Poly(3-hexylthiophene): synthetic methodologies and properties in bulk heterojunction solar cellsAssunta Marrocchi,* Daniela Lanari,Antonio Facchetti and Luigi Vaccaro*Energy Environ. Sci., 2012, 5, 8457-8474

Teacher: Guey-Sheng Liou

Student: Yu-Ting Huang

Date:2013/11/15

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Outline Introduction Metal-assisted cross-coupling reactions

Nickel-catalyzed coupling polymerization

Palladium-catalyzed coupling polymerizations Oxidative coupling polymerization BHJ photovoltaic cells incorporating regioregular

P3HTs Conclusions

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Introduction

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Solar Cells

Solar cell

Silicon

Crystalline

Amorphous

Single crystalline

Poly crystalline

CompoundШ-Ѵ (GaAs, InP)

II-ѴI (CdS, CdTe)

Organic

Dye-sensitized

OSCs

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Advantages of Organic Solar Cells

(1)Manufacturing Process & Cost

(2)Tailoring Molecular Properties

(3)Desirable Properties

(4)Environment Impact

(5)Multiple Uses and Applications

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Characterization of a Solar Cell

開路電壓 (open circuit voltage, Voc)

短路電流 (short circuit current, Jsc)

填充因子 (fill factor, FF)

光電轉換效率 (power conversion efficiency, PCE)

Angew. Chem. Int. Ed., 2012, 51, 2020

Angew. Chem. Int. Ed. 2012, 51, 2020 – 2067 7

Device structure

Planar Heterojunction(PHJ)

Bulk Heterojunction(BHJ)

Donor and Acceptor

Donor : PCBM

Acceptor:P3HT

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S

n

Metal-assisted cross-coupling reactions

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Nickel-catalyzed coupling polymerization

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Enhanced Electrical Conductivity in Regioselectively Synthesized

Poly(3-al kylthiophenes)R. D. McCullough, R. D. Lowe, M. Jayaraman and D. L. Anderson

J. Org. Chem., 1993, 58, 904

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98 %HT P3HT(Mn=12 200 g mol-1, PDI~1.9), yield 36 %

The First Regioregular Head-to-Tail Poly( 3-hexylthiophene-2,5-diyl) and a Regiorandom

Isopolymer: Ni vs Pd Catalysis of 2( 5)-Bromo-5( 2)- (bromozincio) -3-hexylthiophene Polymerization

Tian-An Chen and Reuben D. Rieke*J. Am. Chem. SOC. 1992, 114, 10087-10088

1298 %HT P3HT(Mn=37 680 g mol-1, PDI=1.48), yield 82 %

Regioregular, Head-to-Tail Coupled Poly(3-alkylthiophenes) Made Easy by the GRIM Method:

Investigation of the Reaction and the Origin of Regioselectivity

Robert S. Loewe, Paul C. Ewbank, Jinsong Liu, Lei Zhai, and Richard D. McCullough*Macromolecules 2001, 34, 4324-4333

13~99 %HT P3HT(Mn=20 000- 35 000g mol-1, PDI=1.2-1.4), yield 71 %

GRIM

Chain-Growth Polymerization forPoly(3-hexylthiophene) with a Defined

Molecular Weight and a Low Polydispersity Akihiro Yokoyama, Ryo Miyakoshi, and Tsutomu Yokozawa*

Macromolecules 2004, 37, 1169-1171

14>98 %HT P3HT(Mn=31 700 g mol-1, PDI=1.36), yield 78 %

Extremely regio-regular poly (3-alkylthiophene)s from simplified chaingrowth Grignard metathesis

polymerisations and the modification of their chain-ends

Roger C Hiorns, Abdel Khoukh, Benoit Gourdet and Christine Dagron-Lartigau∗Polym Int, 2006,55,608–620

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100%HT P3HT(Mn=33 400 g mol-1, PDI=1.12), yield 37-48 %

Purification-Free and Protection-Free Synthesis of Regioregular Poly(3-hexylthiophene) and Poly(3-(6-hydroxyhexyl)thiophene) Using a Zincate Complex of t-Bu4ZnLi2

Tomoya Higashihara,* Eisuke Goto, and Mitsuru UedaACS Macro Lett., 2012, 1, 167

16>90 % HT P3HT(Mn=25 000-307 000 g mol-1, PDI<1.2), yield 80-90%

Palladium-catalyzed coupling polymerizations

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Synthesis and characterisation of telechelic regioregular head-to-tail poly(3-alkylthiophenes)

Ahmed Iraqi* and George W. Barker

J. Mater. Chem., 1998, 8, 25–29

18>96 % HT P3HT(Mn=10 000-16 000 g mol-1, PDI=1.2-1.4), yield 10-50 %

Tris[tri(2-thienyl)phosphine]palladium as the CatalystPrecursor for Thiophene-Based Suzuki-Miyaura

Crosscoupling and Polycondensation WEIWEI LI, YANG HAN,1BINSONG LI, CAIMING LIU, ZHISHAN BO*

J. Polym. Sci., Part A: Polym. Chem., 2008, 46, 4556

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97 % HT P3HT(Mn=26 000 g mol-1, PDI=2.3), yield 72 %

Palladium-Catalyzed Dehydrohalogenative Polycondensation of 2-Bromo-3-hexylthiophene:

An Efficient Approach to Head-to-TailPoly(3-hexylthiophene)

Qifeng Wang, Ryo Takita, Yuuta Kikuzaki, and Fumiyuki Ozawa* J. Am. Chem. Soc., 2010, 132, 11420-11421

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Herrmann’s catalyst

98 % HT P3HT(Mn=30 600 g mol-1, PDI=1.6), yield 99%

Oxidative coupling polymerization

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Head-to-Tail Regioregularity of Poly(3- hexylthiophene) in Oxidative Coupling

Polymerization with FeCl3 S. Amou, O. Haba, K. Shirato, T. Hayakawa, M. Ueda*, K. Takeuchi and M. Asai,

J. Polym. Sci., Part A: Polym. Chem., 1999, 37, 1943.

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89 % HT P3HT(Mn=38 000 g mol-1, PDI=2), yield 62%Long time(200 h) 88 % HT P3HT(Mn=68 000 g mol-1, PDI=1.9), yield 100%

Synthesis Of Poly(3 hexylthiophene) by Using the VO(acac)2-FeCl3-O2 Catalyst System

S. Yu, T. Hayakawa and M. Ueda, Chem. Lett., 1999, 559-560.

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BHJ photovoltaic cells incorporating regioregular P3HTs

Effect of the regioregularity of poly(3-hexylthiophene) on the performances of organic

photovoltaic devices

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77 %HT P3HT(Mn=20400 g mol-1, PDI=2.8)

97 %HT P3HT(Mn=20600 g mol-1, PDI=1.2)

Influence of the Molecular Weight of Poly(3-hexylthiophene) on the Performance of Bulk

Heterojunction Solar Cells Pavel Schilinsky,,§ Udom Asawapirom, Ullrich Scherf, Markus Biele, and Christoph J. Brabec

Chem. Mater. 2005, 17, 2175-2180

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Conclusions

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Regioregularity of P3HT is known to be one of the key parameters affecting the related solar cells performance, and critically depend on the regioselectivity of the synthetic approaches to conducting P3HT.

Intensive studies have also revealed that the regioregular polymerization of P3HT proceeds via a chain-growth mechanism and may also exhibit living characteristics.

This feature allows for the precise control of the polymer molecular weight and polydispersity, which were found to be, in turn, critical parameters modulating polymer electronic, optical, electrochemical properties, and solid-state packing, therefore influencing the OPV device performance

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Thank you

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