KR101175207B1 - Organic Dye and Dye-Sensitized Solar Cell - Google Patents

Organic Dye and Dye-Sensitized Solar Cell Download PDF

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KR101175207B1
KR101175207B1 KR1020100046638A KR20100046638A KR101175207B1 KR 101175207 B1 KR101175207 B1 KR 101175207B1 KR 1020100046638 A KR1020100046638 A KR 1020100046638A KR 20100046638 A KR20100046638 A KR 20100046638A KR 101175207 B1 KR101175207 B1 KR 101175207B1
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carbon atoms
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dye
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제종태
정성욱
김시인
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에스에프씨 주식회사
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Abstract

The present invention can provide an organic dye having excellent light absorption and photoelectric conversion efficiency and a dye-sensitized solar cell thereof.

Description

Organic dyes and dye-sensitized solar cells using the same {Organic Dye and Dye-Sensitized Solar Cell}

The present invention relates to an organic dye and a dye-sensitized solar cell using the same.

In general, a representative example of a dye-sensitized solar cell has been published by Gratzel et al., Switzerland. Dyes used in dye-sensitized solar cells can be broadly classified into organometallic dyes and organic dyes depending on the presence or absence of organometallics. Organic dyes require high light absorption and broad absorption wavelength characteristics.

The first object of the present invention is to provide an organic dye having a high light absorption and an absorption band at a long wavelength.

In addition, a second problem to be solved by the present invention is to provide a dye-sensitized solar cell having improved properties by employing this organic dye.

The present invention provides an organic dye represented by one of the following formula.

Figure 112012009525873-pat00001
,
Figure 112012009525873-pat00002

In addition, the present invention provides a dye-sensitized solar cell comprising an organic dye represented by the above formula.

The present invention can provide an organic dye having excellent light absorption and photoelectric conversion efficiency and a dye-sensitized solar cell thereof.

1 is a view showing a dye-sensitized solar cell according to an embodiment of the present invention.
Description of the Related Art
101: first electrode 102: light absorption layer
103: electrolyte layer 104: second electrode

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In describing the embodiments of the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In describing the components of the embodiment of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

The present invention provides an organic dye represented by one of the following Chemical Formulas 1-2.

Figure 112010031942329-pat00003

Figure 112010031942329-pat00004

Where

M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from H 2 O, —Cl, —I, —CN, —NCO and —NCS, and R 1 and R 2 are Each independently selected from CN, COOH, a substituted or unsubstituted hetero group, and a hetero aryl group.

A 1 and A 2 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated form ) Is an anchoring group selected from and wherein at least one of A 1 and A 2 is the anchoring group.

Formula 1 to 2 may be implemented in the form of the following formula (3).

Figure 112010031942329-pat00005

In the above formula

M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 3 and R 4 are each independently CN , COOH, substituted or unsubstituted hetero group, hetero aryl group. R 5 and R 6 are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, Th is each independently

Figure 112010031942329-pat00006
And
Figure 112010031942329-pat00007
Is a functional group selected from m, n and o are integers of 1-4.

Formula 1 to 2 may be implemented in the form of the following formula (4).

Figure 112010031942329-pat00008

In the above formula

M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 7 and R 8 are substituted or unsubstituted An alkyl group having 1 to 20 carbon atoms. In addition, Th is each independently

Figure 112010031942329-pat00009
And
Figure 112010031942329-pat00010
Is a functional group selected from m, n and o are integers of 1-4.

A 1 and A 2 are selected from substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated forms Is an anchoring group, and at least one of A 1 and A 2 is the anchoring group.

Formula 1 to 2 may be implemented in the form of the following formula (5).

Figure 112010031942329-pat00011

In the above formula

M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 9 and R 10 are each independently CN , COOH, substituted or unsubstituted hetero group and hetero aryl group. R 11 and R 12 are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, Th is each independently

Figure 112010031942329-pat00012
And
Figure 112010031942329-pat00013
Is a functional group selected from m, n and o are integers of 1-4.

Formula 1 to 2 may be implemented in the form of the following formula (6).

Figure 112010031942329-pat00014

In the above formula

M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from H 2 O, —Cl, —I, —CN, —NCO and —NCS, and R 11 and R 12 are It is a substituted or unsubstituted C1-C20 alkyl group. In addition, Th is each independently

Figure 112010031942329-pat00015
And
Figure 112010031942329-pat00016
Is a functional group selected from m, n and o are integers of 1-4.

A 1 and A 2 are selected from substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated forms Is an anchoring group, and at least one of A 1 and A 2 is the anchoring group.

Substituted or unsubstituted hetero group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in Formulas 1 to 6 In the case of a substituent, a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a C1-C10 alkylsilyl group, a C1-C40 alkyl group, a C1-C40 alkoxy group, a C1-C40 alkylamino group , An aryl group having 6 to 40 carbon atoms, an aryloxy group having 6 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, or a heteroaryl group having 3 to 40 carbon atoms. .

In addition, in Chemical Formulas 1 to 6, A 1 and A 2, at least one terminal group of the COO -, PO 3 2-, PO 4 2-, SO 3 2-, SO 4 2-, and CONHO - is one of the anions selected from the group consisting of, wherein the terminal group is It may form a salt with one cation selected from the group consisting of ammonium, phosphonium, sulfonium, imidazolium, pyrrolidoneium and pyridinium.

As an embodiment of the present invention, Chemical Formulas 1 to 6 may be implemented in the form of any one compound selected from the group represented by the following Chemical Formulas 7 to 58. In this case, Chemical Formulas 7 to 58 may not be included in Chemical Formulas 1 to 6.

Figure 112010031942329-pat00017

Figure 112010031942329-pat00018

Figure 112010031942329-pat00019

Figure 112010031942329-pat00020

Figure 112010031942329-pat00021

Figure 112010031942329-pat00022

Figure 112010031942329-pat00023

Figure 112010031942329-pat00024

Figure 112010031942329-pat00025

Figure 112010031942329-pat00026

Figure 112010031942329-pat00027

Figure 112010031942329-pat00028

Figure 112010031942329-pat00029

Figure 112010031942329-pat00030

Figure 112010031942329-pat00031

Figure 112010031942329-pat00032

Figure 112010031942329-pat00033

Figure 112010031942329-pat00034

Figure 112010031942329-pat00035

Figure 112010031942329-pat00036

Figure 112010031942329-pat00037

Figure 112010031942329-pat00038

Figure 112010031942329-pat00039

Figure 112010031942329-pat00040

Figure 112010031942329-pat00041

Figure 112010031942329-pat00042

Figure 112010031942329-pat00043

Figure 112010031942329-pat00044

Figure 112010031942329-pat00045

Figure 112010031942329-pat00046

Figure 112010031942329-pat00047

Figure 112010031942329-pat00048

Figure 112010031942329-pat00049

Figure 112010031942329-pat00050

Figure 112010031942329-pat00051

Figure 112010031942329-pat00052

Figure 112010031942329-pat00053

Figure 112010031942329-pat00054

Figure 112010031942329-pat00055

Figure 112010031942329-pat00056

Figure 112010031942329-pat00057

Figure 112010031942329-pat00058

Figure 112010031942329-pat00059

Figure 112010031942329-pat00060

Figure 112010031942329-pat00061

Figure 112010031942329-pat00062

Figure 112010031942329-pat00063

Figure 112010031942329-pat00064

Figure 112010031942329-pat00065

Figure 112010031942329-pat00066

Figure 112010031942329-pat00067

Figure 112010031942329-pat00068

Unlike silicon solar cells, dye-sensitized solar cells are composed of photosensitive dye molecules capable of absorbing visible light to form electron-hole pairs, and transition metal oxides for transferring generated electrons. It is a photoelectrochemical solar cell. Since the photoelectric conversion efficiency of the dye-sensitized solar cell is proportional to the amount of electrons generated by the absorption of sunlight, in order to increase the efficiency, the production of electrons is increased by increasing the absorption of sunlight or increasing the amount of dye adsorption, Alternatively, the efficiency can be increased by preventing the generated exciton from being dissipated by electron-hole recombination.

In order to achieve higher light absorption, the researchers developed a photosensitive organic dye having one or more branched molecules represented by Chemical Formulas 1 to 6 in a simple one-dimensional linear photosensitive organic dye.

Hereinafter, the dye-sensitized solar cell using the organic dye represented by Chemical Formulas 1 to 6 will be described by way of example, but the organic dye is not limited thereto. For example, this organic dye may be used in photodiodes or optical sensors.

1 is a view showing a laminated structure of a dye-sensitized solar cell according to an embodiment of the present invention.

In the dye-sensitized solar cell according to the exemplary embodiment of the present invention, the first electrode 101, the light absorbing layer 102 formed on one surface of the first electrode 101, and the first electrode formed with the light absorbing layer 102 ( The second electrode 104 is disposed to face 101, and an electrolyte 103 interposed in a space between the first electrode 101 and the second electrode 104.

The first electrode 101 is one of two electrodes of the solar cell, and may be a conductive substrate.

The surface of the first electrode 101 may be conductive. The first electrode 101 may be formed of a conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony on a surface of a glass or transparent polymer material, or a metal thin film such as steel, silver, or gold.

The light absorbing layer 102 includes a porous oxide semiconductor particulate film prepared on the first electrode 101 and an organic dye adsorbed on the oxide semiconductor particulate film.

The porous oxide semiconductor fine particle film is formed on the conductive substrate 101 as fine particles of the oxide semiconductor, and the oxide semiconductor fine particle film specifically includes oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium. Can be used. The porous oxide semiconductor fine particle film may be used alone, or may be mixed or coated on the surface of a semiconductor. In addition, the fine particles of the porous oxide semiconductor may be 1-500nm as the average particle diameter, may be used by mixing a large particle size and a small particle size, or may be used in a multi-layer. When the porous oxide semiconductor fine particle film is formed of a multilayer, the porosity of the porous oxide semiconductor film having a small particle size on the first first electrode 101 is made 0-10% as follows to form a recombination blocking layer, and electron recombination blocking. A large particle size porous oxide semiconductor film layer having a porosity of 40-60% is formed on the layer.

Porous oxide semiconductor fine particle film formation can be prepared by applying a paste containing semiconductor fine particles on the first electrode 101, followed by drying, curing and baking. In this method, the paste containing the semiconductor is dispersed in various solvents such as water and ethanol to form a slurry and applied onto the substrate. The substrate coated with the slurry is fired at 400-600 ° C. for about 4 hours. In the dye-sensitized solar cell according to an embodiment of the present invention, the thickness of the porous oxide semiconductor particulate film on the substrate may be 1-2,000 nm, or may be 1-500 nm.

The photosensitive organic dye represented by Chemical Formulas 1 to 4 is adsorbed to the formed semiconductor fine film. The method of adsorbing the photosensitive organic dye represented by Chemical Formulas 1 to 4 on the semiconductor particulate film is not particularly limited, but specifically, a solution or dye obtained by dissolving the compound represented by Chemical Formulas 1 to 4 with a solvent capable of dissolving it. A method of adsorbing a dye by supporting the oxide semiconductor fine particle film in a dispersion obtained by dispersing the resin may be used.

At this time, the concentration of the dye used in the solution or dispersion may be used to suitably match the characteristics of the dye. In addition, the time required to adsorb the dye to the porous oxide after supporting the semiconductor fine particle film is about 1 hour to 48 hours. The solvent used to dissolve or disperse the dye may be ethanol, water, acetonitrile, acetone, dimethylformaldehyde and the like, but is not limited thereto.

The second electrode 104 is formed to face the first electrode 101 and includes the same or similar conductive electrode and conductive layer as the first electrode 101. The conductive layer may be made of carbon black, carbon material such as carbon nanotubes, or platinum. One or both of the first electrode 101 and the second electrode 104 may be transparent.

The electrolyte layer 103 is sealed by a partition wall interposed between the first electrode 101 and the second electrode 104. Examples of the redox electrolyte used in the electrolyte layer 103 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 may be halogen redox electrolytes. It may also be an iodine molecule. As a halogen compound having halogen ions as a counter ion, halogenated metal salts such as LiI, NaI, KI, CaI 2 , CuI or organic ammonium salts of halogen such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, or I 2 Can be used.

Specific examples of the electrolyte layer 103 are as follows, but are not limited thereto.

The electrolyte layer 103 is an iodine-based redox liquid electrolyte such as 1-vinyl-3-hexyl-imidazolium iodide (1-vinyl-3-hexyl-3-immidazolium iodide), and 0.1 M LiI. with electrolyte solution in the - and I 3 was dissolved in 40 mM of I2 (Iodine), a third-butylpyridine (tert-butyl pyridine) 3-methoxy-propionitrile (3-methoxypropionitrile) of 0.2M - / I Can be done.

Example

Hereinafter, the present invention will be described in more detail through synthesis and experimental examples. However, the following synthesis examples and experimental examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  1. Chemical Formula 27  Dye Manufacturing

[Scheme 1]

Figure 112010031942329-pat00069

Referring to Scheme 1, the synthesis examples of the compound described in Formula 27 are as follows.

Preparation of the compound of 1-1; 25 g (0.13 mol) of phenanthroline was added to a 5 L round bottom flask, 13 g of potassium hydroxide was added thereto, dissolved in 1.3 L of water, and then stirred at 90 ° C. for 2 hours. 65 g of potassium permanganate was dissolved in 1 L of warm water and stirred at reflux for 3 hours. After filtering to hot state, the temperature was lowered to room temperature and the solid was filtered to obtain 5.3 g (yield 23%) of intermediate (1-1).

Preparation of compounds of 1-2; 15 g (0.03 mol) of (1-Int) and 5.3 g of Intermediate (1-1) were added to a 5 L round bottom flask, and the mixture was dissolved in 250 mL of tetrahydrofuran. 22 mL of butyllithium was slowly added at -78 ° C and stirred at -78 ° C for 3 hours. 25mL of water was added, and the produced solid was filtered and washed with methanol. 7g (yield 62%) of intermediates (1-2) were obtained.

Preparation of compounds of 1-3; 50 mL into a dichloro (p- cymene) ruthenium (II) dimer (dichloro (p -cymene) ruthenium (II) dimer) 1g To a round bottom flask in 10mL DMF was dissolved. At this time, it blocks the light. 1.2 g of intermediates (1-2) were added to the solution and stirred at 80 ° C for 4 hours. 1.1 g of iBu 2 dcbpy was added to the solution and stirred at 140 ° C. for 4 hours. 7 g of NH 4 NCS was added to the solution and stirred at 140 ° C. for 4 hours. After cooling the reaction solution to room temperature, the reaction solution is removed under reduced pressure, and excess water is added to filter the solid formed. The filtered solid was washed with excess water and ethanol and separated by column chromatography to obtain the intermediate (1-3), 1g (yield 32%).

The preparation of compound 27; Place intermediate (1-3) in a 50 mL round bottom flask and dissolve with 20 mL of acetonitrile. 2 g of tetra-n-butylammonium hydroxide was added thereto, followed by stirring at room temperature for 12 hours. The solvent was concentrated under reduced pressure, dissolved in methanol to pH 2 with nitric acid, and the resulting solid was filtered to yield 0.6 g (70%) of compound 27.

Example  2. Preparation of Dye Containing Formula 28

[Scheme 2]

Figure 112010031942329-pat00070

Referring to Scheme 2, the synthesis examples of the compound described in Formula 28 are as follows.

Preparation of the compound of 2-1; 25 g (0.13 mol) of phenanthroline was added to a 5 L round bottom flask, 13 g of potassium hydroxide was added thereto, dissolved in 1.3 L of water, and then stirred at 90 ° C. for 2 hours. 65 g of potassium permanganate was dissolved in 1 L of warm water and stirred at reflux for 3 hours. After filtering to hot state, the temperature was lowered to room temperature and the solid was filtered to obtain 5.3 g (yield 23%) of intermediate (2-1).

Preparation of the compound of 2-2; 15 g (0.03 mol) of (2-Int) and 5.3 g of Intermediate (2-1) were added to a 5 L round bottom flask, and dissolved in 250 mL of tetrahydrofuran. 22 mL of butyllithium was slowly added at -78 ° C and stirred at -78 ° C for 3 hours. 25mL of water was added, and the produced solid was filtered and washed with methanol. 7 g (yield 62%) of intermediates (2-2) were obtained.

Preparation of the compound of 2-3; 50 mL dichloro (p- cymene) ruthenium (II) dimer to a round bottom flask (dichloro (p -cymene) ruthenium (II) dimer) is dissolved into a 5g in 10mL DMF. At this time, it blocks the light. 1.2 g of intermediates (2-2) were added to this solution, and the mixture was stirred at 80 ° C for 4 hours. 1.1 g of iBu 2 dcbpy was added to the solution and stirred at 140 ° C. for 4 hours. 7 g of NH 4 NCS was added to the solution and stirred at 140 ° C. for 4 hours. After cooling the reaction solution to room temperature, the reaction solution is removed under reduced pressure, and excess water is added to filter the solid formed. The filtered solid was washed with excess water and ethanol and separated by column chromatography to obtain the intermediate (2-3), 1g (yield 32%).

The preparation of compound 28; Place intermediate (2-3) in a 50 mL round bottom flask and dissolve with 20 mL of acetonitrile. 2 g of tetra-n-butylammonium hydroxide was added thereto, followed by stirring at room temperature for 12 hours. The solvent was concentrated under reduced pressure, dissolved in methanol to pH 2 with nitric acid, and the resulting solid was filtered to yield 0.6 g (70%) of compound 28.

Example  3. Preparation of Dye Containing Formula 25

Scheme 3

Figure 112010031942329-pat00071

Referring to Scheme 3, the synthesis example of the compound described in Formula 25 is as follows.

Preparation of 3-1; 25 g (0.13 mol) of phenanthroline was added to a 5 L round bottom flask, 13 g of potassium hydroxide was added thereto, dissolved in 1.3 L of water, and then stirred at 90 ° C. for 2 hours. 65 g of potassium permanganate was dissolved in 1 L of warm water and stirred at reflux for 3 hours. After filtering to hot state, the temperature was lowered to room temperature and the solid was filtered to obtain 5.3 g (yield 23%) of intermediate (3-1).

Preparation of 3-2; In a 100 mL round bottom flask, intermediate (3-1), 5.3 g (0.03 mol), cyanoacetic acid 3.7 g (0.04 mol) and piperidine 2.5 g (0.03 mol) were added and dissolved in 53 mL of acetonitrile. It was stirred at reflux for 6 hours. After cooling the solution to room temperature, the solvent was concentrated under reduced pressure, 50mL of water was added and extracted with dichloromethane. The organic layer is separated to remove moisture, and the solvent is removed by distillation under reduced pressure. After column separation, intermediate (3-2) and 4 g (yield 55%) were obtained.

Preparation of 3-3; 250 mL round bottom flask dichloro (p- cymene) is dissolved into a ruthenium (II) dimer (dichloro (p -cymene) ruthenium (II) dimer) 5g in 100mL DMF. At this time, it blocks the light. 4 g of intermediates (3-2) were added to the solution and stirred at 80 ° C for 4 hours. 5.8 g of iBu 2 dcbpy was added to the solution and stirred at 140 ° C. for 4 hours. 37 g of NH 4 NCS was added to the solution and stirred at 140 ° C. for 4 hours. After cooling the reaction solution to room temperature, the reaction solution is removed under reduced pressure, and excess water is added to filter the solid formed. The filtered solid was washed with excess water and ethanol and separated by column chromatography to obtain the intermediate (3-3), 4g (30% yield).

The preparation of compound 25; Place intermediate (3-3) in a 1 L round bottom flask and dissolve with 400 mL of acetonitrile. 25 g of tetra-n-butylammonium hydroxide was added thereto, followed by stirring at room temperature for 12 hours. The solvent was concentrated under reduced pressure, dissolved in methanol to pH 2 with nitric acid, and the resulting solid was filtered to yield 25 g (30%) of compound 25.

Example  4. Manufacture of Dye-Sensitized Solar Cell

For comparative experiments on the light conversion efficiency, a method for manufacturing a dye-sensitized solar cell is described as follows. The manufacturing method disclosed below should be included in the solar cell manufacturing method disclosed by the present invention without limiting or changing the solar cell manufacturing method already mentioned in the detailed description.

(Formation of First Electrode and Light Absorption Layer)

A titanium oxide dispersion having a particle size of about 5 to 15 nm was coated on an indium-doped tin oxide transparent conductor in a 1 cm 2 area using a doctor blade method, and a porous porous titanium oxide thick film having a thickness of 18 μm was formed through a heat treatment baking process at 450 ° C. for 30 minutes. Produced. After maintaining the specimen at 80 ° C., the compounds represented by the above-described formulas (27), (28) and (5) were immersed in a 0.3 mM dye dispersion dissolved in ethanol, and the dye adsorption treatment was performed for 12 hours or more. After the dye-adsorbed porous titanium oxide thick film was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorption layer.

(Formation of Second Electrode)

As a second electrode, a layer of platinum (Pt) was deposited to a thickness of about 200 nm using a sputter on an indium doped tin oxide transparent conductor. For injection of the electrolyte, a second hole was manufactured by making a minute hole using a 0.75 mm diameter drill.

(Formation of electrolyte layer between the first electrode and the second electrode including the light absorption layer)

The two electrodes were bonded by pressing a 60 μm-thick thermoplastic polymer film between the first electrode and the second electrode for 9 seconds at 100 ° C. A redox electrolyte was injected through the micropores formed in the second electrode, and a dye-sensitized solar cell was manufactured by sealing the micropores using a cover glass and a thermoplastic polymer film. The redox electrolyte used was 0.62M 1,2-dimethyl-3-hexylimidazolium iodide (1,2-dimethyl-3-hexylimidazolium iodide), 0.5M 2-aminopyrimidine (2- aminopyrimidine), 0.1 M LiI and 0.05 M I 2 dissolved in an acetonitrile solvent were used.

Comparative example

As a comparative example, the dye-sensitized solar cell was manufactured in the same manner as in Examples 1 to 3 except that N719 (Formula 59), which is generally well known instead of the organometallic dye, was used. N719 is a ruthenium-based dye commonly used in conventional dye-sensitized solar cells.

Figure 112010031942329-pat00072

Comparative Experimental Example

In order to measure the light conversion efficiency of the dye-sensitized solar cells according to Examples 1 to 3 and Comparative Examples of the present invention, the photovoltage and photocurrent were measured. Xenon lamp (Oriel, 01193) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was standard solar cell (Frunhofer Institute Solare Engeries systeme, Certificate No. C-ISE369, Type of material: Mono-Si). + KG filter). Table 1 shows the light conversion efficiency according to the following equation 1 from the measured photocurrent voltage curve.

Figure 112010031942329-pat00073

In Equation 1, eta denotes the optical conversion efficiency, Jsc denotes the current density, Voc denotes the voltage, FF denotes the fill factor, and Pinc denotes 100mw / cm 2 (1 sun).

Absorption wavelength mole Extinction coefficient Jsc Of mA cm -2 Voc / V Fill Factor Efficiency /% Abs max [ nm ] ε [M -One cm -One ] Formula 25 580 64,000 1420 0.81 0.67 7.70 Formula 27 540 63,700 1440 0.80 0.66 7.60 Formula 28 574 62,200 1410 0.77 0.68 7.38 N719 524 57,000 1390 0.74 0.64 6.58

As can be seen from Table 1, the compounds used in Examples 1 to 3 of the present invention had a maximum absorption wavelength shifted to a longer wavelength than an organometallic complex using a conventional bipyridine derivative as a ligand, and a molar absorption coefficient. It was found that it showed an excellent light conversion efficiency.

As described above, according to the present invention, there is provided a photosensitive organometallic dye having a large molar absorption coefficient and exhibiting excellent light conversion efficiency, and the dye-sensitized solar cell using the organometallic dye has excellent light absorption and photoelectric conversion efficiency. Effect.

The terms "comprise", "comprise" or "having" described above mean that a corresponding component may be included, unless otherwise stated, and thus, excludes other components. It should be construed that it may further include other components. All terms, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Terms commonly used, such as terms defined in a dictionary, should be interpreted to coincide with the contextual meaning of the related art, and shall not be construed in an ideal or excessively formal sense unless explicitly defined in the present invention.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (13)

An organometallic dye represented by one of the following chemical formulas.
Figure 112012009525873-pat00074
(Formula 1),
Figure 112012009525873-pat00075
(2)
M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 1 and R 2 are each independently CN , COOH, substituted or unsubstituted hetero group and hetero aryl group.
A 1 and A 2 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated form ) Is an anchoring group selected from and wherein at least one of A 1 and A 2 is the anchoring group.
The method of claim 1,
An organometallic dye represented by the following formula.
Figure 112012009525873-pat00076
(Formula 3)
In the above formula
M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 3 and R 4 are each independently CN , COOH, substituted or unsubstituted hetero group and hetero aryl group. R 5 and R 6 are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, Th is each independently
Figure 112012009525873-pat00077
And
Figure 112012009525873-pat00078
Is a functional group selected from m, n and o are integers of 1-4.
The method of claim 1,
An organometallic dye represented by the following formula.
Figure 112012009525873-pat00079
(Formula 4)
In the above formula
M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 7 and R 8 are substituted or unsubstituted An alkyl group having 1 to 20 carbon atoms. In addition, Th is each independently
Figure 112012009525873-pat00080
And
Figure 112012009525873-pat00081
Is a functional group selected from m, n and o are integers of 1-4.
A 1 and A 2 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated form ) Is an anchoring group selected from and wherein at least one of A 1 and A 2 is the anchoring group.
The method of claim 1,
An organometallic dye represented by the following formula.
Figure 112012009525873-pat00082
(Formula 5)
In the above formula
M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 9 and R 10 are each independently CN , COOH, substituted or unsubstituted hetero group, hetero aryl group. R 11 and R 12 are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, Th is each independently
Figure 112012009525873-pat00083
And
Figure 112012009525873-pat00084
Is a functional group selected from m, n and o are integers of 1-4. The method of claim 1,
An organometallic dye represented by the following formula.
Figure 112012009525873-pat00085
(Formula 6)
In the above formula
M is a metal selected from Ru, Os and Fe, L 1 and L 2 are each independently selected from -Cl, -I, -CN, -NCO and -NCS, and R 11 and R 12 are substituted or unsubstituted An alkyl group having 1 to 20 carbon atoms. In addition, Th is each independently
Figure 112012009525873-pat00086
And
Figure 112012009525873-pat00087
Is a functional group selected from m, n and o are integers of 1-4.
A 1 and A 2 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, COOH, PO 3 H 2 , PO 4 H 2 , SO 4 H 2 , CONHOH and their deprotonated form ) Is an anchoring group selected from and wherein at least one of A 1 and A 2 is an anchoring group.
The method according to any one of claims 1 to 5,
When a substituted or unsubstituted hetero group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is substituted in Formulas 1 to 6, the substituent is a hydrogen atom or a deuterium atom A halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An organometallic dye characterized by being selected from the group consisting of an aryloxy group having 6 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms.
Organometallic dye, characterized in that any one compound selected from the group represented by the following formula.
Figure 112012009525873-pat00088
Figure 112012009525873-pat00089

Figure 112012009525873-pat00090
Figure 112012009525873-pat00091

Figure 112012009525873-pat00092
Figure 112012009525873-pat00093

Figure 112012009525873-pat00094
Figure 112012009525873-pat00095

Figure 112012009525873-pat00096
Figure 112012009525873-pat00097

Figure 112012009525873-pat00098
Figure 112012009525873-pat00099

Figure 112012009525873-pat00100
Figure 112012009525873-pat00101

Figure 112012009525873-pat00102
Figure 112012009525873-pat00103

Figure 112012009525873-pat00104
Figure 112012009525873-pat00105

Figure 112012009525873-pat00106
Figure 112012009525873-pat00107

Figure 112012009525873-pat00108
Figure 112012009525873-pat00109

Figure 112012009525873-pat00110
Figure 112012009525873-pat00111

Figure 112012009525873-pat00112
Figure 112012009525873-pat00113

Figure 112012009525873-pat00114
Figure 112012009525873-pat00115

Figure 112012009525873-pat00116
Figure 112012009525873-pat00117

Figure 112012009525873-pat00118
Figure 112012009525873-pat00119

Figure 112012009525873-pat00120
Figure 112012009525873-pat00121

Figure 112012009525873-pat00122
Figure 112012009525873-pat00123

Figure 112012009525873-pat00124
Figure 112012009525873-pat00125

Figure 112012009525873-pat00126
Figure 112012009525873-pat00127

Figure 112012009525873-pat00128
Figure 112012009525873-pat00129

Figure 112012009525873-pat00130
Figure 112012009525873-pat00131

Figure 112012009525873-pat00132
Figure 112012009525873-pat00133

Figure 112012009525873-pat00134
Figure 112012009525873-pat00135

Figure 112012009525873-pat00136
Figure 112012009525873-pat00137

Figure 112012009525873-pat00138
Figure 112012009525873-pat00139

 5. The method according to any one of claims 1 to 4,
The A1 and A2 at least one end group of the COO -, PO 3 2-, PO 4 2-, SO 3 2-, SO 4 2-, and CONHO - is one of the anions selected from the group consisting of, wherein the end group An organometallic dye characterized by forming a salt with one cation selected from the group consisting of silver ammonium, phosphonium, sulfonium, imidazolium, pyrrolidoneium and pyridinium.
An optoelectronic device comprising a porous oxide semiconductor film comprising the organometallic dye of any one of claims 1 to 5.
10. The method of claim 9,
The porous oxide semiconductor film is an optoelectronic device, characterized in that composed of fine particles containing one of oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium.
10. The method of claim 9,
The porous oxide semiconductor film is used in the light absorption layer formed between the first electrode and the second electrode opposite thereto. The method of claim 11,
The thickness of the light absorption layer, the thickness of the thin film is a photoelectric device, characterized in that 1-2,000nm.
A first electrode formed on one surface of the first electrode and including a porous film and a light absorbing layer comprising the organic metal dye of any one of claims 1 to 5 and 7 formed on the porous film. A dye-sensitized solar cell comprising a second electrode disposed toward and a electrolyte embedded in a space between the first electrode and the second electrode.
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