KR101540297B1

KR101540297B1 - Polymer with alkyl thienyl thienoindole thereof and photovoltaic device using same

Info

Publication number: KR101540297B1
Application number: KR1020140046425A
Authority: KR
Inventors: 서홍석; 김진우; 백지연
Original assignee: 부산대학교 산학협력단
Priority date: 2014-04-18
Filing date: 2014-04-18
Publication date: 2015-07-30

Abstract

The present invention provides a polymer having an alkylthienylthienoaround functional group represented by the following formula (1).
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently a C _1-20 linear or branched alkyl group, Ar is a thiophene, benzimidazole, dithienylbenzothiadiazole, dithienylbenzimide At least one electron donor aromatic compound selected from dithiol, bithienyl benzimidazole, phenanthrolothiadiazole or dithiophenepyrrolopyrrolidone, and n is an integer of 1 to 1,000.
In the polymer, an alkyl thienyl thienoyl functional group is contained as an electron donor and at least one kind of aromatic monomer is contained as an electron donor, thereby improving solubility and having a low band gap. The photon absorption ability can be increased and the energy conversion efficiency of the solar cell can be improved.
In addition, when applied to an energy conversion device, the driving voltage of the device can be lowered, the photoelectric efficiency can be improved, and the lifetime characteristics of the light energy conversion device can be improved due to the thermal stability of the polymer compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer having an alkylthienyl thienoindole functional group and an energy conversion element using the polymer.

The present invention relates to a polymer having an alkylthienylthienoerythieno functional group and an energy conversion device using the same. More particularly, the present invention relates to a polymer having an alkylthienylthienoindole group A polymer containing a functional group as an electron donor, and an energy conversion element having excellent photoelectric efficiency and excellent solubility in an organic solvent using the same.

Inorganic solar cells have been problematic due to the problems of manufacturing cost, manufacturing process imagination, and environmental pollutants. As a result, interest in solar cells using organic devices has increased.

In the case of organic solar cells, most of the organic materials used are less expensive than inorganic materials used in inorganic solar cells, have very high application possibilities due to process flexibility, have light weight, and have a wide range of possibilities.

In organic solar cell processing, there are two methods of manufacturing thin film using donor and acceptor material deposition method and solution method.

In the case of using a deposition method, a monolayer is used for both the donor and the acceptor, whereas the solution process is generally performed by using a polymer as a donor material and the acceptor is a polymer, a fullerene derivative, a perylene derivative, Quantum dot inorganic nanoparticles and the like are used. Therefore, by using a solution process using a polymer, it is possible to manufacture a large-sized device at a low cost, as compared with the case where a single molecule is deposited and used.

In addition, the organic material processed into a liquid state as described above can be easily prepared into a desired shape, has an easy bending property, and has an advantage of high affinity with various materials including plastics.

In addition, when using the roll-to-roll method, the cost reduction effect can be expected.

In spite of many advantages of such an organic solar cell, the energy conversion efficiency is still low, and research on organic materials for improving it is insufficient.

Accordingly, the present inventors have developed a polymer having an alkylthienylthienoaround functional group having improved solubility and a low band gap and an energy conversion device using the same.

In order to solve the above problems, the present invention provides a polymer compound having improved solubility and low band gap, and using the same to improve energy conversion efficiency of an organic solar cell.

The polymer compound includes an alkylthienylthienoil functional group as an electron donor and various aromatic monomers as an electron acceptor.

Another object of the present invention is to provide a polymer as an electroluminescent device in an organic solar cell luminescent layer.

Another object of the present invention is to provide a light energy conversion device using the polymer.

In order to solve the above problems, the present invention provides a polymer having an alkylthienylthienoaround functional group represented by the following general formula (1).

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently a C _1-20 linear or branched alkyl group, Ar is a thiophene, benzimidazole, dithienylbenzothiadiazole, dithienylbenzimide At least one electron donor aromatic compound selected from dithiol, bithienyl benzimidazole, phenanthrolothiadiazole or dithiophenepyrrolopyrrolidone, and n is an integer of 1 to 1,000.

According to the present invention, as an electron donor, a polymer containing an alkylthienylthienoerythroic functional group and containing at least one kind of various aromatic monomers as an electron acceptor is easily dissolved in a general organic solvent with an improved solubility, Accordingly, the polymer material of the present invention can be used in a device in a soluble form in accordance with the use of an alkyl group, and a high-temperature heat treatment process may not be required, so that an electroluminescent device can be manufactured on a plastic substrate that is excellent in workability and can be bent .

In addition, by having a low band gap, it is possible to improve the energy conversion efficiency of the solar cell by increasing absorption at a long wavelength and increasing the photon absorption capacity.

In addition, according to the present invention, since monomers giving electrons can be different, they can have amorphous or crystalline properties, so that it is possible to satisfy requirements individually required for each device, and when applied to an energy conversion device, The photovoltaic efficiency is improved and the lifetime characteristics of the optical energy conversion device can be improved due to the thermal stability of the polymer compound.

1 is a cross-sectional view of a light energy conversion device using a conjugated polymer according to the present invention.
2 is a graph showing an absorbance spectrum of a solution state using PTTIDTBT and PTTIDTMBI according to an embodiment of the present invention.
3 is a graph showing an absorbance spectrum of a film state using PTTIDTBT and PTTIDTMBI according to an embodiment of the present invention.
4 is a graph illustrating current-voltage characteristics using PTTIDTBT and PTTIDTMBI according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a polymer having an alkylthienylthienoaround functional group represented by the following formula (1).

[Chemical Formula 1]

In the polymer represented by the above formula (1), the alkylthienylthienoerythrene functional group is an electron major group, and Ar is an electron acceptor aromatic monomer.

In the present invention, a low band gap is formed on the electron emitter and the electron receiver, so that the region where the light is absorbed is extended to the long wavelength to increase the photon absorption, thereby increasing the photoelectric efficiency of the solar cell.

The polymer has a mass average molecular weight of 5,000 to 200,000. When the mass average molecular weight is less than 5,000 or more than 200,000, the physical properties of the device are difficult to implement or the photoelectric efficiency is lowered, which is not preferable .

The polymer is characterized in that it is selected from the compounds represented by the following Chemical Formulas 2 to 7 according to the electron acceptor aromatic compound Ar, and more preferably, the polymer is represented by PTTIDTBT, PTTIDTMBI, PTTIBBTMBI, PTTIPT, PTTIDPP and PTTI-iDPP And the respective synthetic reactions are described below.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a C _1-20 linear or branched alkyl group and n is an integer of 1 to 1,000)

Synthesis reaction of PTTIDTBT

Poly (4- (1-octylonyl) -6- (2-thienyl) -2- {5- [7- (2-thienyl) -2,1,3-benzothiadiazol- (2-thienyl) -2- {5- [7- (4-fluorophenyl) (2-thienyl) -2,1,3-benzothiadiazol-4-yl] -2-thienyl} -4H-thieno [3,2- b] indole

As shown in the above scheme, the compound 4-bromo-2-nitroaniline (1) is reacted with potassium iodide to give 4-bromo-1-iodo-2-nitrobenzene (2) Bromo-1-iodo-2-nitrobenzene (2) was reacted with 2-tributylstannyl thiophene to obtain 2- [2-nitro- Phenyl] thiophene (3) was obtained by adding triphenylphosphine to the above 2- [2-nitro-4- (2-thienyl) phenyl] thiophene To give 6- (2-thienyl) -4H-thieno [3,2- b] indole (4) (2-thienyl) -4H-thieno [3,2-b] indole (5) was obtained by reacting 4- (1-octylonyl) Yl) -3,2-b] indole (5) was reacted with trimethyltin chloride to give 4- (1-octyloxy) -Octylonyl) -2- (trimethylstannyl) -6- [4 - (trimethylstannyl) -2-thienyl] -4H-thieno [3,2- b] indole 6 was obtained and also 4,7-dibromo-2,1,3- The diazole (7) was reacted with 2- (tributylstannyl) thiophene to give 4,7-di-2-thienyl-2,1,3-benzothiadiazole (8). The compound 4,7-di-2-thienyl-2,1,3-benzothiadiazole (8) was reacted with N-bromosuccinimide to give 4,7-bis (5-bromo- -Thienyl) -2,1,3-benzothiadiazole (9). (Trimethylstannyl) -2-thienyl] -4H-thieno [3,2-b] pyridin- (2-thienyl) -2- {5- [7- (2-thienyl) -2, 3- 4-yl] -2-thienyl} -4H-thieno [3,2-b] indole) (PTTIDTBT).

Synthesis reaction of PTTIDTMBI

Poly (2- {5- [2,2-dimethyl-7- (2-thienyl) -2H-benzimidazol-4-yl] -2-thienyl} -4- (2-thienyl) -2H-benzimidazo [2,3-b] indole) -4-yl] -2-thienyl} -4- (1-octylononyl) -6- (2-thienyl) -4H-thieno [3,2- b] indole)

As shown in the above scheme, 4,7-dibromo-2,2-dimethyl-2H-benzimidazole (11) was reacted with 2- (tributylstannyl) (7-di (2-thienyl) -2H-benzimidazole (12) 12) was reacted with N-bromosuccinimide to give 4,7-bis (5-bromo-2-thienyl) -2,2-dimethyl-2H-benzimidazole (13). (Trimethylstannyl) -2-thienyl] -4H-thieno [3,2-b] pyridin- (2- {5- [2,2-dimethyl-7- (2-thienyl) -2H-benzimidazol-4-yl] -2- (2-thienyl) -4H-thieno [3,2-b] indole (PTTIDTMBI).

Synthesis reaction of PTTIBBTMBI

Synthesis of poly (4,7-bis (2,2-bicythien-5-yl) -2,2-dimethyl-2H-benzimidazole- 5-yl) -2,2-dimethyl-2H-benzimidazol-4-ylmethyl) -1H-pyrazolo [3,4- 1-octylononyl) -6- (2-thienyl) -4H-thieno [3,2-b] indole)

As shown in the above reaction scheme, 4,7-dibromo-2,2-dimethyl-2H-benzimidazole (11) was reacted with 5- (tributylstannyl) -2,2'-bithiophene to give 4 , 7-bis (2,2-bithian-5-yl) -2,2-dimethyl-2H-benzimidazole (14) 5-yl) -2,2-dimethyl-2H-benzimidazole (14) was reacted with N-bromosuccinimide to give 4,7-bis (5- (5-bromothiophen- -Yl) -thiophen-2-yl)) - 2,2-dimethyl-2H-benzimidazole (15) (4,7-bis (trifluoromethyl) phenyl) -thiophene was obtained through styrene polymerization reaction with 6- [4- (trimethylstyrene) -2-thienyl] -4H- (2,2-bicythien-5-yl) -2,2-dimethyl-2H-benzimidazole-4- (1-octylonyl) -6- (2-thienyl) -4H- Nor [3,2-b] indole)) (PTTIBBTMBI).

Synthesis reaction of PTTIPT

Synthesis of poly (5- [4- (1-octylonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- ] [1,2,5] thiadiazole) (poly5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- 2- yl] phenanthro [9,10-c] [1,2,5] thiadiazole)

As shown in the above reaction scheme, the compound 9,10-phenanthrenequinone (17) was reacted with NaN (Me ₃ Si) ₂ solution and Me ₃ SiCl and then treated with triphenylphosphine to obtain phenanthro [9,10-c ] [1,2,5] thiadiazole (19) and reacting the phenanthro [9,10-c] [1,2,5] thiadiazole (19) (10-diiodo-phenanthro [9,10-c] [1,2,5] thiadiazole (20) (5 - [(4-methoxyphenyl) -1H-pyrazol-3-yl] - (1-octylonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- 5] thiadiazole) (PTTIPT).

Synthesis reaction of PTTIDPP

Synthesis of poly (2,5-dioctyl-3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [3,2- b] 2-thienyl} -6- (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole- -3 - {5- [4- (1-octylononyl) -6- (2-thienyl) -4H-thieno [3,2-b] indol-2- yl] -2-thienyl} -6- thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione)

(Thiophen-2-yl) -2H, 5H-pyrrolo [3,4-d] pyrimidin-2-one was prepared by reacting compound 2-thiophenenitrile 22 with dimethyl succinate as shown in the above scheme. c] pyrrole-1, 4-dione (23), and reacting the 3,6-bis (thiophen-2-yl) -2H, 5H- pyrrolo [ (Thiophen-2-yl) pyrrolo [3,4-c] pyrrole-l, 4-cyanopyridine (23) Pyrido [3,4-c] pyrrole-1,4-dione (24) is obtained by reacting 2,5-dioctyl-3,6-bis (thiophen- (5-bromothiophen-2-yl) -2,5-dioctylpyrrolo [3,4-c] pyrrole-1,4-diamine is reacted with N-bromosuccinimide Ion (25) was obtained, which was treated with the 4-1 (1-octylnonyl) -2- (trimethylstannyl) -6- [4- (trimethylstannyl) -2-thienyl] -4H- (2,5-dioctyl-3- {5- [4- (1-octylonyl) -6- (2- Yl) -4H-thieno [3,2-b] indol-2-yl] - (2-thienyl) -6- (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione) (PTTIDPP).

PTTI - iDPP Synthesis of

Poly (1,4-bis (4-butylphenyl) -3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [ ] Indol-2-yl] -2-thienyl} -6- (2-thienyl) pyrrolo [ 4-bis (4-butylphenyl) -3- {5- [4- (1-octylononyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- thienyl} -6- (2-thienyl) pyrrolo [3,2-b] pyrrole-2,5 (1H, 4H) -dione

As shown in the above scheme, the compound 2-ethylthiophene acetate (27) was reacted with N-bromosuccinimide in THF solvent to give ethyl 2- (5-bromo-thienyl) -2- ). The compound 4-butyl aniline (29) and oxalyl chloride (30) are reacted with phosphorus pentachloride in toluene solvent to yield bis (4-butylphenyl) ethanedimidoyl dichloride (31). The compound (31) and the compound (28) were reacted with sodium bis (trimethylsilyl) amide in THF solvent to obtain 1,4-bis (4-butylphenyl) -3,6-bis {5- [4- 2-thienyl} pyrrolo [3,2-b] pyrrole-2,5-dione (32) (1, 2, 3, 4-tetramethyl-2-thienyl) -4H-thieno [3,2- - bis (4-butylphenyl) -3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [3,2- b] (2-thienyl) pyrrolo [3,2-b] pyrrole-2,5 (1H, 4H) -dione) (PTTI-iDPP) .

The method of synthesizing the above compound is a method of introducing a stannyl functional group into an alkylthienyl thienoin stone and then coupling with a monomer having various electron accepting ability, A polymer containing an electron donor Ar monomer has a low band gap.

Also, since most of the organic solar cells using the polymers are processed by a wet process, the polymer may be easily dissolved in general organic solvents including linear alkyl or branched alkyl chains in order to improve the solubility of the organic solvent .

In addition, since the polymer is a conjugated polymer, it can absorb light of the sun by a thin film (about 100 nm) because of its high extinction coefficient, so that it can be manufactured as a thin device.

According to another aspect of the present invention, there is provided an electroluminescent device.

Wherein the polymer light emitting layer comprises a substrate, a translucent electrode formed on the substrate, a hole transport layer, a polymer light emitting layer and a metal electrode sequentially, and the polymer light emitting layer is made of a polymer having an alkylthienyl thienoyl functional group. Lt; / RTI >

Here, the substrate is characterized by glass or plastic.

The present invention also provides a light energy conversion device using a polymer having an alkylthienyl thienoyl functional group.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by the examples.

Example

&Lt; Example 1 >

Poly (4- (1-octylonyl) -6- (2-thienyl) -2- {5- [7- (2-thienyl) -2,1,3-benzothiadiazol- -Yl] -2-thienyl} -4H-thieno [3,2-b] indole) (PTTIDTBT)

1) Synthesis of 4-bromo-1-iodo-2-nitrobenzene (2)

4-Bromo-2-nitroaniline (10 g, 46.079 mmol) was dissolved in water (38 ml), acetic acid (34.29 ml, 599.027 mmol) and sulfuric acid (34 ml, 645.016 mmol) And stirring was carried out in the presence of a gas. Sodium nitrite (3.8 g, 55.2944 mmol) was dissolved in water (15 ml), added to the reaction mixture, and stirred for 30 minutes. Potassium iodide (9.9 g, 59.9027 mmol) was dissolved in water (15 ml), added to the reaction mixture, refluxed at 60 ° C for 1 hour, cooled to 0 ° C and ether was added.

The reaction mixture was washed three times with 100 ml of water, and the vacuum distillation residue was separated by column chromatography to obtain a yellow solid (15 g, 86%).

_{1H NMR (300 MHz, CDCl 3} ): δ (ppm) 8.01 (s, 1H) 7.90 (d, 1H, J = 8.24 Hz) 7.42 (d, 1H, J = 8.24 Hz)

^{13 C NMR (75 MHz, CDCl} 3): δ (ppm) 153.68,143.16,136.75,128.72,122.89,84.65

HRMS, m / e calcd for C ₆ H ₅ BrN ₂ O ₂ , 326.8392, found 326.8388

2) Synthesis of 2- [2-nitro-4- (2-thienyl) phenyl] thiophene (3)

Thiophene (2.75 ml, 34.310 mmol) was dissolved in tetrahydrofuran (30 ml) and 2.5 M n-butyllithium (9.15 ml, 22.873 mmol) was added under argon gas at -78 캜.

After 1 h at -78 <0> C, trivile tiltin chloride (6.17 ml, 22.873 mmol) was added to the reaction mixture and after 2 h ether and water were added. The reaction mixture was washed three times with 100 ml of water. Bromo-1-iodo-2-nitrobenzene (2) (3 g, 9.149 mmol) obtained in 1) above was reacted with dichloro (bistriphenylphosphine) palladium at room temperature Was dissolved in dimethylformamide (15 ml). The reaction mixture was refluxed under argon gas at 100 DEG C for 1 day. After cooling to room temperature, the vacuum distillation residue was separated through column chromatography to obtain an orange solid (1.4 g, 53%).

_{1H NMR (300 MHz, CDCl 3} ): δ (ppm) 7.96 (s, 1H) 7.78 (d, 1H, J = 8.20 Hz) 7.57 (d, 1H, J = 8.0 Hz) 7.45-7.40 (m, 3H) 7.16-7.09 (m, 3H)

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm) 149.914, 141.238, 137.099, 135.377, 132.892, 128.867, 128.783, 128.131, 127.478, 127.433, 126.940, 125.111, 120.942

HRMS, m / e calcd for C 14 H 9 NO 2 S 2, 287.0075, found 287.0076

3) 6- (2- Cyeenal ) -4H- Thieno [3,2-b] indole (4) Synthesis of

4- (2-thienyl) phenyl] thiophene (3) (1.4 g, 4.87 mmol) and triphenylphosphine (3.19 g, 12.18 mmol) obtained in the above 2) Was dissolved in isododichlorobenzene (20 ml). The reaction mixture was refluxed under argon gas for 1 day. After cooling to room temperature, the vacuum distillation residue was separated by column chromatography to obtain a white solid (0.7 g, 50%).

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 8.23 (s, 1H) 7.74 (d, 1H, J = 8.20) 7.68 (s, 1H) 7.49 (d, 1H J = 8.20) 7.39 (d, 1H, J = 4.9) 7.35 (d, IH, J = 3.5) 7.32

HRMS m / e calcd for C ₁₄ H ₉ NS ₂ , 255.0176, found 255.0176

4) 4- (1- Octyl nonyl ) -6- (2- Cyeenal ) -4H- Thieno [3,2-b] indole (5) Synthesis of

(0.7 g, 2.456 mmol) and potassium hydroxide (0.68 g, 12.180 mmol) obtained in the above step 3) and 6- (2-thienyl) -4H-thieno [3,2- ) Was dissolved in dimethylsulfoxide (20 ml) and then refluxed at 50 DEG C in the presence of argon gas, followed by addition of 1-octylnonyl-4-methylbenzenesulfonate. After refluxing for 1 day, it was cooled to room temperature and water and hexane were added. The reaction mixture was washed three times with 100 ml of water. The vacuum distillation residue was separated by column chromatography to give a white solid (0.8 g, 64%).

_{1H NMR (300 MHz, CDCl 3} ): δ (ppm) 7.74 (d, 1H, J = 8.20) 7.65 (s, 1H) 7.45 (d, 1H, J = 1.09) 7.38-7.35 (m, 2H) 7.28 ( 1H, J = 6.03) 7.14-7.11 (m, 2H) 4.50-4.43 (q ,, 1H) 1.22-1.06 (m, 25H) 0.89-0.81

^{13 C NMR (75 MHz, CDCl} 3): δ (ppm) 146.105, 128.719, 128.014, 126.589, 124.031, 122.453, 121.641, 119.114, 117.582, 112.129, 107.717, 60.261, 59.066, 56.968, 55.222, 50.565, 34.095, 31.785 , 29.395, 29.318, 29.226, 26.576, 22.640, 14.123

HRMS, m / e calcd for C ₃₁ H ₄₃ NS ₂ , 493.2837, found 493.2836

5) Synthesis of 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole (6) Synthesis of

Thieno [3,2-b] indole (5) (1 g, 2.025 mmol) obtained in the above step 4) was dissolved in tetrahydrofuran Was dissolved in furan (10 ml) and 1.7 M t-butyl lithium (4.76 ml, 8.100 mmol) was added under argon gas at -78 ° C. After 1 h at -78 <0> C, 1 M trimethyltin chloride (8.505 ml, 8.505 mmol) was added to the reaction mixture. After stirring for 1 day at room temperature, ether and water were added. The reaction mixture was washed three times with 100 ml of water. To obtain a green oil (0.6 g) which was a vacuum distillation residue.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 7.74 (d, 1H, J = 8.20) 7.65 (s, 1H) 7.45 (d, 1H, J = 1.09) 7.38-7.35 (m, 2H) 7.28 (m, 2H), 0.83 (m, 6H), 1.42 (m, 3H) )

HRMS (FAB +, m / z) calcd for C ₃₇ H ₅₉ NS ₂ Sn ₂ , 819.2138, found 821.2131

6) Synthesis of 4,7-di-2-thienyl-2,1,3-benzothiadiazole (8)

A solution of 4,7-dibromo-2,1,3-benzothiadiazole 7 (1 g, 3.4 mmol), 2- (tributylstannyl) thiophene (3 g, 8.1 mmol) and dichlorobis (Triphenylphosphine) palladium (II) (3 mol%) were dissolved in 50 ml of tetrahydrofuran under argon atmosphere at room temperature. After 12 h at 80 < 0 > C, water and methylene chloride were added to the reaction mixture. The reaction mixture was washed three times with 100 mL of water. After removal of the solvent by vacuum distillation of methylene chloride, the product was isolated via column chromatography to give a red solid (750 mg).

m.p. 124 ℃

Rf = 0.5 (SiO _2, methylene chloride: hexane = 1: 1)

^{1 H NMR (300 MHz, CDCl} 3) δ 8.13 (d, 2H, J = 3.3 Hz), 7.9 (s, 2H), 7.47 (d, 2H, J = 4.9 Hz), 7.22 (t, 2H, J = 4.4 Hz)

¹³ C NMR (75 MHz, CDCl ₃ )? 152.5, 139.3, 127.9, 127.4, 126.7, 125.8, 125.6

HRMS (FAB +, m / z ) calcd for C 14 H 8 N 2 S 3 299.9850, measured 299.9852.

7) Synthesis of 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole (9)

4,7-di-2-thienyl-2,1,3-benzothiadiazole (8) (1 g, 3.3 mmol) was dissolved in 50 mL of dimethylformamide. To the reaction mixture was added N-bromosuccinimide (1.2 g, 6.9 mmol) at room temperature. The residue formed after reaction at room temperature for 12 hours was filtered and then recrystallized to obtain a red solid (1 g).

m.p. 251 ° C

Rf = 0.75 (SiO _2, methylene chloride: hexane = 1: 1)

^{1 H NMR (300 MHz, CDCl} 3) δ 7.28 (d, 2H, J = 3.8 Hz), 7.80 (s, 2H), 7.17 (d, 2H, J = 3.8 Hz)

HRMS (FAB +, m / z ) calcd for C 14 H 6 Br 2 N 2 S 3 455.8060 found 455.8055.

8) Synthesis of poly (4- (1-octyl nonyl) -6- (2-thienyl) -2- {5- [7- (2-thienyl) -2,1,3-benzothiadiazole Yl] -2-thienyl} -4H-thieno [3,2-b] indole) (PTTIDTBT)

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole (0.2 g, 0.436 mmol) was added to a solution of 4,6-bis (5-bromo-2-thienyl) -2,1,3-benzothiazole diazide 6 (0.36 g, 0.436 mmol) And tri-o-tolipospin and tris (dibenzylideneacetone) dipalladium (3 mol%) were dissolved in toluene. The mixture was refluxed under argon for 2 days. After cooling to room temperature, methanol was poured into the mixture, and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol. The polymer obtained was dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

&Lt; Example 2 >

Poly (2- {5- [2,2-dimethyl-7- (2-thienyl) -2H-benzimidazol-4-yl] -2-thienyl} -4- ) -6- (2-thienyl) -4H-thieno [3,2-b] indole) (PTTIDTMBI)

Synthesis of poly (4,7-bis (2,2-bicythien-5-yl) -2,2-dimethyl-2H-benzimidazole- Yl) -4H-thieno [3,2-b] indole)) (PTTIBBRMBI)

1) Synthesis of 2,2-dimethyl-4,7-di (2-thienyl) -2H-benzimidazole (12)

A mixture of 2.7 g (8.9 mmol) of 4,7-dibromo-2,2-dimethyl-2H-benzimidazole (11), 16.6 g (44.4 mmol) of 2- (tributylstannyl) Phosphine) 0.038 g (0.054 mmol) of dichloropalladium was dissolved in 40 ml of tetrahydrofuran, and then the reaction mixture was refluxed at 80 ° C for 24 hours under argon gas. The vacuum distillation residue was separated by column chromatography to obtain 2 g of a red solid.

Rf = 0.3 (SiO _2, methylene chloride: hexane = 3: 1)

mp 172 ° C

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 1.67 (s, 6H), 7.13 (dofd, 2H, J = 3.9 and 5.4 Hz), 7.30 (s, 2H), 7.38 (d of d, 2H J = 1.1 and 4.9 Hz), 8.03 (d of d, 2H, J = 1.1 and 3.5 Hz;

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm) 22.38, 105.40, 126.85, 128.24, 128.28, 128.80, 128.99, 138.94, 157.94.

HRMS (m / z, EI +) calcd C ₁₇ H ₁₄ N ₂ S ₂ 310.0598, found 310.0600.

2) Synthesis of 4,7-bis (5-bromo-2-thienyl) -2,2-dimethyl-2H-benzimidazole (13)

2,2-dimethyl-4,7-di (2-thienyl) -2H-benzimidazole (12) (1.3 g, 4.19 mmol) was dissolved in tetrahydrofuran (50 mL) , N-bromosuccinimide (1.52 g, 8.6 mmol) was added to the reaction mixture. After 3 hours of reaction at room temperature, the vacuum distillation residue was separated by column chromatography to obtain 1.25 g (64%) of a red solid.

Rf = 0.3 (SiO _2, methylene chloride: hexane = 3: 1)

mp 207 ° C

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 1.58 (s, 6H), 7.08 (d, 2H, J = 3.9 Hz), 7.21 (s, 2H), 7.69 (d, 2H, J = 3.9 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm) 22.02, 105.59, 115.11, 127.56, 127.90, 128.08, 130.72, 139.86, 157.45.

HRMS (m / z, EI + ) calcd for C 17 H 12 Br 2 N 2 S 2 465.8809, found 465.8810.

3) Synthesis of 4,7-bis (2,2-bicythien-5-yl) -2,2-dimethyl-2H-benzimidazole (14)

5.0 g (16.5 mmol) of 4,7-dibromo-2,2-dimethyl-2H-benzimidazole (11) and 16.1 g (49.4 mmol) of 5- (tributylstannyl) mmol) and 0.038 g (0.054 mmol) of bis (triphenylphosphine) dichloropalladium were dissolved in 40 ml of tetrahydrofuran, and the reaction mixture was refluxed at 80 ° C for 24 hours under argon gas. The vacuum distillation residue was separated by column chromatography to obtain 3 g of a purple solid.

mp 190 [deg.

^{1 H NMR (300 MHz, Benzene} -d 6): δ (ppm) 1.50 (s, 6H), 6.59 (d of d, 2H, J = 3.6 Hz and 4.8 Hz), 6.67 (d, 2H, J = 4.4 J = 3.8Hz), 6.74 (s, 2H), 7.00 (d, 2H, J = 3.6Hz), 7.04 (d, 2H, J = 3.8Hz), 8.00 (d, 2H, J = 3.5Hz).

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm) 22.46, 105.53, 124.41, 124.93, 125.14, 128.23, 128.29, 128.35, 129.21, 137.52, 137.82, 138.88, 158.03.

HRMS (m / z, EI + ) calcd for C 25 H 18 N 2 S 4 474.0350, found 474.0353.

4) Synthesis of 4,7-bis (5- (5-bromothiophen-2-yl) -thiophen-2-yl)) - 2,2-dimethyl-2H-benzimidazole

2,2-dimethyl-2H-benzimidazole (14) (0.9 g, 1.90 mmol) was dissolved in tetrahydrofuran (20 mL), and N-bromosuccinimide (0.67 g, 3.80 mmol) was added to the reaction mixture. After 3 hours of reaction at room temperature, the residue obtained by vacuum distillation was separated by column chromatography to obtain 1.2 g of a purple solid.

Rf = 0.3 (SiO _2, methylene chloride: hexane = 3: 1)

mp 210 ° C

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 1.58 (s, 6H), 7.00 (s, 4H), 7.11 (d, 2H, J = 3.8 Hz), 7.25 (s, 2H), 7.91 ( d, 2H, J = 4.1 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ): 22.39, 105.65, 111.79, 124.42, 125.06, 128.35, 128.40, 129.06, 131.03, 137.94, 138.15, 138.99, 157.91.

HRMS (m / z, EI + ) calcd for C 25 H 16 Br 2 N 2 S 4 631.8564, found 631.8543.

5) Synthesis of poly (2- {5- [2,2-dimethyl-7- (2-thienyl) -2H-benzimidazol- (2-thienyl) -4H-thieno [3,2-b] indole) (PTTIDTMBI) , poly ( 4,7- (2-thienyl) -4H-thieno [3,2-b] indole)) - 2,2-dimethyl-2H- benzimidazole- (PTTIBBTMBI)

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole 2-thienyl) -2,2-dimethyl-2H-benzimidazole (13) (0.2 g, 0.436 mmol) (0.357 g, 0.436 mmol) ) And tri-o-tolipospin and tris (di-bellied diacetone) dipalladium (3 mol%) were dissolved in toluene, and the mixture was refluxed under argon gas for 2 days. After cooling to room temperature, methanol was poured into the mixture, and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol. The resulting polymer is dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole (0.357 g, 0.436 mmol) and 4,7-bis (5- (5-bromothiophen-2-yl) -thiophen-2-yl)) - 2,2- After dissolving benzimidazole (15) (0,28 g, 0.436 mmol) and tri-o-tolipospin and tris (dibenzylideneacetone) dipalladium (3 mol%) in toluene, the mixture was stirred under argon It was refluxed for 2 days. After cooling to room temperature, methanol was poured into the mixture, and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol. The polymer obtained was dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

&Lt; Example 3 >

Synthesis of poly (5- [4- (1-octylonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- ] [1,2,5] thiadiazole) (PTTIPT)

1) Synthesis of phenanthro [9,10-c] [1,2,5] thiadiazole (19)

1 M NaN (Me ₃ Si) ₂ solution (86.4 mL) dissolved in tetrahydrofuran was added to a solution of 9,10-phenanthrenequinone 17 (6 g, 28.8 mmol) dissolved in toluene (200 mL) And Me ₃ SiCl (10.9 mL, 86.4 mmol) was added after 30 min. After reaction at 70 ° C for 10 hours, water and ethyl acetate were added. The reaction mixture was washed three times with 100 mL of water, and the residue obtained by vacuum distillation of methylene chloride was added with thionyl chloride (5 mL) at room temperature for 5 hours. After removal of the solvent by vacuum distillation, the residue and triphenylphosphine (10.9 g, 41.6 mmol) were dissolved in methylene chloride. After 2 hours, water and ethyl acetate were added. The reaction mixture was washed three times with 100 m of water and the residue was subjected to vacuum distillation, and the product was separated by column chromatography to obtain 2.23 g of a white solid.

m.p. 165.2 DEG C

^{1 H NMR (300 MHz, CDCl} 3) δ 8.72 (d, 2H, J = 7.4 Hz), 8.50 (d, 2H, J = 7.4 Hz), 7.77-7.66 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ )? 153.3, 131.5, 129.6, 128.1, 126.2, 126.0, 123.4

HRMS (EI +, m / z ) calcd for C 14 H 8 N 2 S 237.0486, measured 237.0487.

2) Synthesis of 5,10-diiodo-phenanthro [9,10-c] [1,2,5] thiadiazole (20)

The product 19 (3.9 g, 12.70 mmol) and N-iodosuccinimide (NIS) (5.99 g, 26.66 mmol) were dissolved in 70 ml of sulfuric acid under argon gas at room temperature. After 1 hour at room temperature, 200 mL of water was added. After this time, the reaction mixture was cooled and filtered to give a yellow solid product which was separated by column chromatography to give a white solid (5.95 g).

m.p. 228 ° C

^{1 H NMR (300 MHz, CDCl} 3) δ 9.07 (d, 2H, J = 2.8 Hz), 8.18 (d, 2H, J = 11.21 Hz), 8.04 (dd, 2H, J = 11.21 and 2.8 Hz)

HRMS (EI +, m / z ) calcd for C 14 H 6 I 2 N 2 S 487.8341, measured 487.8343.

3) Synthesis of poly (5- [4- (1-octyl nonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indol- -c] [1,2,5] thiadiazole) (PTTIPT)

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole Dianthio-phenanthro [9,10-c] [1,2,5] thiadiazole (20) (0.21 g, 0.436 mmol) After dissolving tri-o-tolipospin and tris (dibenzylideneacetone) dipalladium (3 mol%) in toluene, the mixture was refluxed under argon gas for 2 days. After cooling to room temperature, methanol was poured into the mixture and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol. The polymer obtained was dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

<Example 4>

Synthesis of poly (2,5-dioctyl-3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [3,2- b] (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione) (PTTIDPP)

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

Thiophenenitrile (22) (55.2 g, 500 mmol) was added to 67.4 g (600 mmol) of potassium t-butoxide and 400 ml of amyl alcohol, followed by stirring at 105 ° C for 1.5 hours. 19 g (130.493 mmol) of dimethyl succinate and 60 ml of amyl alcohol were added and stirred at 105 DEG C for 2 hours. After cooling to 50 DEG C, methanol (300 mL) and water (80 mL) were added, and the mixture was stirred for 45 minutes. Filtered and the resulting solid residue was washed with methanol and water to give 49.7 g of a black solid.

^{1 H NMR (300 MHz, DMSO} ): δ (ppm) 11.00 (s, 2H) 8.23 (d, 2H, J = 3.0 Hz) 7.89 (dd, 2H, J = 3 Hz) 7.27 (t, 2H, J = 3.0 Hz)

¹³ C NMR (75 MHz, DMSO)? (Ppm) 168.2, 142.6, 136.6, 130.5, 128.3, 127.1, 113.6

HRMS, m / e calcd for C 14 H 8 N 2 O 2 S 2, 300.0 found 300.02

Synthesis of 2,5-dioctyl-3,6-bis (thiophen-2-yl) pyrrolo [3,4-c] pyrrole-

Pyrrol-l, 4-dione (23) (13.0 g, 43.3 mmol) synthesized in 1) above ) And potassium carbonate (24 g, 173 mmol) were dissolved in dimethylformamide (250 ml) and stirred at 145 占 폚 in the presence of argon. 1-Bromooctane (21 ml, 200 mmol) was added and the mixture was stirred for 15 hours. After cooling to room temperature, water was added and the solid residue formed by filtration was washed with methanol and water. After vacuum distillation, the product was isolated by tube chromatography to obtain 17.3 g of a black solid.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 8.94 (dd, 2H, J = 4.0 Hz, 0.8 Hz) 7.65 (dd, 2H, J = 4.8 Hz, 3.6 Hz) 7.29 (dd, 2H, J = 5.0 Hz, 3.6 Hz) 4.08 (t, 4H, J = 8.0 Hz) 1.75 (m, 4H) 1.48-1.18

HRMS, m / e calcd for C 30 H 40 N 2 O 2 S 2, 524.78 found 524.31

Synthesis of 3,6-bis (5-bromothiophen-2-yl) -2,5-dioctylpyrrolo [3,4-c] pyrrole-

(24.2) (4.52 g, 17.6 mmol) synthesized in the above 2) and N-bromosuccinimide (3.14 g, 17.6 mmol) were dissolved in chloroform (200 ml). After stirring for 40 hours, 200 ml of methanol was added, and the resulting solid residue was washed with methanol and water to obtain a black solid.

J = 4.0 Hz) 7.25 (d, 2H, J = 4.0 Hz, 2 Hz) 3.99 (t, 4H, J = 8.0 Hz) ¹ H NMR (300 MHz, CDCl ₃ ):? J = 7.2 Hz) 0.86 (t, 6H, J = 7.2 Hz), 1.72 (m, 4H) 1.46-1.22

HRMS m / e calcd for C ₃₀ H ₃₈ Br ₂ N ₂ O ₂ S ₂ , 680.07 found 681.94

4) Synthesis of poly (2,5-dioctyl-3- {5- [4- (1-octylonyl) -6- (2-thienyl) -4H-thieno [3,2- b] indole- 2-thienyl} -6- (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione) (PTTIDPP) synthesis

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole 3,4-c] pyrrole-1,4- diamine (6) (0.357 g, 0.436 mmol) and 3,6-bis (5-bromothiophen- Ion (25) (0.29 g, 0.436 mmol) and tri-o-tolipospin and tris (dibenzylideneacetone) dipalladium (3 mol%) were dissolved in toluene. The mixture was refluxed under argon gas for 2 days. After cooling to room temperature, methanol was poured into the mixture and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol.

The polymer obtained was dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

&Lt; Example 5 >

Poly (1,4-bis (4-butylphenyl) -3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [ ] Indole-2-yl] -2-thienyl} -6- (2-thienyl) pyrrolo [3,2- iDPP)

1) Synthesis of ethyl 2- (5-bromo-thienyl) -2-acetate (28)

2-Ethylthiophene acetate 27 (10 g, 66.66 mmol) was dissolved in THF (100 mL), N-bromosuccinimide (13 g, 73.26 mmol) was added and the mixture was stirred for 24 hours and extracted with methylene chloride The product was isolated by vacuum distillation and column chromatography. 17 g (84%) of a yellow oil were obtained.

Rf 0.5 (SiO ₂ , methylene chloride: hexane = 1: 20)

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 1.29 (t, 3H, J = 7.1 Hz), δ 3.76 (s, 2H), δ 4.19 (q, 2H, J = 7.1 Hz), δ 6.69 (d, IH, J = 3.8 Hz), [delta] 6.90 (d, IH, J = 3.8 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm) 14.35, 36.07, 61.59, 111.55, 127.31, 129.66, 137.09, 170.05

HRMS (m / z, EI + ) calcd for C 8 H 9 BrO 2 S 247.9507, found 247.9509.

2) Synthesis of bis (4-butylphenyl) ethane dimimidoyl dichloride (31)

4-Butylaniline 29 (5 ml, 31.49 mmol) was dissolved in 100 ml of toluene. Oxalyl chloride 30 (8 ml, 84 mmol) was added thereto and the mixture was stirred at room temperature for 20 minutes. Phosphorus pentachloride g, 35.41 mmol). After stirring at 110 ° C for 2 hours, the mixture was cooled, and methylene chloride and ammonium chloride aqueous solution were added thereto. The mixture was stirred at room temperature for 4 hours, extracted with methylene chloride, vacuum distilled, and the product was isolated by column chromatography. 7.21 g (59%) of a yellow solid were obtained.

Rf 0.5 (SiO ₂ , methylene chloride: hexane = 1: 5)

mp 100 ° C

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) δ 2.40 (s, 6H), 7.08 (d, 4H, J = 8.0 Hz), 7.26 (d, 4H, J = 7.7 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ):? (Ppm)? 21.42, 121.09, 129.79, 137.05, 138.07, 143.31

HRMS (m / z, EI + ) calcd for C 14 H 10 Cl 2 N 2 276.0221, found 276.0221.

3) Synthesis of 3,6-bis- {5- [4- (diphenylamino) phenyl] -2-thienyl} -1,4-bis (4-methylphenyl) pyrrolo [ Synthesis of 2,5-dione (32)

The monomer (7.3 g, 29.53 mmol) of bis (4-butylphenyl) ethane diimidoyl dichloride 31 obtained in 2) above was dissolved in 100 ml of THF and sodium bis (trimethylsilyl) amide (23.54 ml, 120.4 mmol ). After stirring at -78 ° C for 1 hour, the compound of Formula 28 (5 g, 12.84 mmol) obtained in 1) above was added and the mixture was stirred at room temperature for 64 hours. The product was recrystallized from an ammonium chloride solution, extracted with methylene chloride, vacuum distilled, and the product was isolated by column chromatography. 2-thienyl} -1,4-bis (4-methylphenyl) pyrrolo [3,2-b] pyrrole- 1.6 g (18%) of 5-dione was obtained.

Rf 0.5 (SiO ₂ , methylene chloride: hexane = 1: 2)

mp 300 ° C

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) δ 2.44 (s, 6H), 5.99 (d, 2H, J = 4.1 Hz), 6.72 (d, 2H, J = 4.1 Hz), δ 7.18 ( d, 4H, J = 8.5 Hz),? 7.26 (d, 4H, J = 6.3 Hz)

¹³ C NMR (75 MHz, CDCl ₃ ): δ 21.25, 100.18, 110.00, 116.33, 126.97, 129.44, 129.79, 129.88, 130.75, 131.16, 138.78, 142.22, 170.04

HRMS (m / z, EI + ) calcd for C 28 H 19 Br 2 N 2 O 2 S 2 636.9255, found 636.9255.

4) Synthesis of poly (1,4-bis (4-butylphenyl) -3- {5- [4- (1-octylnonyl) -6- (2-thienyl) -4H-thieno [ yl) -2-thienyl} -6- (2-thienyl) pyrrolo [3,2-b] pyrrole-2,5 PTTI-iDPP)

The resulting purified 4- (1-octylonyl) -2- (trimethylstannyl) -6- [4- (trimethylsteveryl) -2-thienyl] -4H-thieno [3,2- b] indole (4-methylphenyl) pyrrolo (6) (0.357 g, 0.436 mmol) and 3,6-bis- {5- [4- (Triphenylphosphine) palladium (3 mol%) and tri-o-tolipospin and tris (diisobutylideneacetone) dipalladium (3 mol%) were dissolved in toluene And the mixture was refluxed under argon gas for 2 days. After cooling to room temperature, methanol was poured into the mixture and the precipitate was collected by filtration. The resulting solid material was reprecipitated several times using 100 mL of chloroform and 1.0 L of methanol. The resulting polymer is dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene.

Example 6 Fabrication of optical energy conversion device using PTTIDTBT and PTTIDTMBI

1, a semitransparent electrode 2 made of indium tin oxide (ITO) is formed on a glass or plastic substrate 1, and a 50 nm thick A conductive polymer (Baytron P, HC Starck) hole transporting layer 3 was formed.

A 100 nm thick solar absorbing organic semiconductor layer 4 formed in Examples 1 and 2 was formed on the hole transport layer 3 and aluminum was formed on the organic semiconductor layer 4 using aluminum. A metal electrode 5 was formed.

Example 7 Photoelectric efficiency measurement

The solubility, molecular weight, mass average molecular weight, absorbance, and current-voltage of the PTTIDTBT and PTTIDTMB were measured for the organic solvents prepared in Examples 1 and 2. The energy conversion occurred in the PTTIDTBT and PTTIDTMBI and PCBM mixed layers, The measurement of the fabricated device was performed in air.

In the case of the solubility in the organic solvent, it was confirmed that PTTIDTBT and PTTIDTMBI were dissolved in tetrahydrofuran, chloroform and o-dichlorobenzene used in the production process in Examples 1 and 2, respectively, It was found that the polymer having an enylthienoindole functional group had good solubility in an organic solvent and was completely dissolved in a general organic solvent.

Also, the number average molecular weight of PTTIDTBT and PTTIDTMBI is 7,700 to 10,000, and the mass average molecular weight is 14,000 to 120,000, which satisfies the range of the weight average molecular weight of the polymer (5,000 to 200,000), which affects the physical properties of the device and the improvement of photoelectric efficiency. .

The absorbance, and the current-voltage will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view of a light energy conversion device using a conjugated polymer according to the present invention. In the case of Example 6, a PTTIDTBT and PTTIDTMBI are used as an active layer, Al) are used as a cathode and an anode, respectively.

FIG. 2 shows the absorbance spectrum of a solution state using PTTIDTBT and PTTODTMBI in the present invention, and it can be confirmed that the maximum absorption wavelength appears at about 400 to 800 nm.

FIG. 3 shows the absorbance spectrum of the film state using PTTIDTBT and PTTODTMBI. Referring to FIG. 3, it was confirmed that the maximum absorption wavelength appears at about 427 to 710 nm.

In both FIG. 2 and FIG. 3, the absorption region appears up to 400 to 900 nm, and absorption at a long wavelength is smooth.

FIG. 4 shows the current-voltage characteristics of PTTIDTBT and PTTODTMBI. In the case of PTTIDTBT, HOMO is -5.17 and LUMO is -3.9. In the case of PTTODTMBI, HOMO is -5.12 eV and LUMO is -3.58 eV there was.

Thus, from the results of the above examples, the polymer having an alkylthienylthienoerythieno functional group according to the present invention contains an alkylthienylthienoerythone functional group as an electron donor and various kinds of aromatic monomers as an electron acceptor By including more than one species, the solubility is improved, so that it is easily dissolved in a general organic solvent, and the absorbed amount of the photon is increased by extending the absorption region to a long wavelength, thereby improving the energy conversion efficiency of the solar cell.

In addition, when applied to a light energy conversion device, the HOMO level of the polymer is lowered, so that the voltage difference with the LUMO becomes larger, and thus the photoelectric efficiency can be improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. And various modifications and variations are possible within the scope of the appended claims.

1 ... substrate 2 ... translucent electrode
3 ... Hole transport layer 4 ... Organic semiconductor layer
5 ... metal electrode

Claims

A polymer having an alkylthienylthienoaround functional group represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

The method according to claim 1,
Wherein the polymer is any one selected from compounds represented by the following Chemical Formulas 2 to 7:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

The method according to claim 1,
Wherein the polymer has a mass average molecular weight of 5,000 to 200,000.

Board;
A semi-transparent electrode formed on the substrate;
A hole transport layer;
A polymer light emitting layer formed of the polymer according to any one of claims 1 to 3; And
And a metal electrode are sequentially formed on the substrate.

5. The method of claim 4,
Wherein the substrate is glass or plastic.

A light energy conversion element using the polymer according to any one of claims 1 to 3.