poly(3-hexylthiophene): synthetic methodologies and properties in bulk heterojunction solar cells...
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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
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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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