KR20200142800A - Organic dyes, compositions and dye-sensitized solar cells - Google Patents

Abstract

The present invention relates to a high-efficiency, high-stability, and low-cost organic dye, to a composition comprising the same, and to a dye-sensitized solar cell and, more specifically, to an organic dye into which a twisted pi-spacer and a DPP-based core unit are introduced, to a composition comprising the same, and to a dye-sensitized solar cell.

Description

Organic dyes, compositions containing them, and dye-sensitized solar cells {ORGANIC DYES, COMPOSITIONS AND DYE-SENSITIZED SOLAR CELLS}

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

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

Silicon solar cells have technical limitations in order to be applied to various commercial products beyond the function of a solar cell module that simply generates energy. Since the silicon solar cell has a rapid decrease in efficiency according to the angle of incidence of the sun, the module can be applied only to an outdoor roof, and the conversion efficiency is lowered at a high temperature 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 close to real life.Dye-Sensitized Solar Cells (DSCs) to solve these problems and develop solar cells that are close to real life. There is a growing interest in

In order to apply BIPVs (building integrated photovoltaics) of dye-sensitized solar cells, various colors, stability, high efficiency and low cost of dyes are required, and many red and green dyes with high efficiency/high stability/low cost have been reported, but blue dyes are types. No dyes satisfying both high efficiency/high stability/low cost have been reported. In order to achieve low cost, a dye in which a DPP (diketopyrrolopyrrole) unit is introduced has been reported, and the DPP unit is a unit that absorbs a red region (~600 nm) of visible light, and is suitable as a core unit of a blue dye. However, symmetric DPP (symmetric DPP) is a strong electron acceptor unit and shows low efficiency (~2%) due to the large number of back electron transfer (BET) in which electrons injected into TiO ₂ return back to the oxidized dye. In addition, the introduction of an asymmetric DPP (DPP) unit reduced BET and developed high-efficiency blue dyes, and succeeded in commercialization at Dyenamo. However, it is a long synthesis process that only requires 5-steps to synthesize the core unit, which requires high cost.

The present invention provides an organic dye, which is a high efficiency, high stability, and low cost blue dye based on a DPP (diketopyrrolopyrrole) by controlling an intramolecular electronic coupling.

The present invention is to provide an organic dye composition comprising the organic dye according to the present invention.

The present invention is to provide a dye-sensitized solar cell comprising the organic dye or organic dye composition according to the present invention.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, it relates to an organic dye, which is a compound represented by the following Formula 1 or Formula 2.

[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,

Each of R ¹ to R ² is hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, and 1 to 30 carbon atoms. Of alkoxy, C1-C30 alkylcarbonyl, C6-C30 aryl, and C5-C30 heteroaryl,

R ³ to R ⁶ are, respectively, hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 to 30 carbon atoms Of alkoxy, C1-C30 alkylcarbonyl, C6-C30 aryl, and C5-C30 heteroaryl,

The aryl and heteroaryl are, respectively, unsubstituted or halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 To 30 alkoxy, C 1 to C 30 alkylcarbonyl, C 6 to C 20 aryl, and C 5 to C 20 heteroaryl further substituted by at least one of, the heteroaryl is at least one of N, O and S Contains hetero atoms;

π is selected from π-spacers represented by the following formula.

(Here, two of R ⁷ to R ¹² are linking groups, and the rest are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1 to C 30 alkyl, C 2 to C 30 alkenyl, and C 2 It is selected from alkynyl of to 30))

According to an embodiment of the present invention, R ¹ to R ² may be selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms and heteroaryl having 5 to 30 carbon atoms, respectively.

According to an embodiment of the present invention, R ¹ to R ² may each be selected from the following formula.

(Here, R _a to R _f One of them is a linking group, and the other is selected from hydrogen, halogen, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, and alkoxy having 1 to 20 carbon atoms.)

According to an embodiment of the present invention, two of R ⁷ to R ¹² are linking groups, and the rest are, respectively, hydrogen, halogen, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and alkynes having 2 to 10 carbon atoms. It may be selected from Neil.

According to an embodiment of the present invention, the π-space group may be selected from the following.

,

,

및

,

,

And

(Where, R ⁷ , R ⁹ R ¹⁰ and R ¹² are each, It is selected from C1-C10 alkyl and C2-C10 alkenyl.)

According to an embodiment of the present invention, the π-space group may form a twist angle of 0 ^o to 90 ^o in the molecule of the compound represented by Formula 1 or Formula 2.

According to an embodiment of the present invention, the alkoxy is represented by -OR, and R is in a C1-C30 alkyl, a C2-C30 alkenyl, a C2-C30 alkynyl, and a C2-C30 aryl. It may be selected.

According to an embodiment of the present invention, the organic dye may be selected from Formulas 3 and 4 below.

[Formula 3]

[Formula 4]

(Wherein, R is selected from C 1 to C 10 alkyl, C 2 to C 10 alkenyl, C 2 to C 10 alkynyl and C 2 to C 20 aryl, and R ³ to R ⁶ are defined in Formulas 1 and 2 Same as.)

According to an embodiment of the present invention, the organic dye may be a blue dye.

According to an embodiment of the present invention, it relates to an organic dye composition comprising an organic dye comprising at least one of the compounds represented by the formulas 1 and 2 according to the present invention.

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 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 include at least one selected from the group consisting of.

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

According to an embodiment of the present invention, a first electrode; A light absorbing layer formed on the first electrode; And a second electrode formed on the light absorption layer. Including, the light absorption layer, metal oxide; And it relates to a dye-sensitized solar cell comprising the organic dye according to the present invention.

The present invention can provide a novel blue organic dye capable of reducing the occurrence of back electron transfer (BET), which has been previously problematic, and solving all of efficiency, stability and cost. In addition, the organic dye according to the present invention improves the performance of the dye-sensitized solar cell, and can be manufactured with a low production cost and a simple process, which is advantageous for dissemination of blue dye.

1 is a “Three-state Marcus-Hush diagram” of a DPP-series (HDD|Spacer=0) manufactured in an embodiment of the present invention according to an embodiment of the present invention, and It is an exemplary illustration of the BET phenomenon in the molecule.
Figure 2 is, according to an embodiment of the present invention, (a) UV-Vis spectrum (in THF solution), (b) CV (Cyclic voltammetry) of the DPP-series and commercial dyenamo blue prepared in the embodiment of the present invention And (c) DFT-calculated energy levels and related molecular orbitals (MO) from HOMO-2 to LUMO+2.
Figure 3 is, according to an embodiment of the present invention, (a) JV curve, (b) IPCE, (c) EIS spectrum of the DPP-series and commercial dyenamo blue prepared in the embodiment of the present invention, (d) peripheral It shows the stability test results of bTPA-DPP-DMP under indoor lighting.
4, according to one embodiment of the invention, the DPP- Transient PL series on the Al ₂ O ₃ film with a THF (blue lines) of the DPP- series manufactured by an embodiment of the present invention decays or TCSPC (gray lines) of the experimental IRF (instrument response function), which are (a) DD-DPP-Ph, (b) DD-DPP-MP, (c) DD-DPP-DMP and (d) bTPA-DPP-DMP. (Excitation by 374.6 nm laser and signal detection at 500.0 nm).

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express a preferred embodiment of the present invention, which may vary depending on the intention of users or operators, or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the contents throughout the present specification. The same reference numerals in each drawing indicate the same members.

Throughout the specification, when a member is said to be positioned "on" another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components.

The present invention relates to a DPP (diketopyrrolopyrrole)-based organic dye, according to an embodiment of the present invention, the organic dye is a low-cost symmetric DPP core unit is introduced, DPP and twisted π-space group (π- spacers) is a DPP-based blue organic dye that can reduce BET and increase efficiency through electrical coupling control.

According to an embodiment of the present invention, the organic dye may be a DPP-based organic dye represented by Formula 1 and/or Formula 2 below.

[Formula 1]

The compound represented by Formula 1 has a symmetric DPP core unit introduced, which can reduce the synthesis step and lower the manufacturing cost compared to the synthesis process of the long core unit of 5-steps or more that occurs when the introduction of the existing asymmetric DPP unit. . For example, the organic dye according to the present invention is applied with a symmetric DPP unit that can be synthesized in 1-step.

R ¹ to R ² in Formula 1 are, respectively, hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, It may be selected from alkoxy having 1 to 30 carbon atoms, alkylcarbonyl having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, and heteroaryl having 5 to 30 carbon atoms.

Preferably, R ¹ to R ² may be selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms and heteroaryl having 5 to 30 carbon atoms, respectively. More preferably, each of R ¹ to R ² may be selected from the following formula.

The R _a to R _f One of them is a linking group, and the rest may be selected from hydrogen, halogen, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, and alkoxy having 1 to 20 carbon atoms.

The R ³ to R ⁶ are, respectively, hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 to carbon atoms It may be selected from alkoxy of 30, alkylcarbonyl having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, and heteroaryl having 5 to 30 carbon atoms.

Preferably, R ³ to R ⁶ may be selected from C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 1 to C 20 alkoxy and C 1 to C 20 alkylcarbonyl have.

The π is a π-spacers, and BET by controlling the electronic coupling between the DPP and the π-space group by changing the dihedral angle between the DPP unit and the π-space group. Can be reduced, and the efficiency in DSC can be increased.

The π-space group is 0 ^o to 90 ^o in the molecule of the compound represented by Chemical Formula 1; ^Greater than 0 ^o to 90 ^o ; 5 ^o to 90 ^o ; Alternatively, a twist angle of 10 ^o to 80 ^o is formed, which can control the electrical coupling of the DPP and the π-space group.

The π-space group may be selected by the following formula.

Two of the R ⁷ to R ¹² are linking groups, and the others are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, and 2 to 30 carbon atoms. It may be selected from alkynyl of. The π-space group forms a twisted π-spacer instead of a planar π-spacer in the molecule, and in order to induce a weak electrical coupling with DPP, R ^{All of 7} to R ¹² except for a linking group are not hydrogen.

Preferably, two of R ⁷ to R ¹² are each of hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1 to C 20 alkyl, C 2 to C 20 alkenyl and It is selected from alkynyl having 2 to 20 carbon atoms, and more preferably may be selected from the following formula.

,

,

및

,

,

And

The R ⁷ , R ⁹ R ¹⁰ and R ¹² are each, It may be selected from C1 to C10 alkyl and C2 to C10 alkenyl.

[Formula 2]

In Chemical Formula 2, as in Chemical Formula 1, a symmetric DPP core unit is introduced, which can reduce the synthesis step and lower the manufacturing cost compared to the synthesis process of a long core unit of 5-steps or more that occurs when introducing a conventional asymmetric DPP unit. . For example, the organic dye according to the present invention is applied with a symmetric DPP unit that can be synthesized in 1-step. In addition, by introducing a TPA (triphenylamine) unit, the efficiency can be further improved by reducing the aggregation of dyes in the molecule.

It is in formula 2 R ¹ to R ^2, and represents hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, C 1 -C 30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, It may be selected from alkoxy having 1 to 30 carbon atoms, alkylcarbonyl having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, and heteroaryl having 5 to 30 carbon atoms.

Preferably, R ¹ to R ² may be selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms and heteroaryl having 5 to 30 carbon atoms, respectively. More preferably, each of R ¹ to R ² may be selected from the following formula.

The R _a to R _f One of them is a linking group, and the others are hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms and 5 carbon atoms. It may be selected from heteroaryl of to 20. Preferably, in order to reduce efficiency and dye aggregation by introducing a bulkyl alkyl chain, all of the rest except for the linking group are not hydrogen and/or halogen, and at least one is a C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C It may be selected from 2 to 20 alkynyl and 1 to 20 alkoxy.

The R ³ to R ⁶ are, respectively, hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 to carbon atoms It may be selected from alkoxy of 30, alkylcarbonyl having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, and heteroaryl having 5 to 30 carbon atoms.

Preferably, R ³ to R ⁶ may be selected from C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 1 to C 20 alkoxy and C 1 to C 20 alkylcarbonyl have.

The π is a π-spacers, and by changing the dihedral angle between the DPP unit and the π-space group, the electronic coupling of the DPP and the π-space group is adjusted. It can reduce BET and increase the efficiency in DSC. The π-space group may be selected by the following formula. The π-space group is 0 ^o to 90 ^o in the molecule of the compound represented by Chemical Formula 2; ^Greater than 0 ^o to 90 ^o ; 5 ^o to 90 ^o ; Alternatively, a twist angle of 10 ^o to 80 ^o is formed, which can control the electrical coupling of the DPP and the π-space group.

Two of the R ⁷ to R ¹² are linking groups, and the others are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, and 2 to 30 carbon atoms. It may be selected from alkynyl of. The π-space group forms a twisted π-spacer rather than a planar π-spacer, and in order to induce a weak electrical coupling with DPP, among R ⁷ to R ¹² All other than the linking group are not hydrogen.

Preferably, two of R ⁷ to R ¹² are each of hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, and carbon number except for the linking group. It is selected from 2 to 20 alkynyl, more preferably may be selected from the following formula.

,

,

및

,

,

And

The R ⁷ , R ⁹ R ¹⁰ and R ¹² are each, It may be selected from C1 to C10 alkyl and C2 to C10 alkenyl.

As mentioned in the present specification, the C1-C30 alkyl, C2-C30 alkenyl, and C2-C30 alkynyl may be linear or branched.

As mentioned in the present specification, the alkoxy having 1 to 30 carbon atoms, the alkoxy is represented by -OR, and R is an alkyl having 1 to 30 carbon atoms, an alkenyl having 2 to 30 carbon atoms, an alkynyl having 2 to 30 carbon atoms, and It may be selected from C6-C30 aryl and C5-C30 heteroaryl. For example, 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.

The aryl having 6 to 20 carbon atoms and heteroaryl having 5 to 20 carbon atoms are monocyclic, bicyclic or tricyclic carbocyclic rings, and at least one ring is aromatic. For example, it may be phenyl, biphenyl, naphnyl, indanyl, and the like. Respectively, unsubstituted or halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, 1 carbon atom To 30 alkylcarbonyl, aryl having 6 to 30 carbon atoms, and further substituted by at least one of heteroaryl having 5 to 30 carbon atoms, and the heteroaryl may include at least one hetero atom of N, O and S .

The organic dye may be selected from Formulas 3 and 4 below.

[Formula 3]

[Formula 4]

In Formulas 3 and 4, R is selected from C1 to C10 alkyl, C2 to C10 alkenyl, C2 to C10 alkynyl and C6 to C20 aryl and C5 to C20 heteroaryl, and R ³ To R ⁶ are as mentioned in Formula 1 and Formula 2.

According to an embodiment of the present invention, the organic dye is a dye applicable to an optical device, and may be applied to, for example, a transparent and flexible photoelectrode. For example, it can 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 Formulas 1 to 2.

According to an embodiment of the present 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; Alternatively, it may be 0.1 to 10 parts by weight. If it is included within the above content range, adsorption and coating are well performed on semiconductor oxide, and performance is improved, and a thin and transparent photoactive film and a flexible device using the same, for example, a dye-sensitized solar cell may be provided.

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

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

According to an embodiment of the present invention, the composition may further include a co-adsorbent, and more specifically, carbon nanotubes, graphene, carbon black, deoxycholic acid, dehydrodeoxcholic acid, ke Nodeoxycholic acid, choline acid methyl ester, choline acid sodium 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 metals and metal compounds, and the metal compounds may be oxides, nitrides, alloys, etc. . 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 its It may be an oxide or an alloy thereof. The semiconductor fine particles may be included in an amount of 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 semiconductor fine particles may be porous.

The present invention relates to a dye-sensitized solar cell, and according to an embodiment of the present invention, the dye-sensitized solar cell is a thin-film dye-sensitized solar cell that satisfies high efficiency, high stability, and low cost by applying the organic dye according to the present invention. A battery can be provided.

According to an embodiment of the present invention, the dye-sensitized solar cell includes: a first electrode; A light absorbing 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 be applied without limitation as long as it is applicable to a dye-sensitized solar cell, and may include a transparent substrate and a conductive metal oxide film. 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. I can. The conductive metal oxide film may be formed on a transparent substrate.

The transparent substrate may be glass, quartz, plastic, or the like, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polypropylene, polyimide, and triacetylcellulose.

According to an embodiment of the present invention, the second electrode may be applied without limitation as long as it is applicable to a dye-sensitized solar cell, and may include a transparent substrate, a transparent electrode and/or a catalyst electrode, and the transparent electrode is a transparent substrate. It can be formed on.

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 ). I can. The transparent substrate is as mentioned in the first electrode 110 and may be the same as or different from the first electrode.

The catalytic electrode is formed on the transparent substrate or the transparent electrode, and serves to activate an oxidation-reduction pair (Pt), gold (Au), ruthenium (Ru), palladium (Pd). ), rhodium (Rh), iridium (Ir), osmium (Os), carbon (C), titanium oxide (TiO ₂ ), and at least one selected from the group consisting of a conductive polymer.

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

The semiconductor fine particles may be metals and metal compounds, and the metal compounds may be oxides, nitrides, alloys, or 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, and 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 ), and strontium titanium oxide (TiSrO ₃ ).

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. The semiconductor fine particles may be porous.

According to an embodiment of the present invention, the light-absorbing layer includes a porous film made of semiconductor fine particles, and an organic dye or composition according to the present invention is adsorbed on at least a portion of the film by coating, impregnation, or both. Or, it may be a combination). The coating and impregnation may adsorb an organic dye or composition to the pores, the surface, 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; Alternatively, it may have a 0.5 μm to 3.5 μm. If it is included in the thickness range, it is transparent and efficiency is improved, and a flexible solar cell may be provided by preventing a peeling off phenomenon.

According to an embodiment of the present invention, an electrolyte may be further included between the first electrode and the second electrode, and 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 a dye-sensitized solar cell, and preferably includes a liquid electrolyte, an ionic liquid electrolyte, or both, and, for example, iodine (I ₂ ), lithium ioda Id (LiI), 1-butyl-2-methyl imidazolium iodide, 1-allyl-3-methylimidazolium iodide, 1-Allyl-3-methylimidazolium iodide, 1,3-dimethylimidazolium iodide (1,3-Dimethylimidazolium iodide), 1-hexyl-2,3-dimethylimidazolium iodine (1-Hexyl-2,3-dimethylimidazolium iodide), 1-butyl-2, 3-dimethylimidazolium iodine (1-Butyl-2,3-dimethylimidazolium iodide), 1-dodecyl-3-methylimidazolium iodine (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 Imidazolium iodine (1-Ethyl-3-methylimidazolium iodide), 1-hexyl-3-methylimidazolium iodide (1-Hexyl-3-methylimidazolium iodide), 1-methyl-3-propylimidazolium iodine (1 -Methyl-3-propylimidazolium iodide) and 4-tert-butylpyridine (TBP); Cobalt (II/III) electrolyte; And the like, and those dissolved in methoxyacetonitrile, valeronitrile, and acetonitrile may be applied.

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

According to an embodiment of the present invention, the step of preparing the first electrode and the step of preparing the second electrode may be performed according to a process applied in the technical field of the present invention, such as coating and deposition, according to the above-mentioned configuration. Can be manufactured.

According to an embodiment of the present invention, the step of disposing a light absorption layer between the first photoelectrode and the second electrode includes forming a light absorption layer on the first electrode or preparing a light absorption layer film to provide a first electrode and It can be bonded between the second electrodes in a sandwich form.

The light absorption layer may be formed by coating or impregnating at least a portion of the semiconductor fine particle film with an organic dye or composition, or both.

The light absorption layer may form a porous semiconductor fine particle film by coating a semiconductor fine particle 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, and the coating is 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 described with reference to preferred embodiments of the present invention, the present invention is not limited thereto, and within the scope not departing from the spirit and scope of the present invention described in the following claims, detailed description of the invention, and the accompanying drawings. Various modifications and changes can be made to the present invention.

Example

[Scheme 1]

A dye compound based on DPP (Diketopyrrolopyrrole) was synthesized according to Scheme 1.

(1) 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (3,6-di(thiophen-2-yl) Synthesis of pyrrolo[3,4- c ]pyrrole-1,4(2 H ,5 H )-dione, 2 )

To shrink the reaction flask, elemental sodium (elementary sodium, 3.18 g, 138.26 mmol) in tert- amyl alcohol was added (tert -amyl alcohol, 75 mL), and completely dissolved when drying the mixture was stirred at 110 ℃. The temperature was lowered to 90° C., and 2-thiophenecarbonitrile (6.67 mL, 71.53 mmol) was added at once to obtain a brown substance. A solution of diethyl succinate (4.8 mL, 28.66 mmol) in tert-amyl alcohol (18 mL) was added dropwise, and the reaction mixture was stirred at 110° C. overnight. A solution of acetic acid (AcOH, 20 mL) in methanol (100 mL) was added into the material, and after further stirring at 110° C. for 2 hours, a dark purple solid precipitate was formed and collected by vacuum filtration. The precipitate was washed several times with methanol and purified. The product was dried to obtain a purple solid (7.67 g, 89%). ¹ H NMR (400 MHz, DMSO) δ (ppm): 11.25 (s, 2H), 8.21 (dd, J = 4.0, 1.2 Hz, 2H), 7.97 (dd, J = 4.8, 1.2 Hz, 2H), 7.3 (t, J = 4.4 Hz, 2H).

(2) 2,5-bis(2-ethylhexyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione ( Synthesis of 2,5-bis(2-ethylhexyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4- c ]pyrrole-1,4(2 H ,5 H )-dione, 3 )

Compound 2 (6.0 g, 19.976 mmol) and K ₂ CO ₃ (8.3 g, 59.982 mmol) were added into a 250 mL round bottom flask under argon. An anhydrous degassed solution of DMF (100 mL) was added to the mixture. The reaction solution was refluxed at 120° C. for 1 hour. Next, 2-ethylhexyl bromide (2-Ethylhexyl bromide, 10.3 mL, 59.982 mmol) was added dropwise, and the reaction mixture was refluxed at 130° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. After collecting the organic layer, the solvent was evaporated with a rotary evaporator and concentrated. The remaining crude product was purified by column chromatography using a CH ₂ Cl ₂ mixture as an eluent to obtain a brown solid compound 3 (8.6 g, 82%). ¹ H NMR (400 MHz, CDCl) δ (ppm): 8.90 (dd, J = 3.6, 1.2 Hz, 2H), 7.63 (dd, J = 5.2, 1.2 Hz, 2H), 7.27 (t, J =5.2, 1.2 Hz, 2H), 4.03 (m, 4H), 1.86 (m, 2H), 1.38-1.22 (m, 16H), 0.89-0.83 (m, 12H).

(3) 3-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole- 1,4(2H,5H)-dione(3-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-6-(thiophen-2-yl)pyrrolo[3,4- c ]Synthesis of pyrrole-1,4(2 H ,5 H )-dione, 4 )

To a suspension of compound 3 (1.0 g, 1.906 mmol) in anhydrous CHCl ₃ (190 mL) at 0 °C was added NBS (339 mg, 1.906 mmol) under argon. The reaction solution was slowly heated from 0 °C to RT while stirring while blocking the light and stirred overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, and the solvent was evaporated with a rotary evaporator and concentrated. The residual crude product was purified by column chromatography using a mixture of Hex/CHCl _3- (3:1 = v / v ) as an eluent to obtain a brown solid compound 4 (560 mg, 49%). ¹ H NMR (400 MHz, CDCl) δ (ppm): 8.90 (d, 1H), 8.62 (d, 1H), 7.64 (d, 1H), 7.26 (d, 1H), 7.23 (d, 1H), 4.02 -3.94 (m, 4H), 1.84 (m, 2H), 1.31-1.25 (m, 16H), 0.87 (m, 12H).

(4) 4-(5-(2,5-bis(2-ethylhexyl)-3,6-dioxo-4-(thiophen-2-yl)-2,3,5,6-tetrahydropy Rolo[3,4-c]pyrrol-1-yl)thiophen-2-yl)benzaldehyde (4-(5-(2,5-bis(2-ethylhexyl)-3,6-dioxo-4-( Synthesis of thiophen-2-yl)-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)benzaldehyde, 5a )

Compound 4 (400 mg, 0.663 mmol), 4-formylphenylboronic acid, 199 mg, 1.325 mmol) and Pd(PPh ₃ ) ₄ (38 mg, 0.033 mmol) in a 50 mL round bottom flask under argon Added in. A degassed solution of THF (22 mL) and 2 MK ₂ CO ₃ (1.3 mL) was added to the mixture. The reaction solution was refluxed at 65°C overnight. The resulting solution was worked up with CH ₂ Cl ₂ and H ₂ O. The organic layer was collected, and the solvent was evaporated with a rotary evaporator and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent to obtain compound 5a (400 mg, 96%) as a dark purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.04 (s, 1H), 8.94 (d, J = 4.0 Hz, 1H), 8.93 (dd, J = 3.6, 1.2 Hz, 1H), 7.95 (dd , J = 6.4, 2.0 Hz, 2H), 7.84 (dd, J = 6.4, 2.0 Hz, 2H), 7.66 (dd, J = 5.2, 1.2 Hz, 1H), 7.60 (d, J = 4.0 Hz, 1H) , 7.29 (t, J = 5.2 Hz, 1H), 4.06 (m, 4H), 1.90 (m, 2H), 1.38-1.25 (m, 16H), 0.92-0.83 (m, 12H).

(5) 4-(5-(2,5-bis(2-ethylhexyl)-3,6-dioxo-4-(piopen-2-yl)-2,3,5,6-tetrahydropy Lolo[3,4-c]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde (4-(5-(2,5-bis(2-ethylhexyl)-3,6-dioxo- Synthesis of 4-(thiophen-2-yl)-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde , 5b )

Compound 4 (500 mg, 0.828 mmol), 4-formyl-2-methylphenylboronic acid (4-formyl-2-methylphenylboronic acid, 272 mg, 1.657 mmol) and Pd(PPh ₃ ) ₄ (48 mg, 0.041 mmol) Was added into a 50 mL round bottom flask under argon. A degassing solution of THF (25 mL) and 2 MK ₂ CO ₃ (1.7 mL) was added to the mixture. The reaction mixture was refluxed at 65° C. overnight. The resulting solution was worked up with CH ₂ Cl ₂ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent to obtain compound 5b (444 mg, 83%) as a dark purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.04 (s, 1H), 8.96 (d, J = 4.0 Hz, 1H), 8.93 (dd, J = 3.6, 1.2 Hz, 1H), 7.82 (bs , 1H), 7.78 (dd, J =8.0, 1.2 Hz, 1H), 7.65 (dd, J = 5.2, 1.2 Hz, 2H), 7.36 (d, J = 4.0 Hz, 1H), 7.29 (t, J = 5.2 Hz, 1H), 4.05 (m, 4H), 2.60 (s, 3H), 1.92-1.85 (m, 2H), 1.38-1.25 (m, 16H), 0.92-0.83 (m, 12H). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 191.72, 161.77, 161.68, 146.73, 140.68, 139.73, 138.78, 136.93, 135.90, 135.67, 135.52, 132.38, 130.79, 130.60, 129.77, 128.86, 128.50, 127.50 108.40, 107.99, 45.95, 45.90, 39.29, 39.07, 30.27, 30.24, 30.20, 30.18, 29.69, 28.48, 28.33, 23.56, 23.51, 23.09, 23.06, 21.48, 14.05, 14.03, 10.49.

(6) 4-(5-(2,5-bis(2-ethylhexyl)-3,6-dioxo-4-(thiophen-2-yl)-2,3,5,6-tetrahydropy Rolo[3,4- c ]pyrrol-1-yl)piopen-2-yl)-3,5-dimethylbenzaldehyde(4-(5-(2,5-bis(2-ethylhexyl)-3,6 -dioxo-4-(thiophen-2-yl)-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylbenzaldehyde, 5c ) Synthesis of

Compound 4 (1.5 g, 2.485 mmol), 4-formyl-2,6-dimethylphenylboronic acid, 530 mg, 2.982 mmol), Pd ₂ (dba) ₃ (68 mg, 0.075 mmol), and X-Phos (71 mg, 0.149 mmol) were added in a 150 mL round bottom flask under argon. A degassing solution of THF (40 mL) and 2 MK ₃ PO ₄ (5.0 mL) was added to the mixture. The reaction mixture was refluxed at 75° C. overnight. The resulting solution was worked up with CH ₂ Cl ₂ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent to obtain compound 5c (1.5 g, 98%) as a dark purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.01 (s, 1H), 8.99 (d, J = 3.6 Hz, 1H), 8.91 (dd, J = 3.6, 0.8 Hz, 1H), 7.65 (bs , 1H), 7.64 (dd, J = 5.2, 0.8 Hz, 2H), 7.28 (t, J = 5.2 Hz, 1H), 7.04 (d, J = 3.6 Hz, 1H), 4.03 (m, 4H), 2.28 (s, 6H), 1.98-1.88 (m, 2H), 1.37-1.25 (m, 16H), 0.91-0.81 (m, 12H). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 192.15, 161.76, 161.67, 154.44, 140.47, 139.96, 139.33, 138.96, 136.26, 135.90, 135.35, 130.63, 130.59, 129.79, 128.62, 128.44, 128.25, 108. 107.95, 45.92, 45.89, 39.21, 39.05, 30.18, 30.12, 30.09, 28.35, 28.33, 23.52, 23.40, 23.04, 22.99, 20.86, 14.00, 13.96, 10.47, 10.39.

(7) 4-(5-(4-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6- Tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)benzaldehyde(4-(5-(4-(5-bromothiophen-2-yl)-2,5-bis Synthesis of (2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)benzaldehyde, 6a )

To a suspension of compound 5a (400 g, 0.636 mmol) in anhydrous CHCl ₃ (30 mL) at 25° C. was added NBS (125 mg, 0.700 mmol) under argon. The reaction mixture was stirred at 25° C. for 5 hours while the light was blocked. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent to obtain compound 6a (380 mg, 84%) as a purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.04 (s, 1H), 8.94 (d, J = 4.0 Hz, 1H), 8.68 (d, J = 4.0, 1H), 7.94 (dd, J = 6.8, 2.0 Hz, 2H), 7.83 (dd, J = 6.4, 1.2 Hz, 2H), 7.60 (d, J = 4.4 Hz, 1H), 7.24 (d, J = 4.4 Hz, 1H), 4.08-3.95 ( m, 4H), 1.90 (m, 2H), 1.38-1.25 (m, 16H), 0.93-0.85 (m, 12H).

(8) 4-(5-(4-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6- Tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde (4-(5-(4-(5-bromothiophen-2-yl)-2 ,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde, 6b ) Synthesis

To a suspension of compound 5b (417 g, 0.649 mmol) in anhydrous CHCl ₃ (30 mL) was added NBS (127 mg, 0.713 mmol) under argon at 25°C. The reaction mixture was stirred at 25° C. for 5 hours while blocking the light. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent, and compound 6b (350 mg, 75%) was obtained as a purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.03 (s, 1H), 8.95 (bs, 1H), 8.65 (bs, 1H), 7.81 (bs, 1H), 7.77 (d, J = 6.8 Hz , 1H), 7.64 (d, J = 7.6 Hz, 1H), 7.35 (d, J = 3.6 Hz, 1H), 7.23 (d, J = 3.2 Hz, 1H), 4.04-3.93 (m, 4H), 2.59 (s, 3H), 1.90 (m, 2H), 1.37-1.25 (m, 16H), 0.91-0.85 (m, 12H). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 191.64, 161.47, 146.71, 140.16, 139.73, 138.66, 136.88, 136.57, 135.91, 135.36, 132.37, 132.15, 131.38, 131.21, 130.72, 129.45, 128.88, 127. 127.37, 108.17, 45.96, 39.24, 39.06, 30.21, 30.19, 30.10, 28.43, 28.26, 23.51, 23.05, 23.00, 21.47, 14.02, 14.00, 10.44.

(9) 4-(5-(4-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3, Synthesis of 4- c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylbenzaldehyde ( 6c )

To a suspension of compound 5c (1.06 g, 1.614 mmol) in anhydrous CHCl ₃ (30 mL) at 25° C. was added NBS (316 mg, 1.775 mmol) under argon. The reaction mixture was stirred at 25° C. for 5 hours while blocking the light. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a CHCl3 mixture as an eluent, and compound 6c (880 mg, 74%) was obtained as a purple solid. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.01 (s, 1H), 9.00 (d, J = 4.0 Hz, 1H), 8.65 (d, J = 4.4 Hz, 1H), 7.65 (s, 2H ), 7.24 (d, J = 4.0 Hz, 1H), 7.04 (d, J = 4.0 Hz, 1H), 4.01-3.94 (m, 4H), 2.27 (s, 6H), 1.88-1.85 (m, 2H) , 1.37-1.22 (m, 16H), 0.92-0.81 (m, 12H). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 192.15, 161.61, 161.53, 145.82, 140.44, 139.32, 139.01, 138.89, 136.31, 136.20, 135.20, 131.43, 131.22, 130.51, 128.64, 128.35, 118.77, 108.20 107.92, 46.00, 39.21, 39.11, 30.17, 30.12, 29.69, 29.10, 28.35, 28.32, 23.56, 23.40, 23.03, 23.01, 20.86, 14.02, 13.98, 10.48, 10.39.

(10) 4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta [ b ]Indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4 -c ]pyrrol-1-yl)thiophen-2-yl)benzaldehyde (4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2, 3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6- Synthesis of tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)benzaldehyde , 7a )

Compound 6a (200 mg, 0.283 mmol), Compound D1 (258 mg, 0.565 mmol), Pd ₂ (dba) ₃ (13 mg, 0.014 mmol) X-Phos (13 mg, 0.028 mmol) and K ₃ PO ₄ (180 mg, 0.848 mmol) was added into a 100 mL round bottom flask under argon. A degassing solution of toluene (18 mL), tert-amyl-alcohol (3.0 mL) and H ₂ O (2.0 mL) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was purified by column chromatography using a mixture of CHCl ₃ as an eluent, and the crude product remaining in CHCl ₃ and H ₂ O was triturated with CH ₂ Cl ₂ and MeOH, and then a dark purple solid compound. 7a (260 mg, 88%) was obtained. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.00 (s, 1H), 9.07 (dt, J = 4.4, 1.2 Hz, 1H), 8.88 (d, J = 4.0 Hz, 1H), 7.91 (d , J = 8.4 Hz, 2H), 7.80 (d, J = 3.2 Hz, 2H), 7.56 (d, J = 4.0 Hz, 1H), 7.42-7.34 (m, 5H), 7.34-7.26 (m, 8H) , 7.03 (q, J = 8.0 Hz, 4H), 6.96 (d, J = 8.4 Hz, 1H), 6.94 (s, 1H), 4.76 (m, 1H), 4.07 (m, 4H), 3.82 (m, 1H), 2.12-2.03 (m, 2H), 1.92-1.65 (m, 6H), 1.42-1.26 (m, 16H), 0.94-0.86 (m, 12H). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 191.18, 161.93, 161.31, 152.10, 147.83, 146.30, 143.47, 141.27, 140.89, 140.69, 140.65, 138.81, 138.22, 137.50, 136.28, 131.02, 135.69 130.50, 130.45, 130.33, 128.78, 128.17, 127.48, 127.35, 127.26, 126.14, 126.06, 125.94, 123.87, 122.46, 122.39, 118.46, 118.44, 109.12, 108.50, 107.28, 68.91, 3988,95, 45.08 33.73, 30.90, 30.36, 28.60, 24.35, 23.69, 23.13, 23.09, 14.08, 10.60, 10.54.

(11) 4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta [ b ]Indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4 -c ]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde (4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl))- 1,2,3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3, Synthesis of 5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylbenzaldehyde , 7b )

Compound 6b (350 mg, 0.485 mmol), Compound D1 (444 mg, 0.970 mmol), Pd ₂ (dba) ₃ (22 mg, 0.024 mmol) X-Phos (23 mg, 0.048 mmol) and K ₃ PO ₄ (308 mg, 1.455 mmol) was added into a 100 mL round bottom flask under argon. A degassing solution of toluene (24 mL), tert-amyl-alcohol (4.0 mL) and H ₂ O (3.0 mL) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent, and after trituration with CH ₂ Cl ₂ and MeOH, compound 7b (500 mg, 98%) as a dark purple solid was obtained. . ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.03 (s, 1H), 9.06 (dt, J = 4.4, 1.2 Hz, 1H), 8.90 (d, J = 4.0 Hz, 1H), 7.82 (s , 1H), 7.77 (dd, J = 8.0, 1.2 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.41-7.37 (m, 5H), 7.35-7.31 (m, 6H), 7.28- 7.26 (m, 3H), 7.04 (q, J = 7.2 Hz, 4H), 6.97 (d, J = 8.4 Hz, 1H), 6.94 (s, 1H), 4.78 (m, 1H), 4.08 (m, 4H) ), 3.85 (m, 1H), 2.60 (s, 3H), 2.12-2.03 (m, 2H), 1.93-1.66 (m, 6H), 1.42-1.25 (m, 16H), 0.94-0.86 (m, 12H) ). ¹³ C NMR (100 MHz, CDCl) δ (ppm): 191.74, 162.07, 161.46, 152.00, 147.87, 145.98, 143.50, 141.23, 140.92, 140.78, 140.67, 138.95, 137.98, 136.88, 136.31, 135.80, 134.98, 132.38 131.06, 130.97, 130.76, 130.47, 130.35, 128.80, 128.19, 127.50, 127.38, 127.28, 126.40, 125.98, 123.93, 122.54, 122.44, 118.52, 108.83, 108.52, 107.31, 68.98, 45.98, 33.13, 30.32, 39.32 28.62, 28.53, 24.38, 23.61, 23.10, 21.52, 14.11, 14.06, 10.56.

(12) 4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta [ b ]Indole-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4 -c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylbenzaldehyde (4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)phenyl)) )-1,2,3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2, Synthesis of 3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylbenzaldehyde, 7c )

Compound 6c (350 mg, 0.476 mmol), Compound D1 (326 mg, 0.714 mmol), Pd ₂ (dba) ₃ (22 mg, 0.024 mmol) X-Phos (23 mg, 0.048 mmol) and K ₃ PO ₄ (303 mg, 1.427 mmol) was added into a 100 mL round bottom flask under argon. Toluene (25 mL), tert- amyl-alcohol was added to the degassed solution of (tert -amyl-alcohol, 2.5 mL ) and H ₂ O (1.5 mL) to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent, and after trituration with CH ₂ Cl ₂ and MeOH, compound 7c as a dark purple solid (320 mg, 63%) Was obtained. ¹ H NMR (400 MHz, CDCl) δ (ppm): 10.01 (s, 1H), 9.05 (d, J = 4.0 Hz, 1H), 8.94 (d, J = 3.6 Hz, 1H), 7.65 (s, 2H ), 7.41-7.38 (m, 5H), 7.34-7.31 (m, 5H), 7.29-7.28 (m, 3H), 7.07-7.00 (m, 5H), 6.98 (d, J = 8.0 Hz, 1H), 6.95 (s, 1H), 4.78 (m, 1H), 4.07 (m, 4H), 3.85 (m, 1H), 2.29 (s, 6H), 2.08-1.67 (m, 8H), 1.40-1.26 (m, 16H), 0.95-0.82 (m, 12H).

(13) 4-(5-(4-(5-(4-(bis(2',4'-bis(hexyloxy)biphenyl-4-yl)amino)phenyl)thiophen-2-yl) -2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophene-2- Days)-3,5-dimethylbenzaldehyde (4-(5-(4-(5-(4-(bis(2',4'-bis(hexyloxy)biphenyl-4-yl)amino)phenyl)thiophen- 2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl) Synthesis of -3,5-dimethylbenzaldehyde, 7d )

Compound 6c (120 mg, 0.163 mmol), Compound D2 (181 mg, 1.96 mmol), Pd ₂ (dba) ₃ (7.5 mg, 0.008 mmol) X-Phos (7.8 mg, 0.0163 mmol) and K ₃ PO ₄ (104 mg, 0.489 mmol) was added into a 100 mL round bottom flask under argon. A degassed anhydrous solution of toluene (15 mL), tert- amyl-alcohol (2.0 mL) and H ₂ O (1.0 mL) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ as an eluent, and triturated with CHCl ₃ and MeOH to obtain a dark purple gel compound 7d (187 mg, 79%). R _f = 0.49 (CHCl ₃ , run two times). ¹ H NMR (400 MHz, DMSO) δ (ppm): 10.01 (s, 1H), 9.15 (d, J = 4.0 Hz, 1H), 9.06 (d, J = 4.0 Hz, 1H), 7.70 (s, 2H ), 7.64 (d, J = 8.8 Hz, 2H), 7.56 (d, J = 4.4 Hz, 1H), 7.50 (d, J = 8.4 Hz, 4H), 7.22 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 4.0 Hz, 1H), 7.14 (d, J = 8.8 Hz, 4H), 7.09 (d, J = 8.4 Hz, 2H), 6.61 (d, J = 2.4 Hz, 2H), 6.55 ( dd, J = 8.8, 2.4 Hz, 2H), 3.99 (m, 12H), 2.30 (s, 6H), 1.98-1.89 (m, 2H), 1.80-1.68 (m, 8H), 1.50-1.20 (m, 40H), 0.92-0.79 (m, 24H). ¹³ C NMR (100 MHz, DMSO) δ (ppm): 192.73, 162.21, 161.79, 160.82, 157.94, 151.18, 149.66, 145.93, 145.84, 141.02, 140.09, 139.53, 139.11, 138.42, 137.66, 136.22, 135. 131.57, 131.29, 129.38, 129.27, 128.34, 127.78, 126.90, 125.26, 124.28, 123.24, 123.06, 109.02, 108.22, 106.62, 101.05, 68.97, 68.62, 46.35, 46.31, 40.10, 32.40, 2993, 29.26, 3084.10, 32.26, 3084. 26.58, 26.55, 24.35, 24.12, 23.77, 23.67, 23.33, 21.04, 14.43, 14.40, 14.36, 14.30, 10.85, 10.74.

(1) Synthesis of DD-DPP-Ph

2-cyano-3-(4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexa Hydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropy Rolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)phenyl)acrylic acid (2-cyano-3-(4-(5-(4-(5-(4-(4-( 2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3 ,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)phenyl)acrylic acid, 8a , DD-DPP-Ph )

Compound 7a (85 mg, 0.0817 mmol), cyanoacetic acid (139 mg, 1.63 mmol), and piperidine (0.2 mL, 2.04 mmol) were added into a 150 mL round bottom flask under argon. An anhydrous degassed solution (CHCl ₃ /CH ₃ CN, 2:3 v / v ) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography with a mixture of CHCl ₃ /MeOH/AcOH (10:1:0.1) as an eluent, triturated with CHCl ₃ and MeOH, and then compound 8a (47 mg) as a dark purple solid. , 52%) was obtained. ¹ H NMR (400 MHz, THF) δ (ppm): 8.95 (bs, 1H), 8.82 (bs, 1H), 7.99 (s, 1H), 7.87 (s, 1H), 7.78 (bs, 4H), 7.55 -7.49 (m, 3H), 7.30-7.28 (m, 3H), 7.25-7.16 (m, 6H), 7.13-7.11 (m, 2H), 6.87-6.63 (m, 4H), 6.78 (d, J = 8.4 Hz, 1H), 4.61 (m, 1H), 3.88 (m, 4H), 3.65 (m, 1H), 1.95-1.90 (m, 2H), 1.83-1.57 (m, 6H), 1.32-1.16 (m , 16H), 0.87-0.79 (m, 12H).

(2) Synthesis of DD-DPP-MP

2-cyano-3-(4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexa Hydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropy Rolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylphenyl)acrylic acid (2-cyano-3-(4-(5-(4-(5-(4-( 4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl )-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3-methylphenyl)acrylic acid, 8b , DD-DPP- MP )

Compound 7b (480 mg, 0.455 mmol), cyanoacetic acid (774 mg, 9.10 mmol), and piperidine (piperidine, 0.6 mL, 6.83 mmol) were added into a 150 mL round bottom flask under argon. An anhydrous degassed solution (CHCl ₃ /CH ₃ CN, 2:3 v / v ) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ /MeOH/AcOH (10:1:0.1) as an eluent, and triturated with CHCl ₃ and MeOH, and then a dark purple solid compound 8b ( 436 mg, 87%) was obtained.

¹ H NMR (400 MHz, THF) δ (ppm): 10.84 (bs, 1H), 9.16 (d, J = 3.2 Hz, 1H), 9.11 (d, J = 2.8 Hz, 1H), 8.21 (bs, 1H) ), 7.90 (d, J = 6.4 Hz, 1H), 7.67 (bs, 1H), 7.53 (bs, 1H), 7.37-7.32 (m, 5H), 7.30-7.25 (m, 6H), 7.22-7.20 ( m, 3H), 6.98 (d, J = 8.8 Hz, 5H), 6.89 (d, J = 8.0 Hz, 1H), 4.65 (m, 1H), 3.94 (m, 4H), 3.67 (m, 1H), 2.49 (s, 3H), 1.98 (m, 2H), 1.88-1.79 (m, 6H), 1.39-1.28 (m, 16H), 0.93-0.89 (m, 12H).

(3) Synthesis of DD-DPP-DMP

2-cyano-3-(4-(5-(4-(5-(4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexa Hydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropy Rolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylphenyl)acrylic acid (2-cyano-3-(4-(5-(4-(5-( 4-(4-(2,2-diphenylvinyl)phenyl)-1,2,3,3a,4,8b-hexahydrocyclopenta[ b ]indol-7-yl)thiophen-2-yl)-2,5-bis( 2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophen-2-yl)-3,5-dimethylphenyl)acrylic acid, 8c , DD-DPP-DMP ).

Compound 7c (200 mg, 0.187 mmol), cyanoacetic acid (318 mg, 3.74 mmol) and piperidine (0.46 mL, 4.68 mmol) were added into a 150 mL round bottom flask under argon. An anhydrous degassed solution (CHCl ₃ /CH ₃ CN, 2:3 v / v ) was added to the mixture. The reaction mixture was refluxed at 70°C overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was purified by column chromatography using a mixture of CHCl ₃ /MeOH/AcOH (10:1:0.1) as an eluent, and triturated with CHCl ₃ and MeOH, followed by trituration with a dark purple solid compound 8c ( 192 mg, 91%) was obtained. ¹ H NMR (400 MHz, THF) δ (ppm): 10.86 (bs, 1H), 9.17 (d, J = 3.6 Hz, 1H), 9.12 (d, J = 2.0 Hz, 1H), 8.26 (bs, 1H) ), 7.76 (bs, 2H), 7.49 (bs, 1H), 7.43-7.34 (m, 5H), 7.33-7.26 (m, 5H), 7.24-7.21 (m, 3H), 7.08 (d, J = 8.8 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 4.81 (m, 1H), 4.07 (m, 4H), 3.85 (m, 1H), 2.23 (s, 6H), 2.08-1.84 (m, 8H), 1.43-1.24 (m, 16H), 0.95-0.83 (m, 12H).

(4) bTPA-DPP-DMP

3-(4-(5-(4-(5-(4-(bis(2',4'-bis(hexyloxy)biphenyl-4-yl)amino)phenyl)thiophen-2-yl) -2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1-yl)thiophene-2- Il)-3,5-dimethylphenyl)-2-cyanoacrylic acid (3-(4-(5-(4-(5-(4-(bis(2',4'-bis(hexyloxy)biphenyl-4))) -yl)amino)phenyl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4- c ]pyrrol-1 Synthesis of -yl)thiophen-2-yl)-3,5-dimethylphenyl)-2-cyanoacrylic acid , 8d , bTPA-DPP-DMP )

Compound 7d (154 mg, 0.106 mmol), cyanoacetic acid (180 mg, 2.12 mmol) and piperidine (0.26 mL, 2.65 mmol) were added into a 150 mL round bottom flask under argon. An anhydrous degassed solution (CHCl ₃ /CH ₃ CN, v / v = 2:3) was added to the mixture. The reaction mixture was refluxed at 70° C. overnight. The resulting solution was worked up with CHCl ₃ and H ₂ O. The organic layer was collected, the solvent was removed with a rotary evaporator, and concentrated. The remaining crude product was subjected to column chromatography using a mixture of CHCl ₃ /MeOH/AcOH (10:1:0.1) as an eluent, and triturated with CHCl ₃ and MeOH (or acetone), and then a dark purple solid. Compound 8d (140 mg, 87%) was obtained. ¹ H NMR (400 MHz, THF) δ (ppm): 10.87 (bs, 1H), 9.18 (d, J = 4.0 Hz, 1H), 9.15 (d, J = 4.0 Hz, 1H), 8.27 (bs, 1H) ), 7.70 (s, 2H), 7.60 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 4H), 7.21 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.8 Hz, 6H), 7.05 (d, J = 3.2 Hz, 1H), 6.58 (d, J = 2.4 Hz, 2H), 6.52 (dd, J = 8.4, 2.0 Hz, 2H), 4.09-3.94 (m , 12H), 2.20 (s, 6H), 2.00-1.89 (m, 2H), 1.81-1.69 (m, 8H), 1.50-1.22 (m, 40H), 0.95-0.80 (m, 24H). HRMS (MALDI-TOF, m/z ) [M] calculated for C ₉₆ H ₁₁₈ N ₄ O ₈ S ₂ :1519.8425; found: 1519.8417.

Dye characterization

(1) DFT-calculated electronic coupling calculation

Table 1 shows the DFT-calculated electronic coupling (Hybrid functional: B3LYP, basis set: 6-311G (d, p), and C-PCM: acetonitrile) of the DPP series compounds prepared in Examples. Done.

H _DD|DPP H _DPP|Ph H _DPP|MP H _DPP|DMP Electronic coupling (cm ^-1 ) 2995 1294 1128 678

Looking at Table 1, Planar π-spacer (DD-DPP-Ph) has a strong electronic coupling with _DPP ( H _DPP|Ph = 1294 cm ^-1 ), which may cause a problem of BET. The twsited π-spacer of the dye according to the present invention induces weak electron coupling (DD-DPP-DMP, H _DPP|DMP = 678 cm ^-1 ) with _DPP , so that BET can be effectively reduced.

(2) Optical and electrochemical parameter analysis

The UV-Vis spectrum, CV (Cyclic voltammetry), DFT-calculated energy level and related MO (molecular orbitals) were measured and shown in Table 2 and FIG. 2.

λ _{max, abs} [nm] ε _max [L mol ^-One cm ^-One ] E _0-0 [eV] E _(S+/S) [V] Dyenamo Blue 336, 585 47,900, 53,350 1.867 0.986 DD-DPP-Ph 385, 621 63,150, 82,600 1.712 0.955 DD-DPP-MP 380, 616 50,650, 72,650 1.756 0.946 DD-DPP-DMP 372, 614 35,100, 70,000 1.851 0.840 bTPA-DPP-DMP 333, 603 62,050, 62,200 1.893 1.00

(* The ground-state oxidation potential of DPP-series was measured under the following conditions: electrolyte, 0.1 M NBu ₄ PF ₆ in Acetonitrile; electrode, platinum counter and Ag/AgCl reference were used with a ITO working electrode. .Fc ⁺ /Fc converted to NHE by addition of 0.63 V; Scan rate: 50 mV/s)

Referring to Table 2 and FIG. 2, the dye (DPP-series) according to the present invention is blue that selectively absorbs the remaining visible rays (550-700 nm and 300-450 nm) except for the blue region (450-500 nm). It can be confirmed that it is a dye. In addition, E _ox of the dye obtained through CV can be confirmed in FIG. 2.

2. DPP dye solar cell characteristics analysis

Measure the JV curve, IPCE and EIS spectrum of the solar cell of the DPP dye, and measure the stability test of bTPA-DPP-DMP and the IPCE spectrum and JV curve of bTPA-DPP-DMP/Dyenamo orange under ambient room lighting, Indicated.

Referring to Figure 3, in the JV curve and IPCE spectrum (Incident-photon-to-electron conversion effciency spectra) of DPP dye and commercial dyenamo blue, DD-DPP-Ph and DD-DPP-MP having strong electron coupling are dyenamo. It shows V _oc and power conversion effiency (PCE) lower than blue. On the other hand, DD-DPP-DMP with weak electron coupling significantly increased J _sc and V _oc , and showed higher efficiency than dyenamo blue as well as DD-DPP-Ph and DD-DPP-MP. In addition, it can be seen that bTPA-DPP-DMP, which introduced the same twisted π-spacer, achieved higher efficiency while reducing the aggregation of dyes (iodine electrolyte: 9.0% and cobalt electrolyte: 9.3%). The semicircle of the graph with the electrochemical impedance spectra (EIS) of FIG. 4C represents the charge recombination resistance of DSC. It shows that the smaller the electron coupling, the higher the charge recombination.

Regarding the stability of the dye, looking at (d) of FIG. 3, the DSC was manufactured with bTPA-DPP-DMP under ambient indoor condition (temperature: 25 ^o C, humidity: 40%, light: 500 lux). One DSC maintained 90% of the initial efficiency for 3000 hours (125 days). Regarding the highest efficiency of bTPA-DPP-DMP through co-sensitization, iodine-based DSC was performed using both bTPA-DPP-DMP and dyenamo orange dye in FIGS. 3 (e) to (f). It was produced and it can be seen that 10.0% PCE was achieved.

Transient PL decays of the DPP-series were measured on an Al ₂ O ₃ film with an experimentally measured instrument response function (IRF) of gray lines (TCSPC) or blue lines (THF), and are shown in FIG. 4. 4 shows that the electron-life of the weak electron-coupling dye is longer than that of the strong electron-coupling material even in the result of TCSPC (Time-correlated single photon counting). This shows that, consistent with the results of the device characteristics, weak electron coupling can effectively reduce the BET of DPP and increase the efficiency.

The photovoltaic device and TCSPC parameters of DPP-series dyes were measured and shown in Table 3.

J _SC (mA/cm ² ) V _OC (V) FF PCE ^a) (%) τ _One (ps) [A _One ]
τ ₂ (ps) [A _One ] τ _avg (ps) Dyenamo Blue 11.24 0.70 76.0 5.98 - - DD-DPP-Ph 13.00 0.61 67.1 5.30 117 (94.16%)
1706 (5.84%) 210 DD-DPP-MP 14.28 0.62 66.8 5.92 170 (82.35%)
1634 (17.65%) 429 DD-DPP-DMP 17.71 0.68 71.3 8.60 187 (77.07%)
1724 (22.93%) 540 bTPA-DPP-DMP 17.61 0.75 68.4 9.03 361 (81.98%)
2362 (18.02%) 721
16.74 0.79 71.6 9.31 ^b) bTPA-DPP-DMP + Dyenamo Orange 17.3 0.79 74.9 10.0 -

(a) Measurement: after 10 min light soaking under 1 Sun, TiO ₂ film: 30NR-D x2 with scattering layer, Electrolyte: Iodine electrolyte, Dye solution: 0.025 mM (Tert-Amyl alcohol (TAA)/ACN = 1:1 ) + 1 mM CDCA (chenodeoxycholic acid), Soaking condition: 4 h under 50 ^o C water bath. b) cobalt electrolyte)

Looking at Table 3, it can be seen that the solar cell to which the DPP-series according to the present invention is applied has similar or improved current density, photoelectric change efficiency, device efficiency, and the like to commercial Dyenamo Blue. That is, the DPP-series dye according to the present invention satisfies all of high efficiency, high stability, and low cost, and corresponds to a blue dye applicable to a dye-sensitized solar cell.

As described above, although the embodiments have been described by the limited embodiments and drawings, various modifications and variations are possible from the above description by those of ordinary skill in the art. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved. Therefore, other implementations, other embodiments, and claims and equivalents fall within the scope of the claims to be described later.

Claims (15)

An organic dye that is a compound represented by the following Formula 1 or Formula 2:
[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,
Each of R ¹ to R ² is hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, and 1 to 30 carbon atoms. Of alkoxy, C1-C30 alkylcarbonyl, C6-C30 aryl, and C5-C30 heteroaryl,
R ³ to R ⁶ are, respectively, hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 to 30 carbon atoms Of alkoxy, C1-C30 alkylcarbonyl, C6-C30 aryl, and C5-C30 heteroaryl,
The aryl and heteroaryl are, respectively, unsubstituted or halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 30 carbon atoms, 1 To 30 alkoxy, C 1 to C 30 alkylcarbonyl, C 6 to C 20 aryl, and C 5 to C 20 heteroaryl further substituted by at least one of, the heteroaryl is at least one of N, O and S Contains hetero atoms;
π is selected from π-spacers represented by the following formula.

(Two of Formula 1a, R ⁷ to R ¹² are linking groups, and the rest are each hydrogen, halogen, amide, cyano, hydroxyl, nitro, acyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, and It is selected from alkynyl having 2 to 30 carbon atoms, and all are not hydrogen.))
The method of claim 1,
The R ¹ to R ² are each selected from a substituted or unsubstituted aryl having 6 to 30 carbon atoms and a heteroaryl having 5 to 30 carbon atoms,
Organic dyes.
The method of claim 1,
Each of the R ¹ to R ² is selected from the following formula.

(Here, R _a to R _f One of them is a linking group, and the other is selected from hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, and alkoxy having 1 to 20 carbon atoms.)
The method of claim 1,
Two of the R ⁷ to R ¹² are linking groups, and the remainder are each selected from hydrogen, halogen, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and alkynyl having 2 to 10 carbon atoms,
Organic dyes.
The method of claim 1,
The π-space group is selected from the following organic dyes:

,

,

And

(Where, R ⁷ , R ⁹ , R ¹⁰ and R ¹² are each, It is selected from C1-C10 alkyl and C2-C10 alkenyl.)
The method of claim 1,
The π-space group forms a twist angle of 0 ^o to 90 ^o in the molecule of the compound represented by Formula 1 or Formula 2,
Organic Dye:
The method of claim 1,
The alkoxy is represented by -OR, and R is selected from C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl and C2 to C30 aryl,
Organic dyes.
The method of claim 1,
The organic dye is selected from Formulas 3 and 4 below:
[Formula 3]

[Formula 4]

(Wherein, R is selected from C 1 to C 10 alkyl, C 2 to C 10 alkenyl, C 2 to C 10 alkynyl and C 2 to C 20 aryl, and R ³ to R ⁶ are as defined in claim 1 same.)
The method of claim 1,
The organic dye is a blue dye,
Organic dye
An organic dye comprising at least one of the compounds represented by Formula 1 and Formula 2 of claim 1;
Containing,
Organic dye composition.
The method of claim 10,
The composition further comprises a co-adsorbent;
Organic dye composition.
The method of claim 10,
The composition further comprises a metal oxide;
Organic dye composition.
The method of claim 10,
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. To do,
Organic dye composition.
The method of claim 10,
The metal oxide has a size of 1 nm to 1000 nm,
The metal oxide is porous,
Organic dye composition.
A first electrode;
A light absorbing layer formed on the first electrode; And
A second electrode formed on the light absorbing layer;
Including,
The light absorbing layer may include a metal oxide; And comprising the organic dye of claim 1,
Dye-sensitized solar cell.

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