TW201020295A - Dye compound and photoelectric component using the same - Google Patents

Abstract

The present invention relates to a dye compound and a photoelectric component using the same, and the dye compound is represented by the following formula (I) or its salt derivative: wherein R1, R2, R3, R4, D1, D2, B, and n are defined the same as the specification. The dye compound of the present invention is suitable for Dye-Sensitized Solar Cell (DSSC). Hence, the photoelectric characteristics of the DSSC manufactured with the dye compound of the present invention can be improved.

Description

201020295 VI. Description of the Invention: [Technical Field] The present invention relates to a dye compound and a photovoltaic element produced using the dye compound, in particular to a Dye-Sensitized Solar Cell (DSC) Dye compounds and dye-sensitized solar cells. • [Prior Art] With the development of human civilization, the world faces serious energy crisis and environmental pollution. Among them, photovoltaic solar cells that can directly convert solar energy into electrical energy are one of the important methods to solve the global energy crisis and reduce environmental pollution. In solar cells, dye-sensitized solar cells have become a promising new type due to their low manufacturing cost, large area, flexibility, light transmission and use in buildings. Solar battery. In recent years, Gratzel et al. published a series of dye-sensitized solar cell phases (e.g., O'Regan, B.; GrStzel, M. 1991, 353, 737), showing the utility of dye-sensitized solar cells. In general, the structure of the dye-sensitized solar cell includes a cathode/anode electrode, nano titanium dioxide, a dye, and an electrolyte; wherein the dye has a critical effect on battery efficiency. In dye-sensitized solar cells, an ideal dye must have a characteristic that absorbs a wide range of solar spectrum, high absorption coefficient, high temperature stability, and light stability. 4 201020295 钌 合物 合物 is a photosensitive sensitizing dye with high photoelectric conversion efficiency, but it is costly and will face shortage of supply after being used in large quantities. Organic sensitizing dyes have the advantages of high molar absorption coefficient and large molecular design variation, so it is possible to manufacture dye-sensitized solar cells without color, and increase the flexibility of dye-sensitized solar cells, and can respond to object matching. Different color dye solar cells. Recently, Coumarin (Hara, K.; Sayama, K.; Arakawa, H.; Ohga, Υ·; Shinpo, A.; Sug, S. Chem. Commun. 2001, 569) ' °^I Indoline (Horiuchi, T.; Miura, H.; Sumioka, K.; Uchida, SJ 10 Jm. CTzem. <Soc 2004, 12218), and Merocyanine (Otaka, H.) Kira, M.; Yano, K.; Ito, S.; Mitekura, H.; Kawata, T.; Matsui, FJ Photochem. PAoioWo/. d·. CTzew. 2〇〇4,6*7) Derivatives have been used to make dye-sensitized solar cells. 15 However, the general organic photosensitizing dye synthesis step is cumbersome and the process conditions are not easily controlled. Because dyes in dye-sensitized solar cells have a critical ® effect on cell efficiency. Therefore, finding a dye molecule that can improve the efficiency of a dye-sensitized solar cell is one of the important methods for improving the efficiency of a dye-sensitized solar cell. In addition, simplifying the synthesis of dye compounds can reduce the manufacturing cost of dye-sensitized solar cells, and is also an important issue. SUMMARY OF THE INVENTION The present invention provides a novel dye compound suitable for use in a dye-sensitized 25 solar cell. Since the dye compound of the present invention has a high molar absorption system, the dye-sensitized solar cell produced by using the dye compound of the present invention has excellent photoelectric properties. The invention provides a dye compound with a simple synthesis method, which has fewer synthesis steps, and the process is easy to control, and the synthesis cost is low. 5 The present invention further provides a dye-sensitized solar cell which has a high photoelectric efficiency. ❹ 10 wherein the dye compound of the present invention has a structure of the following formula (1) or a salt thereof:

尺^^广和仏 Each is independently 仏^乂alkyl (4) let ^), CcC丨2 alkoxy, or hal〇gen, and n is an integer from i to 3;

D丨, D2, and N are jointed together as parameters

Cycloheteroalkylene, wherein &, heart, &, &, Ri, Rn, Rn, and R14 are each independently H, Ci~Cu alkyl, c丨~Ci2 6 201020295

Alkoxy 'amino, or halogen, R is Η, or C丨~C丨2 alkyl;

9 κ!2, and R15 are each independent

Lu, 5 10 15 ^~c12, the base, Ci~, c, the second 6, Rl7, and Rl8 are each independently Η, ～ are each independently a base, or 齿 ϋ, %, and Se. Or Cl~C〗 2, and Z is 〇, S, or Ri, r 11, (^丨2垸, (:1~(:^3, and 114) in the above formula (I) may be independent Integer, respectively; preferably, Ri, r2, or halogen, and η is 1 to 3 kc12 alkyl, = base ^ are each independently Η, preferably, R, R2, R or dentate And η is 1 or 2 or C...morphous oxy, =: respectively, H, Cw, and R4 are each independently a heart or 2, more preferably HR3, and ° is optimal, Ri, r 1 ~Cl2 alkyl, or c (~~morphous oxy, or C-wide c, 2 fluorenyl, and "two" and ~ are each independently 4h, the above formula (1) order <

V can be independently C, ~Cl2

Or 7 201020295

, or Dp D2, and N are commonly bonded to or

Re ' R7 ' R8 ' R, (C4 ~ 匸6 cycloheteroalkylene), wherein R5, '10, R", R13, and R14 are each independently H, C 12 alkyl, Cl~c丨2 Alkoxy, amine, or halogen, r9, Ri

Rl5 is each independently H, or CM" alkyl; preferably, d, 12, and ❿ and 〇2 are each independently C丨~c12 alkyl

Wherein miR8 is each independently ^1 12 yuan C丨~C|2 alkoxy, amine, or halogen, R9 alkyl; more preferably, Di, and d2 are each independently -, „! 112 R7 φρ

a base, a hydrazine, a fluorine plant, wherein R5, R6, R, and Rs are each independently H, Γ Γ 7R AH, 卞r / group, or Cl~Cl2 alkoxy, Κ·9 is Η, or C 1~C〗, · Lu set • Very V soil ΛΑ u alkyl, the best, Dl, and A are independent points ~, .R7

Λ ^

Further, the CrCu base group, xy%, or R6, R7, R8, and R9 are each independently Η, or Cl~C, and R5, respectively. In addition, in one embodiment of the present invention, the formula (1); D:, 8 15 201020295 tD2 may each independently be C~alkyl, or ^^ wherein R5, R6, and r7 are each independently H, Ci~c, 2 alkoxy, amine, or dentate; Preferably, D1, C丨~Ci and R7 are each independently H, Ci~c2, respectively, R5, R6, and R7 in 〇1, and 〇2; or Cl~C12 Appearance. And ~ each independently is H, ίο B B in the above formula (I) can be a R20, ~ί>,

R17

'where Rm, each independently H, c and C12 alkyl: ho I丨, and R22 are each independently ^, 17 (12 alkyl, and the art is 〇, S, or Se; preferably, B r ^ 12 alkoxy,

Ri9, or, - \, wherein Ri6 is Η, C, ~Γ~Ci2 alkoxy, erythro 12 alkyl, C 丞 or 素, R19, and R22 are each independently

Or, B is

Cl~Cl2 yard base' and Z is 〇, S, or Se; better 9 201020295

Wherein R16 is hydrazine, Ci-Cu alkyl, Ci (12 alkoxy, or halogen, and R19, and R22 are each independently Η, or

19

CcCu alkyl, and Ζ is S; optimal, Β

, wherein R16, R19, and R22 are each independently Η, or (^~(: 12 alkyl, and Ζ is S. Further, in one embodiment of the present invention, B in the above formula (I) may be

Is \=/ , or ^ , wherein R16 is Η, CcCn alkyl, Ci~C 12 alkoxy, or halogen, R19 is Η, or Ci~C 2-1, and Z is Ο,

Ίο

S, or Se; preferably, B is \=/ or 〜, wherein R16 is Η, CcCu alkyl, CcCn alkoxy, or halogen, and R19 is Η, or C

1~C12 alkyl group' and Ζ is S; preferably, Β is \=/, or Liangzhu 9 wherein Rl6 is H, C丨~C!2 alkyl, or Ci~Ci2 alkoxy, Ri9 is Η Doing 16

Or CcCu alkyl, and Ζ is S; more preferably, Β is w, or h wherein R丨6, and R丨9 are each independently Η, or C丨~C12 alkyl, and Z 15

For S; the best, B is \=

Or ~, where R16, and R 19 201020295 are Η, and Z is S. Specific examples of the dye compound of the above formula (I) are:

Ίο

(13a)

11 201020295

In the present invention, the compound molecule is represented by the form of the free acid, but the actual form may be a salt stagnation, more likely an alkali metal salt or a quaternary ammonium salt. © In addition, the above dye compound is a dye compound for dye-sensitized solar 10 batteries. In another aspect, the present invention also provides a dye-sensitized solar cell comprising the above dye compound. The dye-sensitized solar cell of the present invention comprises: a photoanode containing the above dye compound; a cathode; and an electrolyte layer between the photoanode and the cathode 15. 12 201020295 In the dye-sensitized solar cell of the present invention, the photoanode includes: a transparent substrate, a transparent conductive film, a porous semiconductor film, and a dye compound; wherein the dye compound is a dye compound as described above. In the dye-sensitized solar cell of the present invention, the material of the photoanode is transparent. The material of the substrate is not particularly limited, and any substrate can be used as long as it is transparent. Preferably, the material of the transparent substrate is a transparent substrate having good barrier properties, solvent resistance, and fiscal properties for moisture or gas intruded from the outside of the dye-sensitized solar cell. Specific examples of the transparent substrate include: transparent inorganic substrates such as quartz and bismuth glass; polyethylene terephthalate (PET), poly(naphthalene dicarboxylate) (pEN), and polycarbonate (PC). A transparent plastic substrate such as polyethylene (PE), polypropylene (PP) or polyimine (PI), but is not limited thereto. Further, the thickness of the transparent substrate is not particularly limited, and can be freely selected in accordance with the light transmittance and the characteristics of the dye-sensitized solar cell. Preferably, the transparent substrate is made of glass. Further, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive film may be indium tin oxide (ITO), fluorine-doped tin oxide (FT〇), or oxonium-bis-gallium oxide (ZnO). -GhO3), zinc oxide _ aluminum oxide (ΖηΟ-Α12〇3), or tin-based oxide material. Further, in the dye-sensitized solar cell of the present invention, the porous semiconducting film is made of semiconductive semiconductor particles. Suitable semiconductor microparticles may include: Shi Xi, titanium dioxide, tin trioxide, zinc oxide, trioxane, antimony pentoxide, titanium trioxide, and combinations thereof; preferably, the semiconductor microparticles are titanium dioxide "semiconductor particles The average particle size is from 5 to 5 nanometers, preferably from 10 to 50 nanometers. The thickness of the porous semiconductor film is micrometers. 13 201020295

5 Non-limiting examples of Coco include: platinum, gold, and JTj = two-gap poles, and are suitable for cathode gold, carbon, and the like. Further, the electrolyte layer as the dye-sensitized solar cell is not particularly limited and may include any substrate having electron and/or hole conductivity. In another aspect, the present invention further provides a dye solution comprising: the above-mentioned dye compound in an amount of 0.01 to 1% by weight: and 10 (B) an organic solvent in an amount of 99.99 to 99% by weight, and The organic solvent is selected from the group consisting of acetonitrile, methanol, ethanol, propanol, butanol, dimethylformamide, and N-methylpyrrolidone. [Embodiment] 15 The dye compound of the present invention can be synthesized in the same manner as in Schemes 1 to 3. [Flow 1]

(i) K2C03, DMF. 201020295 (ii) PdCh(dppf), 5-methylamido-2-thiopheneboronic acid or 4-formylphenylboronic acid, K2C〇3, CH3OH/toluene (iii) cyanoacetic acid, piperidine, CH3CN. 5 As shown in Scheme 1, first 7-indolyl-9-bromo-9-amine (7-bromo- 9// -fluoren-2-ylamine) reacts with n-butyl moth to synthesize (7-in-9-shoulder-2-yl)-dibutylamine ((7-Ϊ5Γ〇πιο-9//·ί1ιι〇Γ6η- 2-γ1)-<ϋΙ)ΐιΐγ1 amine)(ll). Then 'will (7-> odor-9-pyridin-2-yl)-dibutylamine (11) with 5-formyl-2-thiopheneboronic acid Synthesis of 5-(7-dibutylamino-9-indol-2-yl)-infrared-2-methyl (5-(7-dibutylamino-9i/-fluoren-2-yl) by Suzuki coupling reaction )-thiophene-2-carbaldehyde) (12a)e Finally, 5-(7-dibutylamino-9-pyridin-2-yl)-thiophene-2-carbaldehyde (5-(4-dibutylamino-9-pyridin-2-yl)-thiophene-2-carbaldehyde (in the acetonitrile) 12a) reacting with cyanoacetic acid to obtain 2-gas-3-[5-(7-dibutylamino-9-span-indol-2-yl)-infrared-2-15yl]-propionic acid S -cyano-SpQ-dibutylamino-P/Z-fluoren-S-yD-thiophen-2-yl]-acrylic acid)(13a) ° φ [Scheme 2] 15 201020295

H2N—+ (ii) PdCl2(dppf), 5-carbamido-2-thiopheneboronic acid or 4-mercaptophenylboronic acid, K2C03, CH3OH/toluene. (iii) Cyanoacetic acid, piperidine, CH3CN. 5 (iv ) KOtBu/KzCOs, 1,4-dioxane (1,4-dioxane>/DMF. As shown in Scheme 2, '7->odor-9-indole-2-amine and n-butyl moth Reaction, synthesis (7-bromo-9,9-dibutyl-9-anthracene-2-yl)-dibutylamine ((7-bromo-9,9-dibutyl-977-fluoren-2-yl) -dibutylamine)(21).^^0 Then 'will (7-> odor-9,9-dibutyl-9 linyl-indol-2-yl)-dibutylamine (21) with 5-methyl fluorenyl Synthesis of 5-(9,9-dibutyl-7-dibutylamino-9-field-2-yl)-porphin-2-methyl ketone by 2-Succinylboronic acid by Suzuki coupling reaction (5- (9,9-Dibutyl-7-dibutylamino-9i/-fluoren-2-yl)-thiophene-2-carbaldehyde) (22a). Finally, in the acetonitrile, the brigade is used as a catalyst, 15 will be 5-(9,9 -Dibutyl-7-dibutylamino-9-fan-2-yl)-thiophene-2-furaldehyde (22a) is reacted with cyanoacetic acid to give 2-cyano-3-[5-(9 , 9-dibutyl-7-dibutylamino _9 s-nonyl-2-yl)-sodium-2-yl]-propionic acid (2-Cyano-3-[5-(9,9-) Dibutyl-7-dibutylamino-9//-fluoren-2-yl) 16 2010202 95-thiophen-2-yl]-acrylic acid) (23a).

[Flow 3]

(ii) PdCh(dppf), 5-carbamido-2-thiopheneboronic acid or 4-methylmercaptoboronic acid, K2C03, CH3OH/toluene. (iii) Cyanoacetic acid, piperidine, ch3cn. (v) KO*Bu , THF. (vi) CuCl, 1,10-phenanthroline, KOH, toluene. φ 10 As shown in Scheme 3, first 7-bromo-9-fan-2-indole-2-amine Reaction with n-butyl iodide to synthesize 7-bromo-9,9-dibutyl-9-fluoren-2-ylamine (7-bromo-9,9-dibutyl-9//-fluoren-2-ylamine) 31). The 2-Iodo-9//-fluorene was reacted with n-butyl moth to synthesize 9,9-dibutyl-2-E-9-shoulder-芴(9,9- Dibutyl-2-iodo-9//-fluorene) (32). Next, 7-17 15 201020295 desert-9,9-dibutyl-9-decan-2-amine (31) and 9,9-dibutyl-2-moth-9 shoulder-苟 (32) by Ullman coupling reaction, synthesis of (7-bromo-9,9-dibutyl-9-fan-2-indol-2-yl)-di-(9,9-dibutyl-9-indole-2-yl)amine ( (7-1) 1"〇111〇-9,9- to 1)111丫1-9//-fluoren-2-yl)-bis-(9,9-dibutyl-9JiT-fluoren-2-yl) Amine) (33 5 ). Then 'will (7-> odor-9,9-dibutyl-9 agro-indol-2-yl)-di-(9,9-dibutyl-9-fluoren-2-indol-2-yl)amine (33 Synthesis of 5-{7-[di-(9,9-dibutyl-9-fan-2-indol-2-yl)amine]-9 by Suzuki coupling reaction with 5-mercapto-2-thiopheneboronic acid 9-dibutyl-9-fan-2-yl-2-yl}-thiophene-2-furaldehyde (5-{7-[1^3-(9,9-(1 plus 71-^ 9if-fluoren-2) -yl)amino]-9,9-dibutyl-9//-fluoren-2-yl}- 10 thiophene-2- carbaldehyde) (34a). Finally, in the acetonitrile with a bite as a catalyst '5-{7 -[bis-(9,9-dibutyl-9 shoulder-indol-2-yl)amine]-9,9-dibutyl-9-fluoren-2-yl}-thiophene-2-furaldehyde ( 34a) by reaction with cyanoacetic acid to give 3-(5-{7-[di-(9,9-dibutyl-9-indol-2-yl)amine]-9,9-dibutyl- 9 or -苟-2-yl}· 吩 phen-2-yl)-2-milo-acrylic acid (3-(5-{7-[bis-15 (9,9-dibutyl-9/i-fluoren) -2-yl)amino]-9,9-dibutyl-9Jfr-fluoren-2-yl}-thiophen-2-yl)-2-cyano-acrylic acid) (35a). The dye-sensitized solar cell of the present invention The manufacturing method is not limited to the standard, and can be produced by a generally known method. The material of the transparent substrate is not particularly limited as long as it is a transparent substrate. 20. It is preferable that the material of the transparent substrate is a transparent substrate having good barrier properties, solvent resistance, weather resistance, and the like for moisture or gas infiltrated from the outside of the dye-sensitized solar cell, and specifically, there is quartz. Transparent inorganic substrates such as glass, polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP) A transparent plastic substrate such as poly(25) imine (PI), but is not limited to these. The thickness of the transparent substrate 18 201020295 is not particularly limited, and can be freely selected by the light transmittance and the characteristics of the dye-sensitized solar cell. In a specific example, the transparent substrate is a glass substrate. 5 Reference 10 15 Ref 20 The material of the transparent conductive film may be selected from indium tin oxide (IT〇), fluorine-doped tin oxide (FTO), and zinc oxide. Di-gallium oxide (Zn〇_Ga2〇3), oxidized-alumina (ΖηΟ-Α12〇3), and tin-based oxide materials. In a specific example, the transparent conductive film is doped with fluorine. Tin oxide. Porous semiconductor The semiconductor fine particles are made. Suitable semi-conducting particles include antimony, titanium dioxide, tin dioxide, zinc oxide, trioxide, pentoxide, titanium oxide, and combinations thereof. First, the semiconductor fine particles are first formulated into a paste, which is then applied to a transparent conductive substrate by a doctor blade, screen printing, spin coating, spraying, or the like, or generally wet coating. Further, in order to obtain an appropriate film thickness, it may be applied one or more times. The semiconductor film layer may be a single layer or a plurality of layers, and the plurality of layers means semiconductor particles having different particle diameters for each layer. For example, semiconductor particles having a particle diameter of 5 to 5 nanometers may be coated first, and the coating thickness is 5 to 2 micrometers, and then semiconductor particles having a particle diameter of 2 to 400 nanometers are coated and coated. The cloth has a thickness of 3 to 5 microns. Then, after drying at 50 to 100 C, it is sintered at 4 to 5 Torr for 30 minutes to obtain a multilayer semiconductor film layer. The dye compound can be dissolved in a suitable solvent to prepare a dye solution. Suitable solvents include acetonitrile, methanol, ethanol, propanol, butanol, dimethylformamide, N-methylpyrrolidone or a mixture thereof, but are not limited thereto. Here, the transparent substrate coated with the semiconductor film is immersed in the dye solution 19 201020295 liquid to allow it to sufficiently absorb the dye in the dye solution, and after the dye absorption is completed, it is taken out and dried to obtain a dye-sensitized solar cell. Photoelectric anode. 5 ❹ 10 15 20 The material used as the cathode is not particularly limited' and may include any material having conductivity. Alternatively, the cathode material may be an insulating material as long as a conductive layer is formed on the surface facing the photoanode. In addition, electrochemically stable materials can serve as the cathode, and non-limiting examples of suitable cathode materials include: Ming, gold, carbon, and the like. The electrolyte layer is not particularly limited and may include any substrate having electron and/or hole conductivity. Further, the liquid electrolyte may be an iodine-containing acetonitrile solution, an iodine-containing N-methylpyrrolidone solution, or an iodine-containing 3 methoxypropionitrile solution. In one embodiment, the liquid electrolyte is an acetonitrile solution containing iodine. A specific manufacturing method of the dye-sensitized solar cell of the present invention is as follows. First, a paste comprising titanium oxide particles having a particle diameter of 20 to 30 nm is coated on a fluorine-doped tin oxide (FTO) glass plate by one or several screen printings. At 450. Sintered for 3 minutes. The dye compound was dissolved in a mixture of acetonitrile and i-butanol (1:1 v/v) to prepare a dye solution. Then, the above glass plate containing the porous oxidized film is immersed in the dye solution, and the dye is absorbed by the dye solution, and then taken out and dried to obtain a photoanode (photoanode) which is covered with a fluorine-doped tin oxide glass plate. Drill a hole with a diameter of 〇75 mm for injection of electrolyte. The vaporized platinum acid out 21 > 圯 16) solution was coated on a fluorine-doped tin oxide glass plate, and then heated to 4 〇〇 20 201020295 C for 15 minutes to obtain a cathode. Then, a thermoplastic polymer film having a thickness of 60 μm was placed between the photoanode and the cathode, and a pressure was applied to the two electrodes at 120 to 140 ° C to bond the two electrodes. 5 Injecting an electrolyte solution (〇.〇3 MI2/0.3 MLiI/0,5 Μtri-butylpyridine in acetonitrile), and sealing the injection port with a thermoplastic polymer film, the dye-sensitized battery of the present invention can be obtained. . The following examples are illustrative of the invention, and the scope of the patent application of the invention is not limited thereby. Wherein the compound molecule is shown in the form of the free acid, but the actual form may be a salt stagnation, more likely an alkali metal salt or a quaternary ammonium salt. "If not specified, the temperature is Celsius, parts and percentage. It is by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. Next, a method of producing the dye compound of the present invention 15 will be described in detail with reference to the above-described Schemes 1 to 3. Example 1 ❷ Synthesis (7---9-residue-field-2-yl)-dibutylamine ((7-1)1*〇111〇-9//-; 〇11〇11-2-yl )-dibutylamine)(ll) 0.52 parts of 7- > 7-bromo-9/ir-fluoren-2-ylamine ' 1.47 parts of n-butyl fluorene under gas (Ι-iodobutane), and 1.38 parts of potassium carbonate were mixed and mixed with 15 parts of dry dimethylformamide, and the reaction mixture was heated to 120 ° C for 24 hours. After the reaction mixture was cooled, the reaction was quenched with water, the hydrazine product was extracted with diethyl ether, and then the water was removed with magnesium sulfate. The solvent was removed after the solvent 21 201020295, and the residue was filtered with a silica gel column to dimethane/ Purification by dichloromethane/hexane elution chromatography gave the compound (11) of this example, which was obtained as a pale yellow solid. 5 Example 2 Synthesis of 5-(7-dibutylamino-9-fan-2-yl)-thiophene-2-carbaldehyde (5-(7-dibutylamino-9if-fluoren-2-yl)-thiophene-2 - carbaldehyde)(12a) ι 0.37 parts (7-bromo-9-fluoren-2-yl)-dibutylamine 10 (11), 0.19 parts of 5-methylindenyl-2-thiophene borate under nitrogen (S-formyld-thiopheneboronic acid), 0.41 parts of carbonic acid clock, and 0.16 parts of [1, bis-bis(diphenylphosphino)ferrocene] palladium (pdCl2 (dppf)) added to 5 parts of toluene ( Toluene) and 5 parts of methanol (CH3OH) were stirred and mixed, and the reaction mixture was heated to 60 ° C for 18 hours. After quenching with water, the product is extracted with diethyl ether, and then the product is removed with magnesium sulfate. The residue obtained by solvent extraction is purified by dichloromethane/hexane eluting with a silica gel column to obtain the compound of the present example. (12a) This compound was an orange-red solid with a yield of 61%. Example 3 20 Synthesis of 4-(7-dibutylamino-9//fluoren-2-yl)-benzaldehyde (4-(7-dibutylamino-9//-fluoren-2-yl)-benzaldehyde) 12 b) The same procedure as in Example 2 was carried out to prepare the compound of this example except that 0.18 parts of 4-formylphenylboronic acid was used in place of 5-methylindenyl-2-thiopheneboronic acid. The compound (12b) of the present invention was obtained in a yellow solid, yield 53%. 22 201020295 Example 4 Synthesis of 2-lact-3-[5-(7-dibutylamino-9-anthracene-2-yl)-porphin-2-yl]-propionic acid (2-cyano-3) -[5-(7-dibutylamino-9//-fluoren-2-yl)-5 thiophen-2-yl]-acrylic acid) (13a) 0.18 parts of 5-(7-dibutylamino) under nitrogen -9-fan-2-yl)-thiophene-2-anthraquinone (lia), 0.05 parts of cyanoacetic acid and 0.017 parts of piperididine were added to 10 parts of acetonitrile and stirred. The reaction mixture was heated to 90 ° C for 6 hours. After the reaction mixture was cooled to room temperature, the solid was filtered off, and then washed with water, diethyl ether and acetonitrile to obtain a dark red solid. Finally, the solid product was applied to a silica gel column with dichloromethane/methanol (dichloromethane/methanol). Purification by chromatography to obtain the compound (13a) of this example, which was dark red solid, yield 73%. 15 Example 5 Synthesis of 2-cyano-3-[4-(7-dibutylamino-9-pyridin-2-yl)-phenyl]-acrylic acid^ (2-cyano-3-[4-(7) -dibutylamino-9/i-fluoren-2-yl)-phenyl]-acrylic acid (13b) 20 The same procedure as in Example 4 was used to prepare the compound of this example except that 0.18 part of 4-(7-dibutylamine) was used. Base-9-miao-2-yl)-benzaldehyde (12b) substituted 5-(7-dibutylamino-9-s--2-inyl)-β-sentene-2-methyl (12 a) The compound (13b) of this example was obtained as a dark red solid, yield 78%. 25 Example 6 23 201020295 Synthesis (7-indol-9,9-dibutyl-9!-Chrysin-2-yl)-dibutylamine ((7-bromo-9,9-dibutyl-9//- Fluoren-2-yl)-dibutylamine) (21) 0.52 parts of 7-bromo-9簏-indol-2-ylamine, 2.21 parts of n-butyl block, 0.67 parts of potassium tributylate (potassium ieri-butoxide), 5 and 0.83 parts of potassium carbonate, 10 parts of water-containing dimethylformamide and 10 parts of 1,4-dioxane were stirred and mixed, and the reaction was carried out. The mixture was heated to 95 ° C for 24 hours. After the reaction mixture is cooled, the reaction mixture is quenched with water, and the product is extracted with diethyl ether, and then water is removed with magnesium sulfate. After solvent removal, the residue of φ is purified by distillation on a silica gel column with di-methane/hexane. The compound (21) of this example was obtained as a pale yellow liquid in a yield of 83%. Example 7 Synthesis of 5-(9,9-dibutyl-7-dibutylamino-9-m-but-2-yl)-snext-2-ene (5-(9,9-dibutyl-7) -dibutylamino-9/f-fluoren-2-yl)-thiophene-15 2-carbaldehyde) (22a) The same procedure as in Example 2 was used to prepare the compound of the present example, except that 0.49 part (7-? 9-Dibutyl-9-indol-2-yl)-dibutylamine (21) ® substituted (7-bromo-9-fluoren-2-yl)-dibutylamine (11), available The compound (22a) of this example was an orange-red solid with a yield of 52%. 20 Example 8 Synthesis of 4-(9,9-dibutyl-7-dibutylamino-9-field-2-yl)- 4-(9,9-dibutyl-7-dibuty lamino) -9/ί-fluoren-2-yl)-benzaldehyde) (22b) 25 The same procedure as in Example 7 was used to prepare the compound of the present example except for 24 201020295 using 0.18 parts of 4-bromophenyl boronic acid in place of 5-methylhydrazine. Base 2 thiopheneboronic acid, which is the compound of the present invention (22a), is a yellow solid, yield 61%. 5 Example 9 Synthesis of 2-cyano-3-[5-(9,9-dibutyl-7-dibutylamino-9-sulfan-2-yl)-thiophen-2-yl]-propanoid: fciMM2 -cyano-3-[5-(9,9-dibutyl-7-dibutylamino-9/f-fluoren-2-yl)-thiophen-2-yl]-acrylic acid) (23a) φ is the same as in Example 4. Procedure The compound of this example was prepared except that 0.23 parts of 5-(9,9-dibutyl-7-dibutylamino-9-fan-2-yl)-thiophene-2-indole (22a) was used. Substituting 5-(7-dibutylamino-9 and -indol-2-yl)-p-phen-2-yl (12a) ' can obtain the compound (23a) of this example, which is a red solid The rate is 86%. 15 Example 10 Synthesis of 2-azin-3-[4-(9,9-dibutyl-7-dibutylamino-9-anthracepin-2-yl)-phenyl]-acrylic acid (2-cyano- 3-[4-(9,9-dibutyl-7-dibutylamino- 9/f-fluoren-2-yl)-phenyl]-acrylic acid) (23b) The same procedure as in Example 9 was carried out to prepare the compound of this example. In addition to 20, 0.23 parts of 4-(9,9-dibutyl-7-dibutylamino-9-fan-2-yl)-benzaldehyde (22b) was substituted for 5-(9,9-dibutyl- 7-Dibutylamino-9-hydan-2-indole-2-yl)-thiophene-2-carbaldehyde (22a) gave the compound (23b) of this example, which was an orange-red solid, yield 68%. 25 Example 11 25 201020295 Synthesis of 7-indol-9,9-dibutyl-9-indole-2-amine (7-1?1*〇111〇-9,9-(1丨1)1^&gt 4-9//-fluoren-2-ylamine) (31) 0.52 parts of 7-bromo-9-fan-2-indole-2-amine, 2.21 parts of n-butyl iodide, and 1.35 parts of tris under nitrogen Potassium butylate was added to 20 parts of dry tetrahydrofuran to mix and mix, and the reaction mixture was heated to 50 ° C for 18 hours. After the reaction mixture is cooled, the reaction is quenched with water, the product is extracted with diethyl ether, and then the water is removed with magnesium sulfate. The residue obtained after solvent removal is purified by distillation on a silica gel column with di-methane/hexane. Compound (31) of φ, this compound was obtained as a tan solid, yield 79%. 10 Example 12 Synthesis of 9,9-dibutyl-2-iodo-9-9-9-dibutyl-2-iodo-9/i-fluorene (32) Under nitrogen, 0.58 parts 2- Iodine-9-iodo-9/f-15 fluorene, 1.10 parts of n-butyl moth, and 0.67 parts of potassium tris-butyl ketone were added to 15 parts of dehydrogenated tetrahydrofuran, and mixed. The reaction mixture was heated to 50 ° C for 12 hours. After the reaction mixture is cooled, the reaction mixture is quenched with water, and the product is extracted with ethyl acetate, and then the mixture is removed with MgSO4, and the residue obtained after solvent removal is purified by hexane-purification chromatography using a hexane column to obtain the compound of the present invention. 20 (32), this compound is a pale yellow liquid, yield 94%. Example 13 Synthesis of (7->Smelly-9,9-dibutyl-9-indol-2-yl)-di-(9,9-dibutyl-9-indolyl-2-yl)amine ((7-bromo-9,9-dibutyl-9/f-fluoren-2-yl)-bis-25 (9,9-dibuty fluoren-2-yl)amine)(33) 26 201020295 Under nitrogen, 0.37 parts of 7-bromo-9,9-dibutyl-9-anthracene-2-amine (31), 0.89 parts of 9,9-dibutyl-2-iodo-9-fan (32), 0.17 parts Hydroxide dehydration, 0.11 part 1,10-徘-phenanthroline, and 0.03 part cuprous chloride were added to 10 parts of toluene to mix and mix, and 5 the reaction mixture was heated to The reaction was refluxed at 125 ° C for 24 hours. After quenching with water, the product was extracted with diethyl ether, and then water was removed with magnesium sulfate. The solvent was removed and the residue was purified by dichloromethane/hexane elution chromatography. The compound (33) of this example was obtained as an orange-red solid, yield 57%. 10 Example 14 Synthesis of 5-{7-[di-(9,9-dibutyl-9-fan-2-indol-2-yl)amine]-9,9-dibutyl-9 scapula-2-yl} -thiophene-2-f@(5-{7-[bis-(9,9-dibutyl-9i/-fluoren-2-yl)amino]-9,9-dibutyi-9/i-fluoren-2-yl }-thiophene -2-carbaldehyde) (34a) 15 The same procedure as in Example 2 was used to prepare the compound of the present Example, except that 0.92 part (7-bromo-9,9-dibutyl-9-s-- (), bis-(9,9-dibutyl-9-purine-2-yl)amine (33) substituted (7-bromo-9-purine-2-yl)-dibutylamine^ (11 The compound (34a) of this example was obtained as an orange-red solid with a yield of 38%. 20 Example 15 Synthesis of 4-{7-[di-(9,9-dibutyl-9ron-indol-2-yl)amine]-9,9-dibutyl-9 shoulder-indol-2-yl }-Benzyl road (4-{7-[1)13-(9,9-<11151^1-9//-1[111〇11·· 2-yl)-amino]-9,9 -dibutyl-9i/-fluoren-2-yl}-benzaldehyde) (34 25 b) 27 201020295 The same procedure as in Example 14 was carried out to prepare the compound of the present example, except that 0.18 parts of 4-methyl-bromobenzenecarboxylic acid was used instead of 5 The compound (34b) of this example was obtained as a yellow solid in a yield of 48%. Example 16 Synthesis of 3-(5-(7-[--(9,9-dibutyl·9-fan·芴_2-yl)amine]_9,9-dibutyl-9-indole-2-yl} -thiophen-2-yl)-2-cyano-acrylic acid (3_(5_{7_[Bis· ❹ (9,9-dibuty1-9 ugly-nuoren-hyUaminoj-^-dibutyl-gH-fluoren 10 -2-yl} -thiophen-2-yl)-2-cyano-acrylic acid) (35a) The compound of this example was prepared in the same manner as in Example 4 except that 0.41 part of 5-{7-[di-(9,9-di) was used. Butyl-9-fluoren-2-yl)amine]-9,9-dibutyl-9-anthrace-2-yl}-porphin-2-methyl (34a) substituted 5-(7-di Butylamino-9-anthracene-2-yl)- phenyl-2-yl (12a) - The compound of the present example 15 (35a) was obtained as an orange-yellow solid, yield 51%. Example 17 © Synthesis of 3-(4-{7-[di-(9,9-dibutyl-9-fan-2-indol-2-yl)amine]-9,9-dibutyl 9-shi-芴-2- }--phenyl:)-2-cyano-acrylic acid (3-(4-{7-[Bis-20 (9,9-dibutyl-9/i-fluoren-2-yl)ainino]-9,9- Dibutyl-9/f-fluoren -2-yl}-phenyl)-2-cyano-acrylic acid) (35b) The same procedure as in Example 16 was used to prepare the compound of the present example, except that 0.42 parts of 4-{7-[ Di-(9,9-dibutyl-9 genus-indol-2-yl)amine]-9 , 9-dibutyl-9 genino-indol-2-yl}-benzaldehyde (34b) substituted 5_{7_[di-(9,9-dibutyl25-9-9-fluoren-2-yl)amine] -9,9-dibutyl-9-n-2-yl}-thiophene-2-furaldehyde 28 201020295 (34a), the compound (35b) of the present example is obtained, which is an orange-red solid. The rate is 65%.Example 18 5 Production of a dye-sensitized solar cell A paste comprising titanium oxide particles having a particle diameter of 20 to 30 nanometers (nm) is coated by one or several times of screen printing. Fluorine-doped tin oxide (FTO) glass plate (thickness 4 mm, resistance ΙΟ Ω / port), so that the thickness of the porous titanium oxide film after sintering is 10 to 12 μm, and then sintered at 450 10 ° C 30 minutes. The dye compound of Example 4 was dissolved in a mixture of acetonitrile & i-butanol (1:1 v/v) to give a dye compound concentration of 0.5. The dye solution of the ruthenium is then immersed in the dye solution in the above-mentioned glass plate containing the porous ruthenium oxide film, and allowed to absorb the dye in the dye solution for 16 to 15 hours, and then taken out and dried to obtain a photoanode. A fluorine-doped tin oxide glass plate is drilled to a diameter of 0.75 mm, for injection into an electrolyte, and then a vaporized platinum acid (H2PtCl6) solution (containing 2 mg of platinum in 1 ml of ethanol) is coated. A cathode was obtained on a tin oxide glass plate and then heated to 400 ° C for 15 minutes. 20 A thermoplastic polymer film having a thickness of 60 μm is disposed between the photoanode and the cathode, and a pressure is applied to the two electrodes at 120 to 140 ° C to bond the electrodes. The dye-sensitized solar cell of the present embodiment 25 was obtained by injecting an electrolyte solution (0.03 Μ I2/0.3 M LiI/0.5 Μ tri-butylpyridine in acetonitrile) and sealing the injection port with a thermoplastic polymer film. 29 201020295 Example 19 Production of dye-sensitized solar cell The dye-sensitized solar cell of this example was prepared in the same manner as in Example 18 except that the dye compound of Example 5 was used instead of the dye compound of Example 4. Example 20 ❿ Production of dye-sensitized solar cell 1 A dye-sensitized solar cell of this example was prepared in the same manner as in Example 18 except that the dye compound of Example 9 was used instead of the dye compound of Example 4. Example 21 15 Production of dye-sensitized solar cell The dye-sensitized φ cation battery of this example was prepared in the same manner as in Example 18 except that the dye compound of Example 10 was used instead of the dye compound of Example 4. 20 Example 22 Production of dye-sensitized solar cell The dye-sensitized solar cell of this example was prepared in the same manner as in Example 18 except that the dye compound of Example 16 was used instead of the dye compound of Example 4. 30 25 201020295 Example 23 Production of dye-sensitized solar cell The dye-sensitized solar cell of this example was prepared in the same manner as in Example 18 except that the dye compound of Example 17 was used instead of the dye compound of Example 14. Test Methods and Results UV-Vis Spectra φ The dye compounds of Inventive Example 4, Example 5, Example 9, Example 10, 10 Example 16 and Example 17 were prepared using dimethyl decylamine as a solvent. A dye solution having a concentration of 1.0 χ1 (Γ5Μ. Then, the UV-Vis spectrum of each dye solution was measured. Photoelectric efficiency test 15 The dye-sensitized solar cells of Examples 18 to 23 were tested for short-circuit current under illumination of AM 1.5 ( Jsc), open circuit voltage (Voc), photoelectric conversion efficiency (η), fill factor (FF), and Incident Photon to Current Conversion Efficiency (IPCE) ° 20 The test results are summarized in Table 1 below: Table 1. Test results for dyes and dye-sensitized solar cells Mohr absorption coefficient of the longest wavelength absorption peak of the dye (IVr^ni'^/AmaxCnm) Jsc (mA/cm) V〇c (V) FF η (%) Example 18 13a 25200 / 421 6.28 0.61 0.66 2.54 3 1 201020295 Example 19 13b 23200 / 384 8.40 0.60 0.63 3.15 Example 20 23a 66200/427 13.16 0.69 0.64 5.82 Example 21 23b 73100/386 11.00 0.68 0.58 4.68 Example 22 35a 668(8)/421 1 0.28 0.69 0.65 4.90 Example 23 35b 35200/380 10.30 0.70 0.63 4.58 The test results of Table 1 show that the dye compound Φ of the embodiment of the present invention has a high molar absorption coefficient; the dye-sensitized solar cell of the embodiment of the present invention has excellent Photoelectric characteristics. 5 In summary, the present invention shows its characteristics different from conventional techniques in terms of purpose, technique and efficacy, or in terms of its technical level and R&D design. However, it should be noted that the above The present invention has been described by way of example only, and is not intended to limit the scope of the invention, and may be modified and modified by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the claims should be based on the scope of the patent application φ, and is not limited to the above embodiments. [Simple description of the diagram] None. [Main component symbol description] None. 32 15

Claims (1)

201020295 VII. Patent application scope: 1. A dye compound whose structure is as follows: (I) or its salts: 5 Wherein I, R2, R3, and R4 are each independently H, CcCu alkyl, C-C12 alkoxy, or halogen, and η is an integer from 1 to 3; R6, R7, 尺 8, Rio, R11, Rl3, and Rl4 are each independently separated from each other by 'J, Cl, Cl~Ci2, Cu~Ci2 alkoxy, amine, or halogen 'R9, Rl2, and R15. Independently Η, or CcCu alkyl; 33 201020295 5 10 B is \—.jf Rl7 Rl8 n/Z, n Wherein, Ri6, R17, and R18 are each independently h, ～c丨2 alkoxy, or halogen, and Rl9, R2〇, R21, and R22 are each independently η, or Cl~Cl2 alkyl, and z is 〇. , s, or Se. 2. The dye compound according to claim 1, wherein η is 1 3. The dye compound according to claim 1, wherein D! and Da are each independently a Cl~c12 alkyl group. R5, or wherein, Re, R7, and 8 are each independently Η, Ci~C丨2 alkyl, C丨~c丨2 alkoxy, amine, or halogen, 1 is 1^, or Ci~ C 12 base. 4. A dye compound as described in claim 3, wherein b ~^Γ, Rl9, or /^^\, where r16 is h, Ci~Ci2 alkyl 'Cpc, 2 alkoxy, or halogen, and Ri9' and ruler 22 are each independently Η, or c丨~C丨2 alkyl, and Z is oxime, S, or Se. 5. The dye compound of claim 4, wherein z is S ' and η is 1. for 34 15 201020295 6. The dye compound according to claim 5, wherein Rl, R2, R3, R4, R5, R6, R"m6 are each independently H, CrCu, or C-C12 7. The dye compound of claim 6, wherein 5 R, R 2 , R 3 , R 4 , R 5 , R 6 , R "HU_M ^ Η , or C ^ C 12 alkyl. 8: The dye compound according to the application, wherein B ❹ wherein R "h, Ci~Ci2 alkyl, Ci~Ci2 alkoxy, or dentate, R19 is Η, or Cl~Cl2 And find 〇, s, 10 or Se ° 9. The dye compound as described in claim 8 of the patent application, wherein D1 and D2 are each independently a Cl~Ci2 alkyl group, an alkoxy group, an amine group, or a dentate. 10. The dye compound of claim 9, wherein ζ is S and η is 1. 11. The dye compound according to claim 1, wherein the centers, R2, R3, R4, R5, R6' r7, and Rl6 are each independently H, Cda alkyl, or Ci-Ciz alkoxy. . The dye compound according to claim 11, wherein R, R2, R3, R4, R5, R6, r7, and r16 are each independently H, or CcCu alkyl. 35 201020295 13. The dye compound of claim 12, wherein Rl6, and Rl9 are Η. 14. The dye compound of claim 1, wherein the dye compound is a dye compound for use in a dye-sensitized solar cell. 15. A dye compound having the structure of the following formula (23a) or the following formula (35a): (35a) ° 16. The dye compound according to claim 15, wherein the dye compound is a dye compound for use in a dye-sensitized solar cell. 17. A dye-sensitized solar cell comprising: (a) a photoanode comprising a dye compound of the formula (I) or a salt thereof; ' 36 201020295 NC COOH H -B wherein 12 R1, R2, R3, & R4_^MH, Cl~Cl2M, Cr alkoxy, or a functional element ' and n is an integer from 1 to 3; Where R5, R6, R7, r8, R 3 ' Or 〇1, 〇2, and 1^ are commonly bonded as u, U, 10 ❹ Η, C丨~C丨2 alkyl, c Γ U oxime, amine, or halogen, Rl2, and Rl5 is each independently Η, or Cl~Cl2 垸; Wherein R16, R丨7, and core 8 are each independently H, 12 alkyl-Cl~Cl2 oxo, or _-, Rl9, R2. , R21, and 22 are each independently H, or C, ~Cl2 alkyl, and Z is 〇, S, or Se; 37 15 201020295 (b) - cathode; and (C) an electrolyte layer in the photoanode Between the cathode and the cathode. 18. A dye solution comprising: (A) a dye compound of the following formula (I) or a salt thereof in an amount of from 5 to 0.01% by weight: Wherein R!, R2, R3, and R4 are each independently H, C丨~C丨2 alkyl, C丨~C1210 alkoxy, or halogen, and η is an integer from 1 to 3; D, and D2 are each independently CrCu alkyl R_6, R7, R>8, R10, Rl1, Rl3, and Rl4 are each independently Η, 15 C!~Ci2 alkyl, Ci~Ci2 alkoxy, amine, or halogen, R9, Rl2, and R15. Each of them is independently Η, or CcCu alkyl; 38 201020295 R22 is each independently Η, or C-C12 alkyl, and Z is Ο, S, or Se; and (B) an organic solvent in an amount of 99.99 to 99% by weight, and the organic solvent is selected from: A group consisting of acetonitrile, methanol, ethanol, propanol, butanol, dimethyl decylamine, and N-decylpyrrolidone. 39 201020295 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Wherein, the definitions of Ri, R2, R3, R4, D, D2, B, and η are as described in the specification. 3