyl group,

   m "is an integer from 1 to 4,

   n is an integer from 1 to 7,

   A is

   

   ,

   

   or

   

   to be

   (And in formula of the A, X is hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group or an acyl group, R ₁₀ and R ₁₁ are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group or C ₁ ~ C ₂₀ alkoxy group, m, m 'is an integer of 1 to 4).
2. The method of claim 1,

   An acridine-based dye, wherein Ar (Y _{m ″} ) _n -A of Formula 1 is one of the following compounds:

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   , or

   

   In the above, A is as defined in formula (1).
3. The method of claim 1,

   Acridine-based dye, characterized in that the dye is one of the compounds represented by the formula 1-1 to 1-8:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   [Formula 1-4]

   

   [Formula 1-5]

   

   [Formula 1-6]

   

   [Formula 1-7]

   

   [Formula 1-8]

   
4. A method for preparing an acridine-based dye represented by Formula 1, comprising reacting a compound of Formula 2 with Formulas 3 and 4 below:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   In Formulas 2 to 4, R _1, R _2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , Ar, Y, m ", n, and A are the same as defined in Formula 1 above. And H ₁ and H ₂ are each independently halogen.
5. The method of claim 4, wherein

   Method for producing a dye of the acridine-based dye represented by the formula (1), characterized in that any one of the following schemes 1-3.

   Scheme 1

   

   Scheme 2

   

   Scheme 3

   
6. A chromone dye represented by the following formula (5):

   [Formula 5]

   

   In Chemical Formula 5,

   R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, an alkyl group of C ₁ to C ₂₀ , an acyl group, an aryl group of C ₆ to C ₃₀ , a heteroaryl group, a halide group or Nitrile group,

   Y is or

   Z is a cyclic compound having a hetero atom (heteroatom) of the aryl group, a heteroaryl group or an aryl group of C ₅ ~ C _30,

   Ar ₁ is C ₁ ~ C ₅₀ alkyl group in the alkoxy group, C ₁ ~ C ₅₀ of, C ₆ ~ is an aryl group, a heteroaryl group or an arylamine group of C _50.
7. The method of claim 6,

   Z in Chemical Formula 5

   

   ,

   

   or

   

   And at least one, and when two or more are included, they are directly connected or connected through an ethylene group (wherein X represents a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, an acyl group, and a C group). _And an alkyl group of ₁ to C ₁₀ or an alkoxy group of C ₁ to C ₁₀ , m is an integer of 0 to 4, and n is an integer of 1 to 7).
8. The method of claim 6,

   Ar ₁ -Z of Formula 5 is

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   or

   

   A chromone dye characterized by the above-mentioned.
9. The method of claim 6,

   Ar ₁ of Formula 5 is

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   , or

   

   A chromone dye characterized by the above-mentioned.
10. The method of claim 6,

    Chromon-based dye, characterized in that the dye is one of the compounds represented by the formula 5-1 to 5-8:

    [Formula 5-1]

    

    [Formula 5-2]

    

    [Formula 5-3]

    

    [Formula 5-4]

    

    [Formula 5-5]

    

    [Formula 5-6]

    

    [Formula 5-7]

    

    [Formula 5-8]

    
11. A method for preparing a chromone dye represented by Formula 5, comprising reacting a compound of Formula 6 with Formulas 7 and 8 below:

    [Formula 6]

    

    [Formula 7]

    

    [Formula 8]

    Y

    In the general formula 6 to 8 Ar _{1, Z,} Y are as defined in Formula 5, H ₁ is a halogen.
12. The method of claim 11,

    Method for preparing the dye is a method for producing a chromone dye represented by the formula (5), characterized in that any one of Schemes 4 to 5.

    Scheme 4

    

    Scheme 5

    
13. A dye-sensitized photoelectric conversion element comprising oxide semiconductor fine particles carrying the dye of claim 1 or 6.
14. The method of claim 13,

    A dye-sensitized photoelectric conversion device characterized in that an acridine-based dye is supported on the oxide semiconductor fine particles in the presence of an inclusion compound.
15. The method of claim 13,

    Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide as an essential component.
16. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device of claim 13 as an electrode.
17. The method of claim 16,

    Wherein the dye-sensitized solar cell, coating the titanium oxide paste on a conductive transparent substrate, firing the substrate coated with the paste to form a titanium oxide thin film, the substrate on which the titanium oxide thin film is formed Impregnating the mixed solution in which the dye is dissolved to form a titanium oxide film electrode to which the dye is adsorbed, providing a second glass substrate having a counter electrode formed thereon, a hole penetrating the second glass substrate and the counter electrode forming a hole, placing a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode on which the dye is adsorbed, and performing a heat compression process to bond the counter electrode and the titanium oxide film electrode to each other; Injecting an electrolyte into the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode, and the heat The dye-sensitized solar cell, characterized in that is produced through the step of sealing the plastic polymer.

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