KR20190107866A - Organic dyes, compositions and dye-sensitized solar cell - Google Patents

Abstract

The present invention relates to an organic dye having improved stability to heat, light and water, to a composition comprising the same, and to a dye-sensitized solar cell and, more specifically, to an organic dye represented by chemical formula 1, to a composition comprising the same, and to a dye-sensitized solar cell. The chemical formula 1 is the same as defined in claim 1.

Description

Organic dyes, compositions and dye-sensitized solar cells comprising the same {ORGANIC DYES, COMPOSITIONS AND DYE-SENSITIZED SOLAR CELL}

The present invention discloses an organic dye, a composition comprising the same, and a dye-sensitized solar cell.

With growing interest in environmentally friendly power generation, the solar cell business is growing rapidly in the renewable energy market. In the case of silicon solar cells, through the long research and development, the price reduction of silicon solar cell modules and the highest efficiency among commercial solar cell products can be achieved.

Silicon solar cells have technical limitations in order to be applied to various practical products beyond the function of solar cell modules that generate energy. Since the silicon solar cell shows a rapid decrease in efficiency according to the angle of incidence of the solar cell, the module can be applied only to an outdoor roof, and the conversion efficiency is lowered at high temperatures compared to other solar cells. In addition, due to the difficulty in manufacturing transparent and flexible solar cells, it is difficult to develop products that are closely related to real life, and interest in DSC (Dye-sensitized Solar Cell) is increasing to solve these problems and develop solar cells that are closely related to real life. .

DSC is not only flexible and transparent, but also has the advantage of high efficiency under low-light indoor lighting, and can be developed as a close-type indoor solar cell. Initial (RuL ₂ (μ- (CN) Ru (CN) L ' ₂ ) ₂ , where L is 2,2'bipyridine-4,4'-dicarboxylic acid and L 'is 2,2'-bipyridine Starting with dyes, most DSC dyes are being developed based on Ru (ruthenium) (N3, N719, black dye, etc.) Ru-based dyes show relatively high efficiencies compared to other dyes ( 9%), Ru is expensive, low stability and difficult to synthesize, there is a high demand for the development of high efficiency and stable organic dyes using metal-free organic dyes.

The present invention is to improve the efficiency of the dye-sensitized solar cell, to provide an organic dye with improved stability to heat, light and water (water).

This invention provides the organic dye composition containing the organic dye by this invention.

The present invention provides a dye-sensitized solar cell containing the organic dye according to the present invention.

According to one embodiment of the present invention, it relates to an organic dye represented by the following formula (1).

(Wherein R ¹ to R ¹⁰ are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, carbon number 1 to 30 alkoxy, 1 to 30 alkylcarbonyl, 2 to 20 aryl and substituted or unsubstituted carbazole,

R ¹¹ and R ¹² each represent hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 1-30 Alkoxy, alkyl of 1 to 30 carbon atoms and aryl of 2 to 20 carbon atoms,

이고,Ar ₁ is,

ego,

R ¹³ to R ¹⁴ each represent hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl and C 2-30 Alkoxy, C1-C30 alkylcarbonyl or C2-C20 aryl.)

According to an embodiment of the present invention, in formula 1

R ¹ to R ¹⁰ are not all hydrogen,

이고, R^a 내지 R^d는, 수소, 할로겐, 아미드, 시아노, 하이드록실, 니트로, 아실, 탄소수 1 내지 30 알킬, 탄소수 2 내지 30 알케닐, 탄소수 2 내지 30의 알키닐, 탄소수 2 내지 30의 알콕시 및 탄소수 1 내지 30 알킬카보닐에서 선택되는 것일 수 있다. The substituted or unsubstituted carbazole,

R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 2-30 It may be selected from alkoxy and alkyl carbonyl of 1 to 30 carbon atoms.

According to an embodiment of the present invention, the alkoxy is represented by -OR, and R is an alkyl of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 30 carbon atoms, and 2 to 20 aryl carbon atoms. It may be selected.

According to an embodiment of the present invention, the alkoxy is methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, hepyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, Dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosanyloxy, pentyloxy, hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, 2-ethylhexyloxy, 2-methylheptyloxy, 2-propylbutyloxy, benzyloxy, methylbenzyloxy, and isomers thereof.

According to an embodiment of the present invention, the organic dye may be selected from the following Chemical Formulas 2 to 3.

[Formula 2]

[Formula 3]

Here, R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 2 -C Selected from alkoxy of 30 and alkylcarbonyl having 1 to 30 carbon atoms,

R to R 'are each selected from alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms and aryl having 2 to 20 carbon atoms.)

According to one embodiment of the present invention, one or more of the organic dyes according to the present invention; It relates to an organic dye composition comprising.

According to an embodiment of the present invention, the composition may further include a co-adsorbent.

According to an embodiment of the present invention, the composition may further include a metal oxide.

According to one embodiment of the invention, the first electrode; A light absorption layer formed on the first electrode; And a second electrode formed on the light absorbing layer; It includes, The light absorption layer, Metal oxide; It relates to a dye-sensitized solar cell comprising, and an organic dye according to the present invention or a composition according to the present invention.

According to an embodiment of the present invention, the metal oxide is Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm and Ga It may be to include one or more selected from the group consisting of.

According to an embodiment of the present invention, the light absorption layer may include a metal oxide film in the form of a porous film, and may be formed on at least a portion of the metal oxide film by coating, impregnation, or both of the composition.

According to an embodiment of the present invention, the metal oxide may have a size of 1 nm to 1000 nm.

According to an embodiment of the present invention, the light absorption layer may be transparent and have a thickness of 10 μm or less.

According to an embodiment of the present invention, between the first electrode and the second electrode, an electrolyte; further comprising, the electrolyte may include an ionic liquid electrolyte or a liquid electrolyte.

According to one embodiment of the invention, preparing a first electrode; Preparing the second electrode; And disposing a light absorption layer on the first electrode, wherein the light absorption layer comprises: a metal oxide; And it relates to a method of manufacturing a dye-sensitized solar cell comprising; and an organic dye of the present invention or a composition of the present invention.

According to one embodiment of the invention, the light absorption layer, may be formed by coating, impregnation or both of the composition on at least a portion of the metal oxide film.

According to one embodiment of the present invention, the present invention can provide a dye-sensitized solar cell having improved thermal, light and water (water) stability, and providing a low-light, high-efficiency organic dye. have. In addition, the present invention, as a metal-free organic dye (metal-free) can improve the performance and cost-effectiveness than conventional metal dyes, for example, Ru-based dyes.

FIG. 1 shows the change in efficiency and the light parameter of a photovoltaic cell of an ionic liquid electrolyte according to the thermal stability evaluation of Evaluation Example 2 (70 ° C dark room conditions) according to an embodiment of the present invention.
Figure 2, according to an embodiment of the present invention, shows the normalized UV absorbance (Normalized UV absorbance) change of the organic dye according to the AM 1.5 roughness time by the light stability evaluation of Evaluation Example 2.
FIG. 3 shows FT-IR spectra changes (0h, 2h) of ID1 dye and RK-2 dye according to AM 1.5 light aging according to one embodiment of the present invention.
Figure 4, according to an embodiment of the present invention, the change in normalized UV absorption over time when the film containing the organic dye adsorbed by the water (water) stability of Evaluation Example 2 is immersed in a solution containing water It is shown.
Figure 5, according to an embodiment of the present invention, shows the mechanism for the water stability of the organic dye according to the present invention.

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. However, various changes may be made to the embodiments so that the scope of the patent application is not limited or limited by these embodiments. It is to be understood that all changes, equivalents, and substitutes for the embodiments are included in the scope of rights.

The terminology used herein is for the purpose of description and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

In addition, in the description with reference to the accompanying drawings, the same components regardless of reference numerals will be given the same reference numerals and duplicate description thereof will be omitted. In the following description of the embodiment, when it is determined that the detailed description of the related known technology may unnecessarily obscure the gist of the embodiment, the detailed description thereof will be omitted.

Although the embodiments have been described with reference to the accompanying drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, the described techniques may be performed in a different order than the described method, and / or components of the described systems, structures, devices, circuits, etc. may be combined or combined in a different form than the described method, or other components. Or even if replaced or substituted by equivalents, an appropriate result can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are within the scope of the following claims.

The present invention relates to an organic dye, and according to an embodiment of the present invention, the organic dye is composed of a triarylamine electron donor and a dithienothiophene-based π-bridge, It is possible to provide a metal-free organic dye having improved hot water stability and efficiency.

According to one embodiment of the invention, the organic dye may be selected from compounds represented by the following formula (1).

[Formula 1]

Here, R ¹ to R ¹⁰ are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 1 It may be selected from alkoxy having 30 to 30, alkylcarbonyl having 1 to 30 carbon atoms, aryl having 2 to 20 carbon atoms and substituted or unsubstituted carbazole.

Preferably, R ¹ to R ¹⁰ are not all hydrogen, which may increase efficiency change and stability as a functional group is introduced into the donor.

The alkoxy is represented by -O-R, and R may be selected from 1 to 30 alkyl, 2 to 30 alkenyl, 2 to 30 alkynyl and 2 to 20 aryl. More specifically, the alkoxy is methoxy, ethoxy, propoxy, appendix, pentoxy, hexyloxy, hepyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tri Decyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosanyloxy, pentyloxy, hexyloxy, 3,3-dimethyl Butyloxy, 2-ethylbutyloxy, 2-ethylhexyloxy, 2-methylheptyloxy, 2-propylbutyloxy, benzyloxy, methylbenzyloxy and isomers thereof.

이고,The substituted or unsubstituted carbazole,

ego,

R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C2-C30 alkoxy And it may be selected from alkyl carbonyl having 1 to 30 carbon atoms.

R ¹¹ and R ¹² each represent hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl and C 1 -C And alkoxy of 30, alkyl of 1 to 30 carbon atoms and aryl of 2 to 20 carbon atoms.

이며, 이러한 Ar₁의 도입으로 디티에노티오펜계 π-bridge는, 상기 전자 주개와 콘주게이트된 디티에노[3,2-b;2',3''-d]티오펜(dithieno[3,2-b;2',3''-d]thiophene, DTT)계 π-브릿지(π-bridge)를 형성할 수 있다. 이는, 강한 안정성과 정공 이동도(hole mobility) 능력에 의해서 안정성이 강화된 저조도 고효율(PCE) 염료를 형성할 수 있다. Ar ₁ is,

With the introduction of Ar ₁ The dithienothiophene-based? -Bridge is a dithieno [3,2-b; 2 ', 3''-d] thiophene conjugated with the electron donor (dithieno [3,2-b; 2', 3 ''-d] thiophene (DTT) -based π-bridge can be formed. This can form a low light high efficiency (PCE) dye having enhanced stability by strong stability and hole mobility ability.

R ¹³ to R ¹⁴ in Ar ₁ are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, It may be alkoxy having 2 to 30 carbon atoms, alkyl carbonyl having 1 to 30 carbon atoms or aryl having 2 to 20 carbon atoms.

According to an embodiment of the present invention, the organic dye may be selected from the following Chemical Formulas 2 to 3.

 [Formula 2]

[Formula 3]

Here, R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 2-30 Is selected from alkoxy and C1-C30 alkylcarbonyl, and R to R 'are each selected from C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl and C2-C20 aryl, respectively. Can be.

According to one embodiment of the invention, the organic dye is a dye applicable to the optical device, for example, can be applied to a transparent and flexible photoelectrode. For example, it may be applied as a photoanode of a dye-sensitized solar cell.

The present invention relates to an organic dye composition comprising at least one of the organic dyes according to the present invention. The organic dye is as mentioned above, and preferably the composition may include one or more of the compounds of the formulas (2) to (3).

According to one embodiment of the invention, the organic dye is less than 100 parts by weight based on 100 parts by weight of the composition; 90 parts by weight or less; Alternatively 0.001 to 80 parts by weight; 0.1 to 50 parts by weight; Or 0.1 to 10 parts by weight. When included in the content range, the adsorption, coating, etc. are well made on the semiconductor oxide, and the performance is improved, and a thin and transparent photoactive film and a flexible dye-sensitized solar cell using the same can be provided.

According to an embodiment of the present invention, the composition may further include a solvent, an additive, and the like according to an application field or a method.

The solvent is an organic solvent, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or tert-butanol; Hydrocarbons such as benzene, toluene, xylene and the like; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF) and the like; Glycol ethers such as ethylene glycol monomethyl, ethylene glycol dimethyl ether, and the like; Ketones such as acetone and the like; Chloride chlorides such as trichloroethylene, 1,2-dichloroethane, tetrachloromethane, chloroform, dichloromethane (DCM), and the like; And acetamide, dimethylacetamide, N-methylpyrrolidone (NMP), dimethyl-formamide (DMF) and the like.

According to one embodiment of the invention, the composition may further comprise a co-adsorbent, more specifically, carbon nanotubes, graphene, carbon black, deoxycholic acid, dehydrodeoxoxic acid, ke Nodeoxycholine acid, choline acid methyl ester, sodium choline salt, crown ether, cyclodextrin, calixarene, polyethylene oxide and the like. The co-adsorbent may be included in an amount of 10 to 200 parts by weight based on 100 parts by weight of the organic dye.

According to an embodiment of the present invention, the composition may further include semiconductor fine particles, for example, the semiconductor fine particles may be a metal and a metal compound, and the metal compound may be an oxide, a nitride, an alloy, or the like. . More specifically, at least one metal selected from the group consisting of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm and Ga, and Oxide or alloys thereof. The semiconductor fine particles may be included in 10 to 300 parts by weight based on 100 parts by weight of the organic dye.

The average particle diameter of the semiconductor fine particles, The average particle diameter of the semiconductor fine particles, 1 nm to 1000 nm; 1 nm to 500 nm; Or 1 nm to 200 nm.

The present invention relates to a dye-sensitized solar cell, and according to an embodiment of the present invention, the dye-sensitized solar cell provides a thin film-type dye-sensitized solar cell having improved stability and efficiency by applying the organic dye according to the present invention. Can be.

According to one embodiment of the invention, the dye-sensitized solar cell, the first electrode; A light absorption layer formed on the first electrode; And a second electrode formed on the light absorption layer.

According to an embodiment of the present invention, the first electrode may be a photoelectrode, and may include a transparent substrate and a conductive metal oxide layer. For example, indium tin oxide (ITO), fluorine tin oxide (FTO), ZnO- (Ga ₂ O ₃ or Al ₂ O ₃ ), tin oxide, antimony tin oxide (ATO), zinc oxide (ZnO), etc. Can be. The conductive metal oxide film may be formed on a transparent substrate.

The transparent substrate may be glass or plastic, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polypropylene, polyimide, and triacetyl cellulose.

According to an embodiment of the present invention, the second electrode may include a transparent substrate, a transparent electrode and / or a catalyst electrode, and the transparent electrode may be formed on the transparent substrate.

The transparent electrode is formed on the transparent substrate and is made of a transparent material such as indium tin oxide, fluorine oxide, antimony tin oxide, zinc oxide, tin oxide, ZnO- (Ga ₂ O ₃ or Al ₂ O ₃ ), and the like. Can be. The transparent substrate is the same as the first electrode 110, and may be the same as or different from the first electrode.

The catalyst electrode is formed on the transparent substrate or the transparent electrode, and serves to activate a redox couple, and includes platinum (Pt), gold (Au), ruthenium (Ru), and palladium (Pd). ), Rhodium (Rh), iridium (Ir), osmium (Os), carbon (C), titanium oxide (TiO ₂ ) and may include one or more selected from the group consisting of conductive polymers.

According to an embodiment of the present invention, the light absorption layer is formed on the first electrode, and may include the semiconductor fine particles and the organic dye or the composition according to the present invention.

The semiconductor fine particles are metals and metal compounds, and the metal compounds may be oxides, nitrides, alloys, and the like. More specifically, selected from the group consisting of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, In, Ta, V and Ga It may be one or more metals, oxides thereof or alloys thereof, preferably metal oxides. For example, the metal oxide may be titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), titanium strontium oxide (TiSrO ₃ ), or the like.

The average particle diameter of the semiconductor fine particles is 1 nm to 1000 nm; 1 nm to 500 nm; Or 1 nm to 200 nm.

According to one embodiment of the invention, the light absorbing layer comprises a porous film form consisting of semiconductor fine particles, the organic dye or the composition according to the present invention to at least a portion of the film is coated, impregnated or adsorbed by both ( Or combined). The coating and impregnation may adsorb organic dyes or compositions to the pores, surfaces or both of the film.

The light absorption layer has a thickness of 10 μm or less; 5 μm or less; Or 4 μm or less; Or 0.5 μm to 3.5 μm. When included in the thickness range, it is transparent and improves efficiency, and may prevent a peeling off phenomenon, thereby providing a flexible solar cell.

According to an embodiment of the present invention, the electrolyte may further include an electrolyte between the first electrode and the second electrode, for example, an electrolyte may be injected between the active layer and the second electrode. The electrolyte may be applied without limitation as long as it is applicable to dye-sensitized solar cells, and preferably includes a liquid electrolyte, an ionic liquid electrolyte, or both, for example, iodine (I ₂ ) and lithium iodine. Id (LiI), 1-butyl-2-methyl imidazolium iodide, 1-allyl-3-methylimidazolium iodide, 1-Allyl-3-methylimidazolium iodide, 1,3-dimethylimidazolium iodine (1,3-dimethylimidazolium iodide), 1-hexyl-2,3-dimethylimidazolium iodide (1-Hexyl-2,3-dimethylimidazolium iodide), 1-butyl-2, 3-dimethylimidazolium iodide (1-Butyl-2,3-dimethylimidazolium iodide), 1-dodecyl-3-methylimidazolium iodide (1-Dodecyl-3-methylimidazolium iodide), 1-butyl-3-methyl Imidazolium iodine (1-Butyl-3-methylimidazolium iodide), 1,2-dimethyl-3-propylimidazolium iodide (1,2-Dimethyl-3-propylimidazolium iodide; DMPII), 1-ethyl-3-methyl Midazolium iodine (1-Ethyl-3-methylimidazolium iodide), 1-hexyl-3-methylimidazolium iodide, 1-methyl-3-propylimidazolium iodine Methyl-3-propylimidazolium iodide) and 4-tert-butylpyridine (TPP), etc., and those dissolved in methoxy acetonitrile, valeronitrile, acetonitrile, etc. may be applied. Can be.

The present invention relates to a method for manufacturing a dye-sensitized solar cell. According to an embodiment of the present invention, the method includes preparing a first electrode; Preparing a second electrode; And bonding the first electrode and the second electrode to form an electrolyte therebetween. It may include.

According to one embodiment of the invention, the step of preparing the first electrode and the step of preparing the second electrode, according to the process applied in the technical field of the present invention, such as coating, deposition, etc. according to the above-mentioned configuration Can be prepared.

According to an embodiment of the present invention, disposing a light absorbing layer between the first photoelectrode and the second electrode, forming a light absorbing layer on the first electrode or preparing a light absorbing layer film to the first electrode and The second electrode may be bonded in the form of a sandwich.

The light absorbing layer may be formed by coating, impregnating, or both of an organic dye or a composition on at least a portion of the semiconductor particulate film.

The light absorption layer may form a porous semiconductor particulate film by coating a semiconductor particulate paste on a substrate or the first electrode.

The impregnation may be impregnated by immersing the semiconductor particulate film in an organic dye or composition, the coating comprising spin coating, spray coating, dip coating, slit die coating, bar coating, screen coating on at least a portion of the semiconductor particulate film. Etc. can be used.

Although the present invention will be described with reference to preferred embodiments, the present invention is not limited thereto, and the present invention is not limited to the scope of the present invention as defined in the following claims, the detailed description of the invention, and the accompanying drawings. Various modifications and variations can be made in the present invention.

[Scheme 1]

[Scheme 2]

Example 1

(E) -2-cyano-3- (5- (6- (5-((4- (diphenylamino) phenyl) ethynyl) -3-hexylthiophen-2-yl) dithieno [3 , 2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) acrylic acid (TP-1)

((E) -2-cyano-3- (5- (6- (5-((4- (diphenylamino) phenyl) ethynyl) -3-hexylthiophen-2-yl) dithieno [3,2-b: 2 ' , 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) acrylic acid)

(TP-1)

(TP-1)

Dye compounds were prepared by coupling and condensation reactions according to scheme 2, using the π-bridges and donor unit portions prepared according to scheme 1.

Compound EF-1 (55 mg, 0.046 mmol) and cyanoacetic acid (15 mg, 0.185 mmol) of Scheme 1 were placed in a 150 ml flask and mixed. Solvent (chloroform: acetonitrile = 12 ml: 4 ml) was injected into the flask. Piperidine (15 mg, 0.185 mmol) was added slowly. The mixture was heated at reflux overnight (60-70 ° C.). When the reaction was completed, the reaction was stopped by pouring water at room temperature. The mixed product was extracted with chloroform and washed with brine. The organic layer was evaporated under reduced pressure and purified by column chromatography at first with MC and finally with MC: MeOH: AcOH mixed solvent (v / v / v = 10: 1: 0.1). A black solid (60 mg, 99%) with a reddish light was obtained.

¹ H NMR (400 MHz, DMSO-d ₆ / CDCl ₃ (v / v = 1: 1) δ (ppm): δδ 0.83 (br m, 6H), 1.31 (br m, 12H), 1.63 (br m, 4H), 2.74 (t, J = 7.6 Hz, 2H), 2.81 (t, J = 7.6, 2H), 6.90 (d, J = 8.4, 2H), 7.04 (m, 5H), 7.09 (s, 1H) , 7.27 (m, 6H), 7.42 (s, 1H), 7.62 (s, 1H), 7.67 (s, 1H), 7.69 (s, 1H), 8.24 (s, 1H); ¹³ C NMR (100 MHz, DMSO-d ₆ / CDCl ₃ (v / v = 1/1)): δ 14.2, 22.5, 29.0, 29.1, 29.2, 30.1, 30.3, 31.5, 81.8, 95.1, 114.8, 117.5, 119.8, 121.0, 121.6, 121.9 , 124.1, 125.2, 129.7, 130.1, 131.3, 131.6, 132.4, 134.3, 134.8, 135.5, 136.6, 139.9, 140.6, 142.1, 142.5, 143.8, 146.8, 148.2, 164.5; HRMS (ESI): Exact mass calcd for C ₅₂ H ₄₆ N ₂ 0 ₂ S ₅ [M] ⁺ : 890.2163, found 890.2158.

Example 2

(E) -3- (5- (6- (5-((4- (bis (4-methoxyphenyl) amino) phenyl) ethynyl) -3-hexthiophen-2-yl) dithieno [ 3,2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid ((E) -3- (5- (6 -(5-((4- (bis (4-methoxyphenyl) amino) phenyl) ethynyl) -3-hexylthiophen-2-yl) dithieno [3,2-b: 2 ', 3'-d] thiophen-2- yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid)

(TP-2)

(TP-2)

Dye compounds were prepared by coupling and condensation reactions according to scheme 2, using the π-bridges and donor unit portions prepared according to scheme 1.

Compound EF-2 (209 mg, 0.236 mmol) and cyanoacetic acid (80 mg, 0.945 mmol) of Scheme 1 were mixed in a 150 ml flask and mixed with a solvent (chloroform: acetonitrile = 21 ml: 7 ml ) Was injected into the flask. Next, piperidine (80 mg, 0.945 mmol) was added slowly. The mixture was heated at reflux overnight (60-70 ° C.). A black solid with reddish light was obtained (100 mg, 44%).

¹ H NMR (400 MHz, DMSO-d ₆ / CDCl ₃ (v / v = 1/1)) δ (ppm): δ 0.82 (br m, 6H), 1.25 (br m, 10H), 1.60 (d, 5H), 2.75 (m, 5H), 3.73 (s, 6H), 6.64 (d, J = 8.7 Hz, 2H), 6.95-6.91 (m, 4H), 7.11-7.06 (m, 4H), 7.22 (s , 1H), 7.28 (d, J = 8.6 Hz, 2H), 7.82 (d, 7.8 Hz, 1H); ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 14.2, 22.5, 29.0, 29.1, 29.2, 30.1, 30.3, 31.5, 55.5, 78.9, 81.2, 95.6, 112.4, 115.0, 118.3, 119.6, 121.0, 122.2, 127.5, 130.0, 131.3, 131.4, 132.2, 134.4, 135.3, 136.8, 139.5, 140.3, 140.6, 142.0, 142.6, 149.2, 156.6; HRMS (ESI): Exact mass calcd for C ₅₄ H ₅₀ N ₂ O ₄ S ₅ [M] ⁺ : 950.2374, found 950.2375.

Example 3

(E) -3- (5- (6- (5-((4- (bis (4- (9H-carbazol-9-yl) phenyl) amino) phenyl) ethynyl) -3-hexylthiophene- 2-yl) dithieno [3,2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid (TP-3 )

(E) -3- (5- (6- (5-((4- (bis (4- (9H-carbazol-9-yl) phenyl) amino) phenyl) ethynyl) -3-hexylthiophen-2-yl) dithieno [3,2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid)

(TP-3)

(TP-3)

Dye compounds were prepared by coupling and condensation reactions according to scheme 2, using the π-bridges and donor unit portions prepared according to scheme 1.

Compound EF-3 (69 mg, 0.060 mmol) and cyanoacetic acid (50 mg, 0.597 mmol) of Scheme 1 were mixed in a 150 ml flask and the solvent (chloroform: acetonitrile = 15 ml: 5 ml) was added to the flask. Infused. Next, piperidine (50 mg, 0.597 mmol) was added slowly. The mixture was heated at reflux overnight (60-70 ° C.). A black solid with reddish light was obtained (58 mg, 79%).

¹ H NMR (400 MHz, DMSO-d ₆ / CDCl ₃ (v / v = 1/1)) δ (ppm): δ 0.82 (br m, 6H), 1.27 (br m, 10H), 1.63 (m, 5H), 2.78 (dt, J = 16.7, 7.7 Hz, 5H), 7.17 (s, 1H), 7.21 (d, J = 1.1 Hz, 1H), 7.23 (m, 2H), 7.24 (m, 2H), 7.36 (d, J = 1.3 Hz, 1H), 7.46-7.38 (m, 14H), 7.49 (m, 2H), 7.54 (m, 4H), 7.61 (s, 1H), 7.64 (s, 1H), 8.11 (dt, J = 7.7, 0.9 Hz, 4H), 8.17 (s, 1H); ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 14.3, 22.5, 22.6, 24.1, 24.2, 25.4, 26.1, 29.0, 29.2, 30.1, 30.3, 31.5, 82.3, 94.9, 110.0, 116.3, 117.5, 120.0, 120.2, 120.5, 121.1, 121.7, 123.1, 123.2, 126.0, 126.2, 128.2, 130.1, 131.3, (131.8), 131.9, 132.8, 132.9, 134.4, 135.1, 135.5, 136.5, 140.4, 140.6, 140.7, 142.2, 142.6, 145.8, 147.7, 164.3; HRMS (FAB ⁺ ): Exact mass calcd for C ₇₆ H ₆₀ N ₄ O ₂ S ₅ [M] ⁺ : 1220.3320, found 1121.3379.

Example 4

(E) -3- (5- (6- (5-((4- (bis (4-((2-ethylhexyl) oxy) phenyl) amino) phenyl) ethynyl) -3-hexylthiophene-2 -Yl) dithio [3,2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid (TP-4) ((E) -3- (5- (6- (5-((4- (bis (4-((2-ethylhexyl) oxy) phenyl) amino) phenyl) ethynyl) -3-hexylthiophen-2-yl) dithieno [3,2-b: 2 ', 3'-d] thiophen-2-yl) -4-hexylthiophen-2-yl) -2-cyanoacrylic acid)

(TP-4)

(TP-4)

Dye compounds were prepared by coupling and condensation reactions according to scheme 2, using the π-bridges and donor unit portions prepared according to scheme 1.

Compound EF-4 (50 mg, 0.046 mmol) and cyanoacetic acid (15 mg, 0.185 mmol) of Scheme 1 were mixed in a 150 ml flask and mixed with a solvent (chloroform: acetonitrile = 7 ml: 7 ml). It was injected into the flask. Piperidine (15 mg, 0.185 mmol) was added slowly. The mixture was heated at reflux overnight (60-70 ° C.). A reddish black solid was obtained (30 mg, 56%).

¹ H NMR (400 MHz, DMSO-d ₆ / CDCl ₃ (v / v = 1/1)) δ (ppm): δ 0.93 (br m, 18H), 1.34 (br m, 16H), 1.46 (br m , 12H), 1.70 (br m, 6H), 2.80 (t, J = 8.0 Hz, 2H), 2.86 (t, J = 7.7 Hz, 2H), 3.85 (d, J = 5.7 Hz, 4H), 6.78 ( d, J = 8 Hz, 2H), 6.90 (d, J = 8.9 Hz, 4H), 7.08 (d, J = 8.9 Hz, 4H), 7.14 (s, 1H), 7.27 (d, J = 8.7 Hz, 2H), 7.49 (s, 1H), 7.57 (s, 1H), 7.62 (s, 1H), 8.16 (s, 1H); HRMS (FAB ⁺ ): Exact mass calcd for C ₆₈ H ₇₈ N ₂ O ₄ S ₅ [M] ⁺ : 1146.4565, found 1146.4563.

Evaluation example 1

Evaluation of DSC Efficiency

The compounds of Examples 1 to 4 are used in DSCs together with conventional electrolytes (liquid electrolytes) or Ionic liquid electrolytes as thin film active layers, and are shown in Table 1 by measuring the efficiency of DSCs.

Photoanode and count electrodes were fabricated on FTO glass (Fluorine-doped Tin Oxide glass, Nippon Sheet Glass Co., Ltd). The FTO glass was washed with an ultrasonic cleaner in acetone, ethanol and isopropanol for 10 minutes followed by UV ozone to induce the formation of a hydrophilic surface. After the washing process, TiO ₂ was deposited on the FTO surface by immersion in 0.04 M aqueous TiCl ₄ solution at 70 ^° C. for 30 minutes.

After washing with ultrapure water and ethanol, the TiO _{2 clear} layer was deposited on the substrate by a screen-printing method using a mask (MESH S / T250, Emulsion 12 μm). Conventional type cells with an organic solvent electrolyte were prepared with a 1.8 μm thick transparent layer of 18 nm TiO ₂ nanoparticles (Dongjin Semichem Co., Ltd). In the case of an ionic liquid electrolyte, a 3.5 μm thick transparent layer of 8-10 nm TiO ₂ nanoparticles (Ti-Nanoxide MC / SP, Solaronix) was prepared. All transparent layers were coated with a 2.5 μm thick second layer of scattering particles (Ti-Nanoxide R / SP, Solaronix) by screen printing. Substrates with printed TiO ₂ layers were sequentially placed at 150 ^o C (10 min), 325 ^o C (5 min), 327 ^o C (5 min), 450 ^o C (15 min) and 500 ^o C (30 min) Sintered at each.

After the sintering process it was cooled to 80 ^° C. and the photoanode was immersed in 0.04 M aqueous TiCl ₄ solution at 70 ^° C. for 30 minutes. After ultrapure water and ethanol rinse, the photoanode was sintered at 500 ^° C. for 30 minutes. This photoanode, together with 10 mM of chenodeoxycholic acid (CDCA) as a co-adsorbent under dark conditions, was added in a 0.2 mM dye solution dissolved in a two-component solvent of chloroform and ethanol (volume ratio, 7L3). Immerse for hours. In the case of TP-2 and TP-4, bicomponent solvents of chloroform, tert-butanol and acetonitrile (volume ratio, 2: 9: 9) were additionally used with 1 mM CDCA. At the counter electrode, the FTO glass was washed in the same way as the photoanode and made a hole with a hand drill for electrolyte injection. The substrate was brushed with 10 mM H ₂ PtCl ₆ · 6H ₂ O ethanol solution to finish the surface and sintered at 400 ° C. for 15 minutes. This photoelectrode and count electrode were assembled into a sandwich cell with a 25 μm thick Surlyn film and sealed under pressure at 110 ^° C. The internal space of the cell was inserted into the electrolyte by means of vacuum back filling, and the injection hole was sealed using Surlyn film and curve glass.

As a liquid electrolyte, the iodine electrolyte is 0.055 MI ₂ , 0.025 M LiI, 0.05 M guanidine thiocyanate, in a mixed solvent of acetonitrile and valeronitrile (acetonitrile, valeronitrile, volume ratio, 85:15). GuSCN), 0.6 M TBP (1,2 -dimethyl-3-propylimidazolium iodide) and 0.5 M 4-t ert - a composition consisting of-butylpyridine (4-t ert -butylpridine). The ionic liquid electrolyte is a eutectic-based electrolyte comprising a mixture of 1-ethyl-3-methylimidazolium iodide (EMII), 1,3-dimethylimidazolium iodide (DMII) and 1-ethyl-3-methylimidazoliumtetracyanoborate (EMITCB). It was used to increase the properties of. That is, the composition of the ionic liquid electrolyte is DMII / EMII / EMITCB / I2 / TBP / GuSCN (molar ratio, 12: 12: 16: 1.67: 3.33: 0.67). In addition, a eutectic electrolyte (TDE-250, Solaronix) sold was used.

In Table 1, it can be seen that DSCs applying the liquid electrolyte and the ionic liquid electrolyte generally provide excellent efficiency. In particular, DSCs of liquid electrolytes show that TP-2 and TP-4 with alkoxy groups achieve high efficiencies (8.70%, 8.86%), with the excellent donating ability of alkoxy groups increasing the HOMO of the dye and TiO ₂ increases charge injection efficiency. On the other hand, the carbazole group in the TP-3 dye is twistedly linked with triphenylamine, which does not affect triphenylamine as an electron donating group and thus does not significantly affect triphenylamine. Compared to the somewhat lower efficiency. In addition, the DSCs may be manufactured in a thin film 3.5 (μm) + 2.5 (μm) to increase the cost-effectiveness and reduce the peeling off phenomenon generated when manufacturing the flexible device.

Evaluation example 2

(1) thermal stability

DSC device using the ionic liquid electrolyte of Table 1 was stored in an oven maintained at 70 ℃ heat to measure the change in efficiency and light parameters with time to compare the characteristics according to the functional groups. The result is shown in FIG.

Referring to FIG. 1, which shows a thermal stability test for 1000 hours, the normalized efficiency graph shows that the methoxy group has the smallest change in efficiency (PCE) due to heat and shows the most excellent thermal stability. The 2-ethylhexyloxy group shows lower thermal stability than the methoxy group, but better thermal stability than the carbazole group, and the carbazole group is used in the functional group due to low charge regeneration efficiency and charge injection efficiency. Shows the lowest thermal stability, but functional groups are always better than those without functional groups (TP-2, TP-3, TP-4). It can be seen that the thermal stability can be enhanced accordingly.

(2) light stability

After forming a 1.8-μm TiO ₂ film, the dyes of Examples 1 to 4 and Ru-based N719 were respectively adsorbed at room temperature for 5 hours to measure absorption spectra. Subsequently, the stability of the materials was compared by measuring the degree of absorption reduction after placing them under light corresponding to AU 1.5G intensity. The results are shown in FIG.

Referring to FIG. 2, TP-2 having a methoxy group showed the best light stability as well as thermal stability, and TP-4 having a 2-ethylhexyloxy group showed a light stability similar to that of TP-2. have. In the case of carbazole groups, the 3,6-position is weak, so it is rather characterized by lower light stability than TP-1 dye without functional groups. However, all TP series dyes showed much better light stability than Ru series N719, which is widely used. This is because dithieno [3,2- b : 2 ', 3'- used as a framework]. d ] thiophene (dithieno [3,2- b : 2 ', 3'- d ] thiophene) (DTT) has strong light stability. That is, in FIG. 3, when the ID1 dye having a DTT skeleton is compared with the RK-2 dye having only a skeletal structure, the change in FT-IR spectra is hardly observed due to the small material change due to light aging. 2 shows a clear FT-IR spectra change with light aging.

(3) water stability

After forming a 1.8-μm TiO ₂ film, the dyes of Examples 1 to 4 were respectively adsorbed at room temperature for 5 hours to measure absorption spectra. Next, it was stored in a solution of acetonitrile: water (Acetonitrile: Water) = 90: 10 to compare the water stability by measuring the change in absorption due to the desorption of the dye. The results are shown in FIG. Looking at Figure 4, TP-3 shows the best water stability, as shown in the mechanism shown in Figure 5, due to the strong hydrophobicity of the carbazole groups, water is anchored (anchoring group) of the dye and TiO ₂ film This is because it interferes with the binding site of. TP-2, on the other hand, exhibits the lowest water stability because methoxy groups and water form hydrogen bonding, which disconnects water because it provides good access to dye and TiO ₂ bonds. to be. In the case of TP-4, which introduced an alkyl chain longer than methoxy to prevent the hydrogen bonding of oxygen to water in the functional group, it actually shows enhanced water stability.

The present invention provides a backbone (i.e., π-bridge) to a dithieno [3,2-b; 2 ', 3' '-d] thiophene (DTT) unit with good stability and hole transport capability. In addition to providing a dye having high efficiency in the thin film, it has a good electron donating ability, and introduces a triphenylamine-based electron donor that is easy to connect functional groups, the methoxy group, carbazole group and 2-ethylhexyl jade in the triphenylamine Time can be introduced to provide organic dyes with improved efficiency (PCE) and stability according to functional groups.

Although the embodiments have been described with reference to the accompanying drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, the techniques described may be performed in a different order than the described method, and / or the components described may be combined or combined in a different form than the described method, or replaced or substituted by other components or equivalents. Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are within the scope of the following claims.

Claims (16)

Organic dyes represented by the following formula (1):

(Wherein R ¹ to R ¹⁰ are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, carbon number 1 to 30 alkoxy, 1 to 30 alkylcarbonyl, 2 to 20 aryl and substituted or unsubstituted carbazole,
R ¹¹ and R ¹² each represent hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 1-30 Alkoxy, alkyl of 1 to 30 carbon atoms and aryl of 2 to 20 carbon atoms,

Ar ₁ is,

ego,
R ¹³ to R ¹⁴ each represent hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl and C 2-30 Alkoxy, C1-C30 alkylcarbonyl or C2-C20 aryl.)
The method of claim 1,
In Chemical Formula 1
R ¹ to R ¹⁰ are not all hydrogen,
The substituted or unsubstituted carbazole,

ego,
R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C2-C30 alkoxy And it is selected from alkyl carbonyl having 1 to 30 carbon atoms, organic dyes.
The method of claim 1,
The alkoxy is represented by -OR, wherein R is selected from C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl and C 2-20 aryl, organic dyes.
The method of claim 1,
The alkoxy is methoxy, ethoxy, propoxy, appendix, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, Tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosanyloxy, pentyloxy, hexyloxy, 3,3-dimethylbutyloxy, 2 An organic dye selected from ethylbutyloxy, 2-ethylhexyloxy, 2-methylheptyloxy, 2-propylbutyloxy, benzyloxy, methylbenzyloxy and isomers thereof.
The method of claim 1,
Will be selected from the following formulas 2 to 3, an organic dye.
[Formula 2]

[Formula 3]

Here, R ^a to R ^d are hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1-30 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 2 -C Selected from alkoxy of 30 and alkylcarbonyl having 1 to 30 carbon atoms,
R to R 'are each selected from alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms and aryl having 2 to 20 carbon atoms.)
At least one of the organic dyes of claim 1;
Including,
Organic dye composition.
The method of claim 6,
The composition will further comprise a co-adsorbent; composition.
The method of claim 6,
The composition, a metal oxide; will further comprise.
A first electrode;
A light absorption layer formed on the first electrode; And
A second electrode formed on the light absorption layer;
Including,
The light absorption layer is a metal oxide; And the organic dye of claim 1 or the composition of claim 6; comprising, dye-sensitized solar cell.
The method of claim 9,
The metal oxide includes at least one selected from the group consisting of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm and Ga. Dye-sensitized solar cell.
The method of claim 9,
The light absorbing layer comprises a metal oxide film in the form of a porous film, and formed on at least a portion of the metal oxide film by coating, impregnation or both of the composition, dye-sensitized solar cell.
The method of claim 9,
The metal oxide is, having a size of 1 nm to 1000 nm, dye-sensitized solar cell.
The method of claim 9,
The dye-sensitized solar cell, wherein the light absorption layer is transparent and has a thickness of 10 μm or less.
The method of claim 9,
Between the light absorption layer and the second electrode, an electrolyte; further comprising,
The electrolyte comprises a ionic liquid electrolyte or a liquid electrolyte, dye-sensitized solar cell.
Preparing a first electrode;
Preparing the second electrode; And
Disposing a light absorption layer between the first electrode and the second electrode;
Including,
The light absorption layer is a metal oxide; And the organic dye of claim 1 or the composition of claim 6; comprising a, method for producing a dye-sensitized solar cell.
The method of claim 15,
The light absorbing layer is formed by coating, impregnating, or both of the composition on at least a portion of the metal oxide film, method of manufacturing a dye-sensitized solar cell.

Images