KR20100026373A - Copolymers with 4h-cyclopenta[def]phenanthrene (cpp) back-bone and organic polymer thin film solar cells comprising the same - Google Patents

Abstract

PURPOSE: A copolymer with 4H-cyclopenta[def]phenanthrene(CPP) back-bone is provided to ensure broad sunlight absorption band, excellent electroconductivity and photoelectric power, and to be useful for an organic polymer solar cell, organic thin film transistor, and organic electroluminescent device. CONSTITUTION: A copolymer has a 4H-cyclopenta[def]phenanthrene(CPP) back-bone represented by chemical formula 1. In chemical formula 1, A is an electron acceptor, D is a 4H-cyclopenta[def]phenanthrene derivative, and n is 10-150. The D is a compound represented by chemical formulas 2 or 3. In chemical formulas 2 and 3, R1 and R2 are independently C1-20 linear or branched alkyl group. The A is a compound represented by chemical formula 4.

Description

Copolymers with 4H-cyclopenta [def] phenanthrene (CPP) back-bone and organic polymer thin film solar cells comprising the copolymer having a skeleton of 4H-cyclopenta phenanthrene same}

The present invention relates to a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton and a device comprising the same, and more particularly, to a 4 H -cyclopenta [ def ] phenanthrene derivative skeleton having a narrow band gap. The present invention relates to an alternating copolymer and an organic polymer thin film solar cell device using the same.

In 1992, UCSB's Heeger first demonstrated the possibility of solar cells using organic polymers. It is a thin-film device made of a bulk heterojunction between organic polymer and C _{60. The} electron generated after the organic polymer receives sunlight has a principle of C _{60, which} has high electron affinity, attracts the electron and converts it into electricity. . Thus, the highest efficiency of the organic polymer thin film solar cell using the organic polymer is 6.5% ( Science , 2007 , 307 , 222-225).

However, the maximum efficiency of the solar cell using silicon is 39%, which is much higher than that of the organic polymer solar cell. Thus, the development of organic polymer solar cells with higher efficiency is required.

Accordingly, an object of the present invention is to provide a novel copolymer capable of spin coating at room temperature by dissolving in an organic solvent while having a wider solar absorption band.

It is also an object of the present invention to provide an organic polymer thin film solar cell device comprising the organic polymer.

Another object of the present invention is to provide an organic thin film transistor including the organic polymer as an organic semiconductor material.

Another object of the present invention to provide an organic light emitting device comprising the organic polymer as a light emitting material.

In order to achieve the above object, the present invention

It provides a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by the following formula (1):

<Formula 1>

Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and repeating unit n is an integer from 10 to 150.

In order to achieve the above another object, the present invention

An organic polymer thin film solar cell comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to the present invention as a solar absorbing material.

The copolymer having a skeleton of the 4 H -cyclopenta [ def ] phenanthrene of the present invention not only has a wide solar absorption band but also is well dissolved in a general organic solvent, allowing room temperature spin coating to be bent through a simple process. It has the great advantage of fabricating organic polymer thin film solar cell on plastic substrate.

The present invention provides a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by the following formula (1):

Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and repeating unit n is an integer from 10 to 150.

The phenanthrene derivative represented by D in Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3:

Wherein, R ₁ and R ₂ are each independently a linear or branched alkyl group of C _{1 -20.}

Wherein, R ₁ and R ₂ are each independently a linear or branched alkyl group of C _{1 -20.}

The electron acceptor represented by A in Formula 1 may be represented by Formula 4 below:

More specifically, Chemical Formula 1 may be represented by the following Chemical Formula 5 or Chemical Formula 6.

In the above formula, repeating unit n is an integer of 10 to 150.

The organic polymer includes a 4 H -cyclopenta [ def ] phenanthrene derivative as an electron donor and a di (2-thienyl-2-yl) -2,1,3-benzothiazole as an electron acceptor. .

The polymer according to one embodiment of the present invention is a new backbone, 4 H -cyclopenta [ def ] phenanthrene derivative, as an electron donor, as a di (2-thien-2-yl) -2,1,3-benzothia By using the diazole as an electron acceptor, it has a characteristic of absorbing light in a wavelength band that is longer than that of a conventional solar cell polymer, that is, that the conventional polymer does not absorb.

The 4H -cyclopenta [ def ] phenanthrene derivative of the present invention and the di (2-thienyl-2-yl) -2,1,3-benzothiadiazole alternating polymer can be prepared using conventional methods known in the art. It can be synthesized, and is not particularly limited. More specifically, the compounds represented by Formula 5 and Formula 6 may be synthesized according to the following Schemes 1 and 2.

Poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy Yen-yl) - Synthesis of 2,1,3-benzothiadiazole)))

As shown in Scheme 1, 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b) was obtained through hydrogenation of 4H -cyclopenta [ def ] phenanthrene (Formula 1a). , 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] through bromination of the 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b) A phenanthrene (Formula 1c) was obtained and the 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1c) was reacted with bromine to give 2,6-dive Obtain lomo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d), and hydroxylate the 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) with 2-ethylhexylbromide It is reacted with sodium 2,6-dibromo-4,4-bis (2-ethylhexyl) -4 H - to give the cyclopenta [def] phenanthrene (formula 1e), wherein the 2,6-dibromo- 4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene (Formula 1e) of bis (pinacolato) boron was reacted with dimethyl 4,4-bis (2-ethylhexyl) 2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H - cyclopenta [def] phenanthrene Tren (Formula 1f) was obtained and the 4,4-bis (2-ethylhexyl) -2,6-bis (4 ′, 4 ′, 5 ′, 5′-tetramethyl-1 ′, 3 ′, 2 '- dioxane Sabo Lauren-2'-yl) -4 H-cyclopenta [def] phenanthrene (formula 1f) and 4,7-bis (5-bromo-2-Im yen yl) -2,1,3 - benzothiazol Oh oxadiazole (formula 1h) via a Suzuki coupling reaction of poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt -((4,7-di ((2-thienyl) -2,1,3-benzothiadiazole))) (Formula 1 g) is obtained.

Poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di (( Synthesis of 2-thienyl) -2,1,3-benzothiadiazole)))

As shown in Scheme 2, 2,6-dibromo -4 H-cyclopenta [def] phenanthrene (Formula 1d) of 2,6-dibromo -4 H through the oxidation-cyclopenta [def] phenanthrene 4-one (Formula 2a) was obtained, and the 2,6-dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 2a) was mixed with phenol, zinc chloride (II), and hydrogen chloride gas. reacting 2,6-dibromo-4,4-bis (4'-hydroxyphenyl) -4 H - cyclopenta [def] phenanthrene (formula 2b) of the 2,6-dibromo-4, to give , 4-bis (4'-hydroxyphenyl) -4 H - cyclopenta [def] phenanthrene (formula 2b) was reacted with 2-ethylhexyl bromide and 2,6-dibromo-4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene give the (formula 2c), and wherein the 2,6-dibromo-4,4-bis (4 - ((2 -ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene (formula 2c) of bis (pinacolato 4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1' , 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H-cyclopenta [def] phenanthrene (formula 2d) to obtain, and the 4,4-bis (4 - ((2-ethylhexyl )) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioctyl Sabo Lauren-2'-yl) -4 H - cyclopenten Suzuki coupling reaction between penta [ def ] phenanthrene (Formula 2d) and 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole (Formula 1g) via a poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ( (2-thienyl) -2,1,3-benzothiadiazole))) is obtained by formula (2e).

The present invention also provides an organic polymer thin film solar cell device using the organic polymer (copolymer having a 4H -cyclopenta [ def ] phenanthrene skeleton) as a light absorbing material, and a 4H -cyclopenta [ def ] phenanthrene skeleton. An organic electroluminescent element using a copolymer having a light emitting material and an organic thin film transistor using an organic semiconductor material are provided.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited by the following examples.

Example

Example  One

Poly (2,6-((4,4- Vis (2- Ethylhexyl )-4 H Cyclopenta [ def ] Phenanthrene)- alt -((4,7-die ((2- Cynyl ) -2,1,3- Benzothiadiazole Manufacture of)))

1) Synthesis of 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1b)

1.0 g (5.3 mmol) and 100 palladium / carbon 0.50 g of 4H -cyclopenta [ def ] phenanthrene (Formula 1a) were dissolved in 20 ml of methanol, followed by stirring at room temperature for 20 hours under hydrogen gas. After filtering off the catalyst, the solid residue produced by vacuum distillation of the solvent was separated by column chromatography. 0.90 g (87%) of a white solid was obtained.

R _f = 0.8 (SiO ₂ , hexane100%)

FT-IR (KBr, cm ^-1 ): 3043, 3017, 2925, 2888, 2830, 2830, 1452, 1432, 1389, 810, 767, 726, 693

¹ H NMR (300 MHz, CDCl ₃ ) δ7.37 (d, 2H, J = 7.4 Hz), 7.24 (t, 2H, J = 7.4 Hz), 7.17 (d, 2H, J = 7.4 Hz), 3.92 ( s, 2H), 3.18 (s, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 140.67, 139.65, 130.76, 127.51, 124.92, 122.95, 37.69, 26.51

HRMS, m / e, C ₁₅ H ₁₂ , 192.0943 (calcd. 192.0939)

2) Synthesis of 2,6-Dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1c)

0.90 g (4.6 mmol) of the compound of Formula 1b thus obtained was dissolved in 80 ml of carbon tetrachloride, and then 12 g of aluminum tribromide complex was added, followed by stirring at 80 ° C. for 5 hours. After filtering the solids, the solid residue resulting from vacuum distillation of the solvent was separated by column chromatography. 1.5 g (93%) of a pale yellow solid was obtained.

R _f = 0.5 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 2925, 2894, 2828, 1574, 1433, 1411, 1394, 1065, 861, 839, 788

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.47 (s, 2H), 7.46 (s, 2H), 3.83 (s, 2H), 3.08 (s, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 141.81, 137.56, 131.91, 128.43, 126.43, 121.33, 37.35, 25.95

HRMS, m / e, C ₁₅ H ₁₀ Br ₂ , 347.9153 (calcd. 347.9149)

3) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d)

1.5 g (4.3 mmol) of the compound of Chemical Formula 1c thus obtained was dissolved in 30 ml of carbon disulfide, and 0.27 ml (5.2 mmol) of bromine was slowly added at room temperature for 2 hours, followed by stirring for 1 hour. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1.2 g (80%) of a pale yellow solid was obtained.

R _f = 0.53 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3043, 2926, 1570, 1419, 1403, 1309, 1211, 1063, 863, 831, 808, 711, 688

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.99 (s, 2H), 7.80 (s, 2H), 7.75 (s, 2H), 4.32 (s, 2H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 143.03, 132.91, 128.97, 127.97, 126.41, 125.62, 125.31, 37.16

HRMS, m / e, C ₁₅ H ₈ Br ₂ , 345.8993 (calcd. 345.8993)

Synthesis of the cyclopenta [def] phenanthrene (Formula 1e) - 4) 2,6- dibromo-4,4-bis (2-ethylhexyl) -4 H

3.1 g (9.0 mmol) of the compound of Chemical Formula 1d and a catalytic amount of triethylbenzylammonium chloride were dissolved in 175 ml of dimethyl sulfoxide, and 4.8 ml (27 mmol) of 2-ethylhexyl bromide was added thereto. After stirring at 60 ° C. for 1 hour, 10 ml of 50% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred at room temperature for 5 hours. Excess ethyl acetate was added to form sodium hydroxide precipitate, which was then filtered and the organic layer was extracted with distilled water. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 3.6 g (70%) of white crystals were obtained.

R _f = 0.6 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3046, 2959, 2926, 2872, 2858, 2728, 1909, 1744, 1593, 1577, 1460, 1416, 1390, 1379, 1367, 1306, 1222, 1213, 1066

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.95 (s, 2H), 7.74 (s, 2H), 7.64 (s, 2H), 2.17 (d, 4H, J = 5.1 Hz), 0.87-0.47 (m , 30H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 150.97, 135.44, 128.64, 125.89, 125.63, 124.68, 121.84, 59.72, 44.03, 35.45, 34.06, 28.28, 27.55, 22.86, 14.20, 10.53

HRMS, m / e, C ₃₁ H ₄₀ ⁷⁹ Br ⁷⁹ Br, 570.1532 (calcd. 570.1497), C ₃₁ H ₄₀ ⁷⁹ Br ⁸¹ Br, 572.1495 (calcd. 572.1476), C ₃₁ H ₄₀ ⁸¹ Br ⁸¹ Br, 574.1454 (calcd 574.1456)

5) 4,4-bis (2-ethylhexyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2'-dioxaborene-2' Synthesis of -H ) -4H-cyclopenta [ def ] phenanthrene (Formula 1f)

2.2 g (3.8 mmol) of the compound of formula 11e, 4.9 g (19 mmol) of bis (pinacolato) diboron and 2.3 g (23 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. 0.18 g (0.23 mmol) of 1,1'-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex was added at room temperature, followed by stirring at 60 ° C for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite, and distilling off the solvent under vacuum distilled off the product, the product was separated by column chromatography. 2.0 g (78%) of white crystals were obtained.

R _f = 0.42 (SiO ₂ , ethyl acetate: hexane = 1:20)

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.31 (s, 2H), 7.98 (s, 0.5H by chirality of 2H), 7.96 (s, 1H by chirality of 2H), 7.94 (s, 0.5H by chirality of 2H), 2.16 (d, 4H, J = 4.67 Hz), 1.41 (s, 24H), 0.82-0.44 (m, 30H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 149.19, 139.71, 130.79, 128.23, 127.91, 126.04, 125.71, 83.91, 59.04, 44.03, 35.41, 33.98, 28.18, 27.73, 25.14, 22.90, 14.27, 10.61

HRMS, m / e, C ₄₃ H ₆₄ B ₂ O ₄ , 666.4996 (calcd. 666.5005)

6) a poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy Yen days ) -2,1,3-benzothiadiazole))) Synthesis of Formula 1e)

Thus obtained 0.29 g (0.43 mmol) of the compound of Formula 1f, 0.22 g (0.43 mmol) of the compound of Formula 1h, 2.1 ml of an aqueous 2M potassium carbonate solution and 15 mg (0.013 mmol) of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 11 ml of toluene and stirred at 80 ° C. for 4 days. The solution was filtered after the resultant solid was slowly added to 500 ml of methanol, washed, and dried to the desired product of poly (2,6 - ((4,4-bis (2-ethylhexyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy yen-yl) -2,1,3- oxadiazole benzothiazol O)) of the target compound) 100mg.

Example  2

Poly (2,6- (4,4- Vis (4-((2- Ethylhexyl ) Oxy ) Phenyl )-4 H Cyclopenta [ def ] Phenanthrene)- alt -((4,7- die ((2- Cynyl ) -2,1,3- Benzothiadiazole Manufacture of)))

1) Synthesis of 2,6-Dibromo- 4H -cyclopenta [ def ] phenanthren-4-one (Formula 2a)

1.2 g (3.5 mmol) of 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) was dissolved in 100 ml of benzene, followed by addition of 5.0 g (58 mmol) of 85% manganese dioxide (IV). It stirred at 12 degreeC. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 1.0 g (80%) of a yellow solid was obtained.

R _f = 0.2 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3442, 1720, 1628, 1454, 1417, 1218, 1066, 881, 773, 678

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.10 (s, 2H), 7.90 (s, 2H), 7.72 (s, 2H)

¹³ C NMR (75 MHz, Benzene-d6) δ 190.08, 137.89, 133.97, 129.52, 126.79, 126.72, 125.14, 124.27

HRMS, m / e, C ₁₅ H ₆ ⁷⁹ Br ⁷⁹ BrO, 359.8781 (calcd. 359.8785)

Synthesis of the cyclopenta [def] phenanthrene (formula 2b) - 2) 2,6- dibromo-4,4-bis (4'-hydroxyphenyl) -4 H

1.0 g (2.8 mmol) of the compound of Formula 2a, 20 ml of phenol and 0.76 g (5.6 mmol) of zinc chloride (II) were injected at 50 ° C. for 3 hours, and the product was separated by column chromatography. . 1.2 g (84%) of a white solid were obtained.

R _f = 0.2 (SiO ₂ , ethyl acetate: hexane = 1: 3)

FT-IR (KBr, cm ^-1 ): 3853, 3648, 3277, 3032, 1574, 1508, 1230, 1066, 899, 858, 762, 707

¹ H NMR (300 MHz, Acetone-d6) δ 8.35 (s, 2H, OH), 8.15 (d, 2H, J = 1.2 Hz), 8.00 (s, 2H), 7.80 (d, 2H, J = 1.2 Hz ), 7.10 (d, 2H, J = 4.4 Hz), 7.09 (d, 2H, J = 8.9 Hz), 6.75 (d, 2H, J = 4.4 Hz), 6.74 (d, 2H, J = 8.9 Hz)

¹³ C NMR (75 MHz, Acetone-d6) δ 157.49, 153.05, 135.54, 134.48, 130.11, 129.84, 127.16, 126.84, 126.69, 122.75, 116.22, 68.56

HRMS, m / e, C ₂₇ H ₁₆ ⁷⁹ Br ⁷⁹ BrO ₂ , 529.9518 (calcd. 529.9517)

Synthesis of the cyclopenta [def] phenanthrene (Formula 2c) - 3), 2,6- dibromo-4,4-bis (4 '- ((2' - ethylhexyl) oxy) phenyl) -4 H

1.2 g (2.3 mmol) of the compound of Formula 2b thus obtained was dissolved in 100 ml of acetone, and 0.35 g (2.3 mmol) of sodium iodide, 4.9 g (1.4 mmol) of cesium carbonate, and 1.7 ml (9.3 mmol) of 2-ethylhexylbromide were added thereto. After stirring at 70 ° C. for 24 hours. The solid residue resulting from the vacuum distillation of the solvent was separated by column chromatography. 0.46 g (26%) of a white solid were obtained.

R _f = 0.74 (SiO ₂ , hexane 100%)

FT-IR (KBr, cm ^-1 ): 3750, 2960, 2930, 2850, 1610, 1580, 1510, 1470, 1410, 1300, 1280, 1170, 1030, 854, 764, 729

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.98 (s, 2H), 7.79 (s, 2H), 7.66 (s, 2H), 7.12 (d, 4H, J = 8.8 Hz), 6.78 (d, 4H, J = 8.8 Hz), 3.78 (d, 4H, J = 5.8 Hz), 1.65-1.69 (m, 4H), 1.25-1.51 (m, 24H), 0.85-0.91 (m, 16H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.78, 151.89, 135.71, 134.08, 129.27, 129.11, 126.51, 126.15, 125.95, 122.46, 114.64, 70.57, 67.76, 39.58, 30.72, 29.29, 24.13, 23.26, 14.30, 11.33

HRMS, m / e, C ₄₃ H ₄₈ ⁷⁹ Br ⁷⁹ BrO ₂ , 754.2000 (calcd. 754.2021)

4) 4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -2,6-bis (4 ', 4', 5 ', 5'-tetramethyl-1', 3 ', 2 '- synthesis of cyclopenta [def] phenanthrene (formula 2d) - dioxane Sabo Lauren-2'-yl) -4 H

0.72 g (0.95 mmol) of the compound of formula 2c, 1.2 g (4.8 mmol) of bis (pinacolato) diboron and 0.47 g (4.8 mmol) of potassium acetate were dissolved in 40 ml of N , N -dimethylformamide. At room temperature, 50 mg (0.050 mmol) of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloro dichloromethane complex were added, followed by stirring at 60 ° C. for 12 hours. Extraction with ether and distilled water, drying with magnesium sulfite and distillation of the solvent in a liquid residue produced by column chromatography to separate the product. 0.70 g (87%) of yellow liquid was obtained.

R _f = 0.36 (SiO ₂ , ethyl acetate: hexane = 1:20)

FT-IR (KBr, cm ^-1 ): 3744, 2914, 2852, 1617, 1521, 1469, 1381, 1328, 1245, 1130, 1020, 951, 841, 718, 525

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.37 (s, 2H), 8.00 (s, 2H), 7.86 (s, 2H), 7.23 (d, 4H, J = 9 Hz), 6.77 (d, 4H, J = 8.8 Hz), 3.79 (d, 4H, J = 5.7 Hz), 1.64-1.70 (m, 2H), 1.27-1.50 (m, 40H), 0.84-0.93 (m, 12H)

¹³ C NMR (75 MHz, CDCl ₃ ) δ 158.29, 150.47, 138.30, 137.23, 131.43, 129.59, 128.55, 127.43, 126.08, 114.30, 84.08, 70.51, 67.59, 39.62, 30.76, 29.31, 25.21, 24.09, 23.29, 14. , 11.35

HRMS, m / e, C ₅₅ H ₇₂ Br ₂ O ₆ , 850.5507 (calcd. 850.5515)

5) a poly (2,6- (4,4-bis (4 - ((2-ethylhexyl) oxy) phenyl) -4 H-cyclopenta [def] phenanthrene) - alt - ((4,7- dimethyl Synthesis of ((2-thienyl) -2,1,3-benzothiadiazole)))

0.32 g (0.38 mmol) of the compound of Formula 2d, 0.19 g (0.38 mmol) of the compound of Formula 1h, 1.9 ml of a 2M potassium carbonate solution, and 13 mg (0.011 mmol) of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 11 ml of toluene and stirred at 80 ° C. for 4 days. The solution was slowly added to 500 ml of methanol, and the resulting solid was filtered, washed and dried to give the desired product poly (2,6- (4,4-bis (4-((2-ethylhexyl) oxy) phenyl) -4 H - cyclopenta [def] phenanthrene) - alt - ((4,7- di ((2-Sy yen-yl) -2,1,3- oxadiazole benzothiazol O)) of the target compound) 100mg.

The polymers synthesized in Examples 1 and 2 had good solubility in organic solvents and were completely dissolved in general organic solvents. The molecular weight was measured using GPC, and the measured molecular weight was 5,000, number average molecular weight, 8,000 mass average molecular weight, and dispersion degree 1.6. These polymers exhibited maximum absorption near 530 nm.

FIG. 1 is a cross-sectional view of an organic polymer thin film solar cell device using these polymers as a solar absorption layer. A thin film solar cell device is fabricated by using ITO and aluminum (Al) coated on glass as a cathode and an anode, respectively.

Example  3

Fabrication of Organic Polymer Thin Film Solar Cell Devices

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

The polymers prepared in Examples 1 and 2 and [6,6] -phenyl-C61-butyric acid methylester (PCBM) were mixed 1: 4 (w / w) on the hole transport layer 3 to spin coating. To form a 100 nm-thick photovoltaic organic semiconductor layer 4 and to form an aluminum (Al) metal electrode 5 using aluminum on the organic semiconductor layer 4 to fabricate a device for measuring photoelectric efficiency. It was.

Evaluation and Results

FIG. 2 shows an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 1. FIG. Referring to Figure 2, by using the polymer prepared in Example 1 shows a broad light absorption spectrum band in the visible light region. According to the present invention, a characteristic of absorbing light in a wavelength band that is absorbed by a longer wavelength than that of a conventional solar cell polymer, that is, a conventional polymer does not appear.

FIG. 3 shows the device fabricated in this way by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 3 was found to be 1.00% at 100 mW / cm ² light.

4 illustrates an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 2. FIG. Referring to Figure 4, by using the polymer prepared in Example 2 shows a wide light absorption spectrum band in the visible light region. According to the present invention, a characteristic of absorbing light in a wavelength band that is absorbed by a longer wavelength than that of a conventional solar cell polymer, that is, a conventional polymer does not appear.

The device manufactured as described above is illustrated in FIG. 5 by measuring photoelectric efficiency under AM 1.5 conditions. The photoelectric efficiency calculated from FIG. 3 was found to be 1.12% at 100 mW / cm ² light.

6 shows voltage and current density test results of an organic thin film transistor manufactured using the polymer prepared in Example 2. FIG. Referring to FIG. 6, the characteristics of a typical semiconductor in which current density increases with increasing voltage is shown. Therefore, it can be seen that the polymer according to the present invention can be used as a semiconductor material of an organic thin film transistor.

The polymer compound according to the present invention can be applied to an organic polymer solar cell, an organic thin film transistor, and an organic electroluminescent device because the spin coating process is possible when the device is applied and it can provide excellent electrical conductivity, organic electroluminescence, and photovoltaic characteristics. .

1 is a cross-sectional view of an organic polymer thin film solar cell device using a polymer according to the present invention.

FIG. 2 is a graph illustrating an absorption spectrum of an organic polymer thin film solar cell device using the polymer of Example 1. FIG.

3 is a graph illustrating photoelectric efficiency measurement of an organic polymer thin film solar cell device using the polymer of Example 1. FIG.

4 is a graph showing an absorption spectrum of an organic polymer thin film solar cell device manufactured using the polymer prepared in Example 2. FIG.

FIG. 5 is a graph illustrating an absorption spectrum of an organic polymer thin film solar cell device using the polymer of Example 2. FIG.

FIG. 6 is a graph illustrating voltage and current density test results of an organic thin film transistor manufactured using the polymer of Example 2. FIG.

<Description of the symbols for the main parts of the drawings>

1: substrate 2: translucent electrode

3: hole transport layer 4: solar absorption organic semiconductor layer

5: metal electrode

Claims (10)

Co-polymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton represented by Formula 1 below: <Formula 1>

Wherein A is an electron acceptor, D is a 4H -cyclopenta [ def ] phenanthrene derivative, and n is from 10 to 150. The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein D is a compound represented by Formula 2 or Formula 3. <Formula 2>

or <Formula 3>

Wherein, R ₁ and R ₂ are each independently a linear or branched alkyl group of C _{1 -20.} The copolymer having a 4H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein A is a compound represented by the following Chemical Formula 4: <Formula 4>

The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the number average molecular weight is 3,000 to 6,000 and the mass average molecular weight is 7,000 to 10,000. The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 5. <Formula 5>

In the above formula, repeating unit n is an integer of 10 to 150. The copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 6. <Formula 6>

In the above formula, repeating unit n is an integer of 10 to 150. An organic polymer thin film solar cell comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as a solar absorbing material. The organic polymer thin film solar cell of claim 7, wherein the solar light absorbing material is thinned by using a spin coating method. An organic thin film transistor comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as an organic semiconductor material. An organic electroluminescent device comprising a copolymer having a 4 H -cyclopenta [ def ] phenanthrene skeleton according to any one of claims 1 to 6 as a light emitting material.

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