CN102250484B - Method for preparing carbazolyl organic dye used for dye-sensitized solar cells - Google Patents

Abstract

The invention relates to a pure organic dye which adopts a carbazole group as the electron donor and is used for dye-sensitized solar cells and a preparation method thereof. With a molecular structure of D-Pi-A and a good light-capturing capacity, the dye has an adsorption spectrum and a fluorescence spectrum that are adjustable by aromatic nucleuses of different kinds and numbers. Belonging to pure organic dyes, the dye of the invention, compared with ruthenium dyes, has simple-structured and cheap raw materials that are in abundant supply and easy for purification, thus having the advantages of low cost and simple production, etc. In addition, the dye of the invention can effectively improve the electron lifetime and the open circuit photovoltage, and can obtain energy conversion efficiency over 5%. Compared with dyes without a long alkyl chain side group, the dye provided in the invention can inhibit the charge recombination degree to less than one-tenth of the original, thus boasting good development and application prospects in the field of dye-sensitized solar cells.

Description

The preparation method who is used for the carbazyl organic dye of dye sensitization solar battery

Technical field

The present invention relates to the organic photoelectrical material field, particularly relate to a kind of for dye sensitization solar battery novel take carbazole group as electron donor, aromatic nucleus is as the bridge chain and connect the preparation method of the pure organic dye of carbazyl of alpha-cyanoacrylate.

Background technology

Along with shortage of resources and problem of environmental pollution become increasingly conspicuous, people day by day strengthen the care of energy problem, sun power is the desirable energy of human long-term survival as a kind of renewable and clean energy resource, taught in 1991 dye sensitization solar battery (the Dye-sensitized solar cells that at first proposes by Switzerland M. Gr tzel, DSSC) as a kind of novel solar battery, for the mankind provide at a low price, efficiently, green regenerative energy sources is brought hope, this battery is based on the development of plant chlorophyll photosynthesis principle and goes out, battery structure is simple, mainly by working electrode, electrolytic solution and electrode formed.Working electrode is by sintering one deck nano porous titanium dioxide film in the conductive glass substrate, and adsorbs one deck light-sensitive coloring agent in the above and make; Electrolytic solution can be liquid, also can be accurate solid-state and solid-state, the most frequently used I ₃ ^-/ I ^-Redox couple; Generally be the conductive glass that is coated with one deck platinum to electrode.

Important component part as battery, the photosensitizers dyestuff can absorb sunlight effectively, and produce thus excitation electron, then be injected in the semi-conductive conduction bands such as titanium dioxide, so the photoelectric properties of dyestuff have vital impact to the photoelectric transformation efficiency of dye sensitization solar battery.At present, the best dye sensitizing agent of performance is the title complex that contains noble ruthenium, and wherein the most classical is N3 and black dyestuff, yet, expensive precious metal price and rare Precious Metals Resources so that its extensive industrialization be limited by very large.Meanwhile, pure organic dye more and more is subject to people's attention owing to having the advantages such as with low cost, high molar absorptivity and structure easy-regulating, and become the study hotspot in this field, and take carbazole group as electron donor, aromatic nucleus is that the associated viscera of bridge chain and the pure organic dye of carbazyl that connects alpha-cyanoacrylate is not also reported at present.

Summary of the invention

The technical problem to be solved in the present invention provides a kind of preparation method of the pure organic dye take carbazole group as electron donor, this application in dye sensitization solar battery, electron lifetime that can the Effective Raise battery and open circuit photovoltage, and can obtain to surpass 5% effciency of energy transfer.

For solving the problems of the technologies described above, the technical solution used in the present invention is: the synthetic route of described carbazyl organic dye is as follows, and in the formula, R1 ~ R4 is hydrogen, alkyl or aralkyl, and n is 1 ~ 4 integer:

The synthetic method of this organic dye is carried out according to following steps:

(1) by compound a synthetic compound b: under nitrogen protection, a certain amount of compound a is dissolved in the tetrahydrofuran (THF) (THF) fully, reaction system places-20 ° below the C, slowly splash into 0.9 ~ 2 times the n-Butyl Lithium that molar weight is compound a with syringe, after reacting 0.1 ~ 2 h under the low temperature, splashing into molar weight is 1.1 ~ 2.5 times of tributyltin chlorides of compound a again, after dropwising reaction system is warming up to room temperature, stir 2 ~ 36 h, reaction stops with ammonium chloride solution, then uses dichloromethane extraction, deionized water wash, use again anhydrous sodium sulfate drying, eliminate solvent and get compound b, be not further purified processing and be directly used in next step reaction;

(2) by compound b and c synthetic compound d: under nitrogen protection, with compound b, c and Pd (PPh ₃) ₄Be that the ratio of 1.1 ~ 2:1:0.005 ~ 0.2 is dissolved in the DMF (DMF) according to mol ratio, more than the 80 ° of above reaction of C 4 h, eliminate solvent, the post separating-purifying obtains compound d;

(3) by compound d synthetic organic dye e: with compound d, cyanoacetic acid and ammonium acetate are that the ratio of 1:1 ~ 2.5:0.05 ~ 0.5 is dissolved in the Glacial acetic acid according to mol ratio, more than refluxed under nitrogen 4 h, the methylene dichloride dilution, deionized water repeatedly washs, use anhydrous sodium sulfate drying again, eliminate solvent, the post separating-purifying obtains described carbazyl organic dye e.

In addition, carbazyl organic dye of the present invention is applied in the dye sensitization solar battery, this dye sensitization solar battery prepares through following steps:

(1) conductive glass pre-treatment: the FTO conductive glass is cut into 1.5 * 1.5 cm size, in acetone, ethanol and deionized water, fully clean with ultrasonic wave successively, and dry up with nitrogen gas stream;

(2) preparation of titania slurry: dropwise be added drop-wise to isopropyl oxygen titanium in the deionized water, and at ambient temperature more than stirring reaction 1 h, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the round bottom reaction flask, slowly drip the tetramethylammonium hydroxide aqueous solution of equivalent, add again the deionized water constant volume, strong stirring reaction 1 ~ 5 h in 100 ~ 150 ° of C oil baths, naturally cool to room temperature, the white colloid that obtains after reaction finished is transferred in the autoclave and constant volume, at Water Under thermal treatment 6 ~ 24 h of 150 ~ 300 ° of C, take out behind the naturally cooling and carry out supersound process, obtain milky TiO 2 sol;

(3) preparation of dye solution: described carbazyl organic dye is dissolved in the dry toluene, is mixed with the solution of 0.3 mmol/L;

(4) electrolytical preparation: contain 0.1 mol/L lithium iodide, 0.05 mol/L iodine, 0.6 mol/L iodo 1,2-dimethyl, the different eyeball solution of 3-n-propyl imidazoles and 0.5 mol/L 4-tert .-butylpyridine with the anhydrous acetonitrile preparation;

(5) preparation of working electrode: the resulting titania slurry of step (2) is formed one deck sol pellicle by rotation film forming, silk screen printing or pulling film forming method at the conductive glass that cleans up, dried film is put into retort furnace, temperature slowly is warming up to 450 ~ 550 ° of C, constant temperature 0.5 ~ 10 h, naturally cool to room temperature, with gained TiO ₂Electrode directly immerses in the dye solution of step (3) gained and keeps 24 h;

(6) to the preparation of electrode: with the aqueous isopropanol of 0.1 ~ 50 mmol/L Platinic chloride be coated in equably clean in the step (1) and punching after conductive glass surface, then place in the retort furnace in 400 ~ 500 ° of C roasting 30 min, be cooled to room temperature and place in the moisture eliminator for subsequent use;

(7) cell package: with nitrogen gas stream with the absorption of step (5) gained the TiO of carbazyl organic dye ₂The platinum of working electrode and step (6) gained blows clean electrode, and two electrodes are staggered relatively, conducting surface inwardly, thermoplastic film is inserted at the edge, heats 5 ~ 30 s under 100 ~ 120 ° of C conditions and solidifies, and the used for electrolyte syringe of step (4) gained is injected in the battery by the aperture to electrode, and utilize wicking action so that be full of electrolytic solution in the cavity of two electrodes, in two electrodes without bubble after, with seal gum aperture is sealed, namely make described dye sensitization solar battery.

Carbazyl dyestuff of the present invention has D-π-A molecular structure, has good light capture ability, its absorption spectrum and fluorescence spectrum can be regulated by the aromatic nucleus of different sorts and number, belong to pure organic dye, compare with ruthenium class dyestuff, its raw material mix is simple, cheap and easy to get, and in liberal supply, be easy to purifying, therefore have with low costly, produce the advantages such as easy.In addition, carbazole and derivative thereof have good photoelectric properties, such as cavity transmission ability and strong electron supplying capacity, it is the good photoelectric material of a class, this class organic dye is applied in the dye sensitization solar battery, can effectively improve life-span and the open circuit photovoltage of electronics, and can obtain to surpass 5% energy conversion efficiency, in addition, compare with the dyestuff that does not comprise the long alkyl chain side group, such dyestuff can be suppressed to the charge recombination degree original below 1/10th, so such dyestuff has good development and application prospect in field of dye-sensitized solar cells.

Embodiment

The present invention is further detailed explanation below in conjunction with drawings and Examples.

Embodiment 1:Synthesizing of dyestuff 1

Synthetic route is as follows:

(1) compound 1b's is synthetic:

Under nitrogen protection; 0.63 g (1.63 mmol) 1a is dissolved among the 20 mL THF; reaction system places-78 ° of C; slowly splash into 1.2 mL (1.96 mmol) n-Butyl Lithiums (1.6 mol/L) with syringe; after reacting 1 h; splash into again 0.6 mL (2.21 mmol) tributyltin chloride; after dropwising reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; then use dichloromethane extraction; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 0.94 g compound 1b; yield 97% is not further purified processing and is directly used in next step reaction.

(2) compound 1d's is synthetic:

Under nitrogen protection; with 0.94 g (1.58 mmol) 1b, (preparation of compound 1c is referring to document R. Chen et al., Chem. Mater. 2007 for 0.43g (1.58 mmol) 1c; 19,4007) and 91 mg (0.08 mmol) Pd (PPh ₃) ₄Be dissolved among the 40 mL DMF, 90 ° of C react 10 h, eliminate solvent, and the post separating-purifying obtains 0.50 g compound 1d, yield 63%.

(3) dyestuff 1 is synthetic:

With 450 mg (0.90 mmol) 1d, 115 mg (1.35 mmol) cyanoacetic acid and 21 mg (0.27 mmol) ammonium acetate are dissolved in the 60 mL Glacial acetic acid, refluxed under nitrogen 7 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 260 mg dyestuffs 1, yield 51%.

Embodiment 2:Synthesizing of dyestuff 2

Synthetic route is as follows:

(1) compound 2b's is synthetic:

Under nitrogen protection; 0.54 g (1.57 mmol) 2a is dissolved among the 40 mL THF; reaction system places-78 ° of C; slowly splash into 1.1 mL (1.73 mmol) with syringe) n-Butyl Lithium (1.6mol/L); after reacting 2 h; splash into again 0.5 mL(2.04 mmol) tributyltin chloride; after dropwising reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; then use dichloromethane extraction; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 0.81 g compound 2b; yield 93% is not further purified processing and is directly used in next step reaction.

(2) compound 2d's is synthetic:

Under nitrogen protection, with 0.81 g (1.46 mmol) 2b, 0.64 g (1.46 mmol) 2c and 84 mg (0.073 mmol) Pd (PPh ₃) ₄Be dissolved among the 40 mL DMF, 85 ° of C react 8 h, eliminate solvent, and the post separating-purifying obtains 466 mg compound 2d, yield 51%.

(3) dyestuff 2 is synthetic:

With 435 mg (0.69 mmol) 2d, 89 mg (1.04 mmol) cyanoacetic acid and 16 mg (0.21 mmol) ammonium acetate are dissolved in the 60 mL Glacial acetic acid, refluxed under nitrogen 6h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 220 mg dyestuffs 2, yield 46%.

Embodiment 3:Synthesizing of dyestuff 3

Synthetic route is as follows:

(1) compound 3b's is synthetic:

Under nitrogen protection; with 3a; be that (synthetic method is seen document S. O. Jeon et al. to 3-bromo-9-phenyl-carbazole; Adv. Funct. Mater. 2009; 19; 3644.) 253 mg (0.79 mmol) are dissolved among the 30 mL THF; reaction system places-78 ° of C, slowly splashes into 0.5 mL (1.73 mmol) n-Butyl Lithium (1.6 mol/L) with syringe, react 2 h after; splash into again 0.25 mL(1.03 mmol) tributyltin chloride; after drip finishing reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; then use dichloromethane extraction; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 412 mg compound 3b; yield 98% is not further purified processing and is directly used in next step reaction.

(2) compound 3d's is synthetic:

Under nitrogen protection, with 412 mg (0.78 mmol) 3b, 484 mg (0.70 mmol) 3c and 45 mg (0.039 mmol) Pd (PPh ₃) ₄Be dissolved among the 40 mL DMF, 80 ° of C reaction 9h eliminate solvent, and the post separating-purifying obtains 317 mg compound 3d, yield 53%.

(3) dyestuff 3 is synthetic:

With 294 mg (0.34 mmol) 3d, 44 mg (0.52 mmol) cyanoacetic acid and 8 mg (0.10 mmol) ammonium acetate are dissolved in the 20 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 119 mg dyestuffs 3, yield 38%.

Embodiment 4:Synthesizing of dyestuff 4

Synthetic route is as follows:

(1) compound 4b's is synthetic:

Under nitrogen protection; 275 mg (1.06 mmol) 4a is dissolved among the 40 mL THF; reaction system places-78 ° of C; slowly splash into 0.7 mL (1.17 mmol) n-Butyl Lithium (1.6mol/L) with syringe; after reacting 2 h; splash into again 0.33 mL (1.38 mmol) tributyltin chloride; after drip finishing reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; then use dichloromethane extraction; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 489 mg compound 4b; yield 98% is not further purified processing and is directly used in next step reaction.

(2) compound 4d's is synthetic:

Under nitrogen protection, with 489 mg (1.04 mmol) 4b, 517 mg (1.04 mmol) 4c and 60 mg (0.052 mmol) Pd (PPh3) 4 are dissolved among the 40 mL DMF; 85 ° of C react 8 h; eliminate solvent, the post separating-purifying obtains 292 mg compound 4d, yield 47%.

(3) dyestuff 4 is synthetic:

With 278 mg (0.46 mmol) 4d, 59 mg (0.69 mmol) cyanoacetic acid and 11 mg (0.14 mmol) ammonium acetate are dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 150 mg dyestuffs 4, yield 49%.

Embodiment 5:Synthesizing of dyestuff 5

Synthetic route is as follows:

(1) compound 5b's is synthetic:

Under nitrogen protection; 53 mg (0.19 mmol) 5a is dissolved among the 20 mL THF; reaction system places-78 ° of C; slowly splash into 0.13 mL (1.17 mmol) n-Butyl Lithium (1.6 mol/L) with syringe; after reacting 2 h; splash into again 0.07 mL (0.24 mmol) tributyltin chloride; after dropwising reaction system is warming up to room temperature, keeps 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; then use dichloromethane extraction; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 87 mg compound 5b; yield 95% is not further purified processing and is directly used in next step reaction.

(2) compound 5c's is synthetic:

Under nitrogen protection, with 87 mg(0.18 mmol) 5b, 137 mg (0.20 mmol) 3c and 21 mg (0.018 mmol) Pd (PPh ₃) ₄Be dissolved among the 20 mL DMF, the 80 ° of above reaction of C 8 h eliminate solvent, and the post separating-purifying obtains 89 mg compound 5c, yield 60%.

(3) dyestuff 5 is synthetic:

With 77 mg (0.095 mmol) 5c, 12 mg (0.14 mmol) cyanoacetic acid and 2 mg(0.029 mmol) ammonium acetate is dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 57 mg dyestuffs 5, yield 69%.

Embodiment 6:Synthesizing of dyestuff 6

Synthetic route is as follows:

(1) compound 6b's is synthetic:

Under nitrogen protection, with 271 mg (0.31 mmol) 6a, 300 mg (0.62 mmol) 5b and 50 mg(0.043 mmol) Pd (PPh ₃) ₄Be dissolved among the 20 mL DMF, the 80 ° of above reaction of C 8 h eliminate solvent, and the post separating-purifying obtains 236 mg compound 6b, yield 77%.

(2) dyestuff 6 is synthetic:

With 218 mg (0.22 mmol) 6b, 28 mg (0.33 mmol) cyanoacetic acid and 5 mg (0.066 mmol) ammonium acetate are dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, the post separating-purifying obtains 171 mg dyestuffs 6, yield 73%.

Embodiment 7:Dyestuff 1 is applied to dye sensitization solar battery as sensitizing agent

The FTO conductive glass is cut into 1.5 * 1.5 cm size, in acetone, ethanol and deionized water, fully clean with ultrasonic wave successively, and dry up with nitrogen gas stream, isopropyl oxygen titanium dropwise is added drop-wise in the deionized water, and at ambient temperature more than stirring reaction 1 h, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the round bottom reaction flask, slowly drip the tetramethylammonium hydroxide aqueous solution of equivalent, add again the deionized water constant volume.Strong stirring reacts 2 h in 140 ° of C oil baths, naturally cools to room temperature, and the white colloid that obtains after reaction is finished is transferred in the autoclave and constant volume, at Water Under thermal treatment 12 h of 220 ° of C.Take out behind the naturally cooling and carry out supersound process, obtain milky TiO 2 sol.Form one deck sol pellicle by the silk screen printing film at the conductive glass that cleans up.Dried film is put into retort furnace, and temperature slowly is warming up to 500 ° of C, constant temperature half an hour naturally cools to room temperature, namely obtains TiO ₂Working electrode is with gained TiO _{2 work}Electrode directly immerses the anhydrous toluene solution (0.3 mmol/L) of dyestuff 1.

With the aqueous isopropanol of 0.1 ~ 50m mol/L Platinic chloride be coated in equably clean in the step (1) and punching after conductive glass surface, then place in the retort furnace in 400 ~ 500 ° of C roasting 30 min, be cooled to room temperature and obtain platinum to electrode, be positioned in the moisture eliminator for subsequent use

Working electrode obtained above and platinum are blown clean electrode, and two electrodes are staggered relatively, conducting surface inwardly, thermoplastic film is inserted at the edge, puts into that heating 10 s solidify under 110 ° of C after fixing.With 0.1 mol/L lithium iodide, 0.05 mol/L iodine, 0.6 mol/L iodo 1, the 2-dimethyl, the acetonitrile solution of 3-n-propyl imidazoles and 0.5 mol/L 4-tert .-butylpyridine is injected in the battery by the aperture to electrode, and utilizes wicking action so that be full of electrolytic solution in the cavity of two electrodes, in two electrodes without bubble after, with seal gum aperture is sealed, prepare dye sensitization solar battery, wherein cell area is 0.2304 cm ²Record the current-voltage curve of dye sensitization solar battery under the AM1.5 simulated solar irradiation, the photovoltage (Voc) that obtains opening a way is 0.72 V, and short-circuit photocurrent (Jsc) is 6.32 mA/cm ², packing factor (FF) is 75%, effciency of energy transfer (η) is 3.4%.

Embodiment 8:Dyestuff 2 is applied to dye sensitization solar battery as sensitizing agent

Dyestuff 2 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.75 V, and short-circuit photocurrent (Jsc) is 6.97 mA/cm ², packing factor (FF) is 71%, effciency of energy transfer (η) is 3.7%.

Embodiment 9:Dyestuff 3 is applied to dye sensitization solar battery as sensitizing agent

Dyestuff 3 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.77 V, and short-circuit photocurrent (Jsc) is 8.22 mA/cm ², packing factor (FF) is 73%, effciency of energy transfer (η) is 4.6%.

Embodiment 10:Dyestuff 4 is applied to dye sensitization solar battery as sensitizing agent

Dyestuff 4 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.79 V, and short-circuit photocurrent (Jsc) is 7.71 mA/cm ², packing factor (FF) is 75%, effciency of energy transfer (η) is 4.6%.In addition, by the intensity modulation electrochemical analysis, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.

Embodiment 11:Dyestuff 5 is applied to dye sensitization solar battery as sensitizing agent

Dyestuff 5 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.76 V, and short-circuit photocurrent (Jsc) is 8.83 mA/cm ², packing factor (FF) is 75%, effciency of energy transfer (η) is 5.1%.In addition, by the intensity modulation electrochemical analysis, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.

Embodiment 12:Dyestuff 6 is applied to dye sensitization solar battery as sensitizing agent

Dyestuff 6 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.77 V, and short-circuit photocurrent (Jsc) is 6.38 mA/cm ², packing factor (FF) is 75%, effciency of energy transfer (η) is 3.7%.In addition, by the intensity modulation electrochemical analysis, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.

Claims (1)

1. a synthetic method that is used for the carbazyl organic dye of dye sensitization solar battery is characterized in that the synthetic route of this organic dye is as follows, and in the formula, R1 ~ R4 is hydrogen, alkyl or aralkyl, and n is 1 ~ 4 integer:

The synthetic method of this organic dye is carried out according to following steps:

(1) by compound a synthetic compound b: under nitrogen protection, a certain amount of compound a is dissolved in the tetrahydrofuran (THF) (THF) fully, reaction system places-20 ° below the C, slowly splash into 0.9 ~ 2 times the n-Butyl Lithium that molar weight is compound a with syringe, after reacting 0.1 ~ 2 h under the low temperature, splashing into molar weight is 1.1 ~ 2.5 times of tributyltin chlorides of compound a again, after dropwising reaction system is warming up to room temperature, stir 2 ~ 36 h, reaction stops with ammonium chloride solution, then uses dichloromethane extraction, deionized water wash, use again anhydrous sodium sulfate drying, eliminate solvent and get compound b, be not further purified processing and be directly used in next step reaction;

(2) by compound b and c synthetic compound d: under nitrogen protection, with compound b, c and Pd (PPh ₃) ₄Be that the ratio of 1.1 ~ 2:1:0.005 ~ 0.2 is dissolved in the DMF (DMF) according to mol ratio, more than the 80 ° of above reaction of C 4 h, eliminate solvent, the post separating-purifying obtains compound d;

(3) by compound d synthetic organic dye e: with compound d, cyanoacetic acid and ammonium acetate are that the ratio of 1:1 ~ 2.5:0.05 ~ 0.5 is dissolved in the Glacial acetic acid according to mol ratio, more than refluxed under nitrogen 4 h, the methylene dichloride dilution, deionized water repeatedly washs, use anhydrous sodium sulfate drying again, eliminate solvent, the post separating-purifying obtains described carbazyl organic dye e.