Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

Shen, Xiaobo; Hu, Weiguo; Russell, Thomas P.

doi:10.1021/acs.macromol.6b00799

Title: Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

Journal Article · Tue Jun 14 00:00:00 EDT 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b00799· OSTI ID:1370277

Shen, Xiaobo ^[1]; Hu, Weiguo ^[1]; Russell, Thomas P. ^[1]

Univ. of Massachusetts, Amherst, MA (United States)

By using a combination of wide-angle X-ray diffraction (WAXD), mass density, and ¹³C solid-state nuclear magnetic resonance (NMR) measurements, a quantification of the absolute degree of crystallinity in regioregular poly(3-hexylthiophene) (rr-P3HT) is presented. A regiorandom P3HT (rra-P3HT), lacking long-range order, was used to separate the crystalline contribution from the total scattering in WAXD, thus yielding degrees of crystallinity in the range of 47–56% at room temperature for three different rr-P3HTs. For the same rr-P3HT with identical processing history, NMR yields degrees of crystallinity that are consistently ~10% greater than that obtained by WAXD, which can only be explained by ordered chain segments in the amorphous phase. NMR results also suggest that rra-P3HT contains weakly ordered chain segments, which likely contribute to an underestimation of degree of crystallinity when determined from mass density measurements, if rra-P3HT is used to approximate a fully amorphous P3HT. The results shown in this study provide direct proof of three different types of P3HT chain segments: crystallites (i.e., long-range ordered chain packing), amorphous phase (i.e., disordered chain packing), and short-range ordered chain packing embedded in the amorphous phase. Here, the presence of the short-range ordered chain packing is particularly important when correlating the morphology to macroscopic charge transport properties in P3HT-based devices. In general, those locally ordered chain segments, though not constituting a distinct phase, are believed to be of critical importance in determining the transport characteristics of conjugated semiconducting polymers with or without a distinct crystalline phase present.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Polymer-Based Materials for Harvesting Solar Energy (PHaSE)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001087; N00014-15-1-2244

OSTI ID:: 1370277

Journal Information:: Macromolecules, Vol. 49, Issue 12; Related Information: PHaSE partners with University of Massachusetts, Amherst (lead) and Lowell; Oak Ridge National Laboratory; Pennsylvania State University; Renssalaer Polytechnic Institute; University of Pittsburgh; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 73 works

Citation information provided by
Web of Science

References (42)

On the morphology of polymer-based photovoltaics Liu, Feng; Gu, Yu; Jung, Jae Woong Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 15 https://doi.org/10.1002/polb.23063	journal	March 2012
Characterization of the morphology of solution-processed bulk heterojunction organic photovoltaics Liu, Feng; Gu, Yu; Shen, Xiaobo Progress in Polymer Science, Vol. 38, Issue 12 https://doi.org/10.1016/j.progpolymsci.2013.07.010	journal	December 2013
Polymer–Fullerene Composite Solar Cells Thompson, Barry C.; Fréchet, Jean M. J. Angewandte Chemie International Edition, Vol. 47, Issue 1, p. 58-77 https://doi.org/10.1002/anie.200702506	journal	January 2008
Poly(3-hexylthiophene) and [6,6]-Phenyl-C ₆₁ -butyric Acid Methyl Ester Mixing in Organic Solar Cells Ro, Hyun Wook; Akgun, Bulent; O’Connor, Brendan T. Macromolecules, Vol. 45, Issue 16 https://doi.org/10.1021/ma3008527	journal	July 2012
Miscibility, Crystallinity, and Phase Development in P3HT/PCBM Solar Cells: Toward an Enlightened Understanding of Device Morphology and Stability Collins, Brian A.; Tumbleston, John R.; Ade, Harald The Journal of Physical Chemistry Letters, Vol. 2, Issue 24 https://doi.org/10.1021/jz2014902	journal	November 2011
A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene:fullerene solar cells Kim, Youngkyoo; Cook, Steffan; Tuladhar, Sachetan M. Nature Materials, Vol. 5, Issue 3 https://doi.org/10.1038/nmat1574	journal	February 2006
PBDT-TSR: a highly efficient conjugated polymer for polymer solar cells with a regioregular structure Yao, Huifeng; Zhao, Wenchao; Zheng, Zhong Journal of Materials Chemistry A, Vol. 4, Issue 5 https://doi.org/10.1039/C5TA08614K	journal	January 2016
Determination of the Crystallinity of Semicrystalline Poly(3-hexylthiophene) by Means of Wide-Angle X-ray Scattering Balko, Jens; Lohwasser, Ruth H.; Sommer, Michael Macromolecules, Vol. 46, Issue 24 https://doi.org/10.1021/ma401946w	journal	December 2013
Molecular Weight Dependence of Chain Packing and Semicrystalline Structure in Oriented Films of Regioregular Poly(3-hexylthiophene) Revealed by High-Resolution Transmission Electron Microscopy Brinkmann, Martin; Rannou, Patrice Macromolecules, Vol. 42, Issue 4 https://doi.org/10.1021/ma8023415	journal	February 2009
Determining exciton bandwidth and film microstructure in polythiophene films using linear absorption spectroscopy Clark, Jenny; Chang, Jui-Fen; Spano, Frank C. Applied Physics Letters, Vol. 94, Issue 16, Article No. 163306 https://doi.org/10.1063/1.3110904	journal	April 2009
Quantitative Determination of Organic Semiconductor Microstructure from the Molecular to Device Scale Rivnay, Jonathan; Mannsfeld, Stefan C. B.; Miller, Chad E. Chemical Reviews, Vol. 112, Issue 10 https://doi.org/10.1021/cr3001109	journal	June 2012
Vertical confinement and interface effects on the microstructure and charge transport of P3HT thin films Jimison, Leslie H.; Himmelberger, Scott; Duong, Duc T. Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 7 https://doi.org/10.1002/polb.23265	journal	February 2013
Important thermodynamic characteristics of poly(3-hexyl thiophene) Lee, Cameron S.; Dadmun, Mark D. Polymer, Vol. 55, Issue 1 https://doi.org/10.1016/j.polymer.2013.11.033	journal	January 2014
Quantifying Crystallinity in High Molar Mass Poly(3-hexylthiophene) Snyder, Chad R.; Nieuwendaal, Ryan C.; DeLongchamp, Dean M. Macromolecules, Vol. 47, Issue 12 https://doi.org/10.1021/ma500136d	journal	June 2014
Temperature and Molecular Weight Dependent Hierarchical Equilibrium Structures in Semiconducting Poly(3-hexylthiophene) Wu, Zhiyong; Petzold, Albrecht; Henze, Thomas Macromolecules, Vol. 43, Issue 10 https://doi.org/10.1021/ma902566h	journal	May 2010
Measuring Order in Regioregular Poly(3-hexylthiophene) with Solid-State ¹³ C CPMAS NMR Nieuwendaal, Ryan C.; Snyder, Chad R.; DeLongchamp, Dean M. ACS Macro Letters, Vol. 3, Issue 2 https://doi.org/10.1021/mz4005343	journal	January 2014
A Strategy for Revealing the Packing in Semicrystalline π-Conjugated Polymers: Crystal Structure of Bulk Poly-3-hexyl-thiophene (P3HT) Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie Angewandte Chemie International Edition, Vol. 51, Issue 44 https://doi.org/10.1002/anie.201205075	journal	October 2012
High Crystallinity and Nature of Crystal−Crystal Phase Transformations in Regioregular Poly(3-hexylthiophene) Pascui, Ovidiu F.; Lohwasser, Ruth; Sommer, Michael Macromolecules, Vol. 43, Issue 22 https://doi.org/10.1021/ma102205t	journal	November 2010
Thermal and Structural Characteristics of Oligo(3-hexylthiophene)s (3HT) _n , n = 4–36 Koch, Felix Peter Vinzenz; Heeney, Martin; Smith, Paul Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja405792b	journal	September 2013
On the degree of crystallinity in natural rubber IV: The degree of crystallization in frozen raw rubber and stretched vulcanized rubber Goppel, J. M.; Arlman, J. J. Flow, Turbulence and Combustion, Vol. 1, Issue 1 https://doi.org/10.1007/BF02120347	journal	December 1949
The Relation between Structure and Properties of Crystalline Polymers Mandelkern, Leo Polymer Journal, Vol. 17, Issue 1 https://doi.org/10.1295/polymj.17.337	journal	January 1985
Phase structure of lamellar crystalline polyethylene by solid-state high-resolution carbon-13 NMR detection of the crystalline-amorphous interphase Kitamaru, Ryozo; Horii, Fumitaka; Murayama, Koichi Macromolecules, Vol. 19, Issue 3 https://doi.org/10.1021/ma00157a026	journal	May 1986
X-ray determination of crystallinity and diffuse disorder scattering Ruland, W. Acta Crystallographica, Vol. 14, Issue 11 https://doi.org/10.1107/S0365110X61003429	journal	November 1961
A Simple Method to Prepare Head-to-Tail Coupled, Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis Loewe, Robert S.; Khersonsky, Sonya M.; McCullough, Richard D. Advanced Materials, Vol. 11, Issue 3 https://doi.org/10.1002/(SICI)1521-4095(199903)11:3<250::AID-ADMA250>3.0.CO;2-J	journal	March 1999
Regiocontrolled Synthesis of Poly(3-alkylthiophenes) Mediated by Rieke Zinc: Their Characterization and Solid-State Properties Chen, Tian-An; Wu, Xiaoming; Rieke, Reuben D. Journal of the American Chemical Society, Vol. 117, Issue 1, p. 233-244 https://doi.org/10.1021/ja00106a027	journal	January 1995
Towards quantitative CP-MAS NMR Metz, Günther; Ziliox, Martine; Smith, Steven O. Solid State Nuclear Magnetic Resonance, Vol. 7, Issue 3 https://doi.org/10.1016/S0926-2040(96)01257-X	journal	December 1996
A Study on the Correlation Between Structure and Hole Transport in Semi-Crystalline Regioregular P3HT Shen, Xiaobo; Duzhko, Volodimyr V.; Russell, Thomas P. Advanced Energy Materials, Vol. 3, Issue 2 https://doi.org/10.1002/aenm.201200509	journal	September 2012
Glassy Carbon as an Absolute Intensity Calibration Standard for Small-Angle Scattering Zhang, Fan; Ilavsky, Jan; Long, Gabrielle G. Metallurgical and Materials Transactions A, Vol. 41, Issue 5 https://doi.org/10.1007/s11661-009-9950-x	journal	August 2009
Structure and X-ray spectrum of crystalline poly(3-hexylthiophene) from DFT-van der Waals calculations: Ab initio determination of the structure of crystalline P3HT Colle, Renato; Grosso, Giuseppe; Ronzani, Alberto physica status solidi (b), Vol. 248, Issue 6 https://doi.org/10.1002/pssb.201046429	journal	January 2011
X-ray scattering from poly(thiophene): crystallinity and crystallographic structure Mo, Z.; Lee, K. B.; Moon, Y. B. Macromolecules, Vol. 18, Issue 10 https://doi.org/10.1021/ma00152a028	journal	October 1985
On the Role of Single Regiodefects and Polydispersity in Regioregular Poly(3-hexylthiophene): Defect Distribution, Synthesis of Defect-Free Chains, and a Simple Model for the Determination of Crystallinity Kohn, Peter; Huettner, Sven; Komber, Hartmut Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja210871j	journal	March 2012
Effect of Polymorphism, Regioregularity and Paracrystallinity on Charge Transport in Poly(3-hexylthiophene) [P3HT] Nanofibers Poelking, Carl; Andrienko, Denis Macromolecules, Vol. 46, Issue 22 https://doi.org/10.1021/ma4015966	journal	November 2013
Structural Model of Regioregular Poly(3-hexylthiophene) Obtained by Electron Diffraction Analysis Kayunkid, Navaphun; Uttiya, Sureeporn; Brinkmann, Martin Macromolecules, Vol. 43, Issue 11, p. 4961-4967 https://doi.org/10.1021/ma100551m	journal	June 2010
Polymer Order and Polymer Density Robertson, Richard E. The Journal of Physical Chemistry, Vol. 69, Issue 5 https://doi.org/10.1021/j100889a021	journal	May 1965
Ring currents Lazzeretti, P. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 36, Issue 1 https://doi.org/10.1016/S0079-6565(99)00021-7	journal	February 2000
A Refined Model of the Chlorosomal Antennae of the Green Bacterium Chlorobium tepidum from Proton Chemical Shift Constraints Obtained with High-Field 2-D and 3-D MAS NMR Dipolar Correlation Spectroscopy van Rossum, B. -J.; Steensgaard, D. B.; Mulder, F. M. Biochemistry, Vol. 40, Issue 6 https://doi.org/10.1021/bi0017529	journal	January 2001
Synthetic Principles Directing Charge Transport in Low-Band-Gap Dithienosilole–Benzothiadiazole Copolymers Beaujuge, Pierre M.; Tsao, Hoi Nok; Hansen, Michael Ryan Journal of the American Chemical Society, Vol. 134, Issue 21 https://doi.org/10.1021/ja301898h	journal	May 2012
Three-Phase Morphology of Semicrystalline Polymer Semiconductors: A Quantitative Analysis Remy, Roddel; Wei, Sujun; Campos, Luis M. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00481	journal	September 2015
Unraveling Charge Transport in Conjugated Polymers Street, R. A. Science, Vol. 341, Issue 6150 https://doi.org/10.1126/science.1242935	journal	September 2013
Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer Zhang, Xinran; Bronstein, Hugo; Kronemeijer, Auke J. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3238	journal	July 2013
Ultrahigh Mobility in Polymer Field-Effect Transistors by Design Tsao, Hoi Nok; Cho, Don M.; Park, Insun Journal of the American Chemical Society, Vol. 133, Issue 8 https://doi.org/10.1021/ja108861q	journal	March 2011
A general relationship between disorder, aggregation and charge transport in conjugated polymers Noriega, Rodrigo; Rivnay, Jonathan; Vandewal, Koen Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3722	journal	August 2013

Cited By (7)

Mapping Polymer Molecular Order in the SEM with Secondary Electron Hyperspectral Imaging Masters, Robert C.; Stehling, Nicola; Abrams, Kerry J. Advanced Science, Vol. 6, Issue 5 https://doi.org/10.1002/advs.201801752	journal	January 2019
Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers Zhang, Wenlin; Bombile, Joel H.; Weisen, Albree R. Macromolecular Rapid Communications https://doi.org/10.1002/marc.201900134	journal	May 2019
In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials Manley, Eric F.; Strzalka, Joseph; Fauvell, Thomas J. Advanced Energy Materials, Vol. 8, Issue 23 https://doi.org/10.1002/aenm.201800611	journal	May 2018
Enhancement of Out-of-Plane Hole Mobility in Poly(3-Hexylthiophene)- b -Poly(styrene) Film Tomita, Eri; Kim, Kyusun; Minegishi, Kazushi Macromolecular Chemistry and Physics, Vol. 219, Issue 18 https://doi.org/10.1002/macp.201800186	journal	August 2018
Miscibility-Function Relations in Organic Solar Cells: Significance of Optimal Miscibility in Relation to Percolation Ye, Long; Collins, Brian A.; Jiao, Xuechen Advanced Energy Materials, Vol. 8, Issue 28 https://doi.org/10.1002/aenm.201703058	journal	January 2018
The Role of Ordering on the Thermoelectric Properties of Blends of Regioregular and Regiorandom Poly(3‐hexylthiophene) Lim, Eunhee; Glaudell, Anne M.; Miller, Rachel Advanced Electronic Materials, Vol. 5, Issue 11 https://doi.org/10.1002/aelm.201800915	journal	April 2019
Thermodynamic features of perfectly crystalline poly(3-hexylthiophene) based on Flory's relation Alizadehaghdam, Mina; Siegenführ, Silvia; Abbasi, Farhang Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 8 https://doi.org/10.1002/polb.24796	journal	February 2019

Similar Records

The Role of Ordering on the Thermoelectric Properties of Blends of Regioregular and Regiorandom Poly(3‐hexylthiophene)

Journal Article · Thu Apr 25 00:00:00 EDT 2019 · Advanced Electronic Materials · OSTI ID:1370277

Lim, Eunhee; Glaudell, Anne M.; Miller, Rachel; +1 more

Local Intermolecular Order Controls Photoinduced Charge Separation at Donor/Acceptor Interfaces in Organic Semiconductors

Journal Article · Wed Mar 23 00:00:00 EDT 2016 · Advanced Energy Materials (Online) · OSTI ID:1370277

Feier, Hilary M.; Reid, Obadiah G.; Pace, Natalie A.; +5 more

A study of the degree of fluorination in regioregular poly(3-hexylthiophene)

Journal Article · Tue Dec 27 00:00:00 EST 2016 · Macromolecules · OSTI ID:1370277

Blaskovits, J. Terence; Bura, Thomas; Beaupre, Serge; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystallinity
Organic polymers
Scattering
Physical and chemical processes
Order

Title: Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

Citation Formats

References (42)

Cited By (7)

Similar Records

Related Subjects