Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Systematic Fluorination of P3HT: Synthesis of P(3HT-co-3H4FT)s by Direct Arylation Polymerization, Characterization, and Device Performance in OPVs

Journal Article · · Macromolecules
 [1];  [1];  [1];  [2];  [1];  [3];  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
We present a strategy for tuning physical properties of P3HT-based copolymers by incorporating a fluorinated thiophene repeat unit. The synthesis and characterization of a series of fluorinated polythiophene P(3HT-co-3H4FT) materials are described, where the percentage of fluorinated repeat units in the polymer backbone is systematically varied from 0 to 100%. These P(3HT-co-3H4FT)s (P0, P25, P50, P75, and P100) were synthesized via direct arylation polymerization (DArP) methods. By varying the feed ratio of the two monomers, the percent of fluorinated repeat units (3H4FT) could be precisely controlled. As fluorination is increased, there is a strong effect on the electronic properties of the polymers, evidenced by a 0.4 eV drop in the EHOMO level for P100 when compared to P0. GIWAXS and TEM were used to determine the crystallinity and morphology. TEM analysis of thin film polymer/PCBM bulk-heterojunction blends indicates that increased fluorination does not result in stronger phase separation. As a result, organic photovoltaic devices were fabricated to evaluate changes in device performance as a result of fluorination.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Polymer-Based Materials for Harvesting Solar Energy (PHaSE)
Sponsoring Organization:
National Science Foundation Graduate Research Fellowship Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001087
OSTI ID:
1370306
Journal Information:
Macromolecules, Journal Name: Macromolecules Journal Issue: 8 Vol. 49; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (45)

Functional Organic Field-Effect Transistors journal September 2010
P3HT:PCBM, Best Seller in Polymer Photovoltaic Research journal July 2011
Synergistic Effect of Fluorination on Molecular Energy Level Modulation in Highly Efficient Photovoltaic Polymers journal November 2013
Semiconducting Polymers Prepared by Direct Arylation Polycondensation journal March 2012
MALDI-ToF analysis of polythiophene: use of trans-2-[3-(4-t-butyl-phenyl)-2-methyl- 2-propenylidene]malononitrile-DCTB-as matrix journal March 2011
Synthesis of End-capped Regioregular Poly(3-hexylthiophene)s via Direct Arylation journal April 2012
Synthesis and characterization of poly(3-hexylthiophene)-poly(3-hexyloxythiophene) random copolymers with tunable band gap via Grignard metathesis polymerization journal May 2014
Semi-random P3HT analogs via direct arylation polymerization
  • Rudenko, Andrey E.; Wiley, Calvin A.; Stone, Shiloh M.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, Issue 18, p. 3691-3697 https://doi.org/10.1002/pola.26175
journal June 2012
Optimization of direct arylation polymerization conditions for the synthesis of poly(3-hexylthiophene) journal March 2013
Random poly(3-hexylthiophene- co -3-cyanothiophene) copolymers with high open-circuit voltage in organic solar cells journal January 2014
Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure journal June 2014
Fluorinated conjugated polymers in organic bulk heterojunction photovoltaic solar cells journal August 2015
Fine Tuning Surface Energy of Poly(3-hexylthiophene) by Heteroatom Modification of the Alkyl Side Chains journal June 2015
Direct (Hetero)Arylation: A New Tool for Polymer Chemists journal April 2013
Synthesis of Conjugated Polymers for Organic Solar Cell Applications journal November 2009
The first regioregular head-to-tail poly(3-hexylthiophene-2,5-diyl) and a regiorandom isopolymer: nickel versus palladium catalysis of 2(5)-bromo-5(2)-(bromozincio)-3-hexylthiophene polymerization journal December 1992
Tetradecafluorosexithiophene:  The First Perfluorinated Oligothiophene journal May 2001
Controlling Phase Separation and Optical Properties in Conjugated Polymers through Selenophene−Thiophene Copolymerization journal June 2010
Palladium-Catalyzed Dehydrohalogenative Polycondensation of 2-Bromo-3-hexylthiophene: An Efficient Approach to Head-to-Tail Poly(3-hexylthiophene) journal August 2010
Mobility-Controlled Performance of Thick Solar Cells Based on Fluorinated Copolymers journal October 2014
Highly Efficient Solar Cell Polymers Developed via Fine-Tuning of Structural and Electronic Properties journal June 2009
Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes journal May 2015
3-Fluoro-4-hexylthiophene as a Building Block for Tuning the Electronic Properties of Conjugated Polythiophenes journal February 2013
Thermochromism in Oligothiophenes:  The Role of the Internal Rotation journal November 2002
Fine-Tuning of Fluorinated Thieno[3,4-b]thiophene Copolymer for Efficient Polymer Solar Cells journal February 2013
Influence of Fluorination and Molecular Weight on the Morphology and Performance of PTB7:PC 71 BM Solar Cells journal May 2014
Importance of Side Chains and Backbone Length in Defect Modeling of Poly(3-alkylthiophenes) journal March 2009
Single-Bond Torsional Potentials in Conjugated Systems:  A Comparison of ab Initio and Density Functional Results journal October 1997
A Theoretical Investigation of the Torsional Potential in 3,3‘-Dimethyl-2,2‘-bithiophene and 3,4‘-Dimethyl-2,2‘-bithiophene:  A Comparison between HF, MP2, and DFT Theory journal August 1999
Rational Design of High Performance Conjugated Polymers for Organic Solar Cells journal January 2012
Impact of Copolymer Sequence on Solid-State Properties for Random, Gradient and Block Copolymers containing Thiophene and Selenophene journal July 2012
Compositional Influence on the Regioregularity and Device Parameters of a Conjugated Statistical Copolymer journal January 2013
C–H Arylation Reaction: Atom Efficient and Greener Syntheses of π-Conjugated Small Molecules and Macromolecules for Organic Electronic Materials journal August 2013
Functionalized Poly(3-hexylthiophene)s via Lithium–Bromine Exchange journal December 2014
Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP) journal January 2015
Random Poly(3-hexylthiophene- co -3-cyanothiophene) Copolymers via Direct Arylation Polymerization (DArP) for Organic Solar Cells with High Open-Circuit Voltage journal March 2014
Identifying Homocouplings as Critical Side Reactions in Direct Arylation Polycondensation journal August 2014
Polymer solar cells journal February 2012
Open circuit voltage of organic solar cells: an in-depth review journal January 2016
Solution-processable single-material molecular emitters for organic light-emitting devices journal January 2011
Poly(3-hexylthiophene): synthetic methodologies and properties in bulk heterojunction solar cells journal January 2012
Influence of β-linkages on the morphology and performance of DArP P3HT–PC 61 BM solar cells journal December 2013
Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions journal December 1995
Outlook Brightens for Plastic Solar Cells journal April 2011
Impact of Backbone Fluorination on π-Conjugated Polymers in Organic Photovoltaic Devices: A Review journal January 2016

Cited By (5)

Synthesis of a Hominal Bis(difluoromethyl) Fragment journal August 2019
Random D1–A1–D1–A2 terpolymers based on diketopyrrolopyrrole and benzothiadiazolequinoxaline (BTQx) derivatives for high-performance polymer solar cells journal January 2019
ipso -Arylative polymerization as a route to π-conjugated polymers: synthesis of poly(3-hexylthiophene) journal January 2018
Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems journal January 2020
Tuning the optoelectronic properties of oligothiophenes for solar cell applications by varying the number of cyano and fluoro substituents for solar cell applications: A theoretical study journal December 2019

Figures / Tables (13)

Figure 1(p. 2)figure Figure 1
Scheme 1(p. 2)figure Scheme 1
Figure 2(p. 3)figure Figure 2
Scheme 2(p. 3)figure Scheme 2
Figure 3(p. 4)figure Figure 3
Table 1(p. 4)table Table 1
Figure 4(p. 5)figure Figure 4
Figure 5(p. 5)figure Figure 5
Figure 6(p. 5)figure Figure 6
Figure 7(p. 6)figure Figure 7
Figure 8(p. 7)figure Figure 8
Table 2(p. 7)table Table 2
Figure 9(p. 8)figure Figure 9

Similar Records

Linking the HOMO-LUMO gap to torsional disorder in P3HT/PCBM blends
Journal Article · Sun Dec 13 23:00:00 EST 2015 · Journal of Chemical Physics · OSTI ID:22493328
Guided crystallization of P3HT in ternary blend solar cell based on P3HT:PCPDTBT:PCBM
Journal Article · Tue Dec 31 23:00:00 EST 2013 · Energy & Environmental Science · OSTI ID:1370269
A study of the degree of fluorination in regioregular poly(3-hexylthiophene)
Journal Article · Mon Dec 26 19:00:00 EST 2016 · Macromolecules · OSTI ID:1336363

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Copolymers
Fluorine
Halogenation
Monomers
Polymers