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Title: Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold

Abstract

The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chain composition or by adding linear P3HT chains to the bottlebrush copolymers. Coarse-grained molecular dynamics simulations reveal that linear P3HT chains preferentially associate with P3HT side chains of bottlebrush copolymers, which tends to reduce the aggregation. The nanoscale morphology of microphase segregated thin films created by casting P3HT–PLA random bottlebrush copolymers is highly dependent on the composition of P3HT and PLA side chains, while domain spacing of nanostructures is mainly determined by the length of the side chains. The selective removal of PLA side chains under alkaline conditions generates nanoporous P3HT structures that can be tuned by manipulating molecular design ofmore » the bottlebrush scaffold, which is affected by molecular weight and grafting density of the side chains, and their sequence. Furthermore, the ability to exploit the unusual architecture of bottlebrushes to fabricate tunable nanoporous P3HT thin film structures may be a useful way to design templates for optoelectronic applications or membranes for separations.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [2];  [2]; ORCiD logo [2];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pusan National Univ., Busan (Korea)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1376375
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 9; Journal Issue: 21; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Ahn, Suk-kyun, Carrillo, Jan-Michael Y., Keum, Jong K., Chen, Jihua, Uhrig, David, Lokitz, Bradley S., Sumpter, Bobby G., and Kilbey, II, S. Michael. Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold. United States: N. p., 2017. Web. doi:10.1039/C7NR00015D.
Ahn, Suk-kyun, Carrillo, Jan-Michael Y., Keum, Jong K., Chen, Jihua, Uhrig, David, Lokitz, Bradley S., Sumpter, Bobby G., & Kilbey, II, S. Michael. Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold. United States. doi:10.1039/C7NR00015D.
Ahn, Suk-kyun, Carrillo, Jan-Michael Y., Keum, Jong K., Chen, Jihua, Uhrig, David, Lokitz, Bradley S., Sumpter, Bobby G., and Kilbey, II, S. Michael. Fri . "Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold". United States. doi:10.1039/C7NR00015D. https://www.osti.gov/servlets/purl/1376375.
@article{osti_1376375,
title = {Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold},
author = {Ahn, Suk-kyun and Carrillo, Jan-Michael Y. and Keum, Jong K. and Chen, Jihua and Uhrig, David and Lokitz, Bradley S. and Sumpter, Bobby G. and Kilbey, II, S. Michael},
abstractNote = {The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chain composition or by adding linear P3HT chains to the bottlebrush copolymers. Coarse-grained molecular dynamics simulations reveal that linear P3HT chains preferentially associate with P3HT side chains of bottlebrush copolymers, which tends to reduce the aggregation. The nanoscale morphology of microphase segregated thin films created by casting P3HT–PLA random bottlebrush copolymers is highly dependent on the composition of P3HT and PLA side chains, while domain spacing of nanostructures is mainly determined by the length of the side chains. The selective removal of PLA side chains under alkaline conditions generates nanoporous P3HT structures that can be tuned by manipulating molecular design of the bottlebrush scaffold, which is affected by molecular weight and grafting density of the side chains, and their sequence. Furthermore, the ability to exploit the unusual architecture of bottlebrushes to fabricate tunable nanoporous P3HT thin film structures may be a useful way to design templates for optoelectronic applications or membranes for separations.},
doi = {10.1039/C7NR00015D},
journal = {Nanoscale},
number = 21,
volume = 9,
place = {United States},
year = {2017},
month = {4}
}

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Works referenced in this record:

Ueber die Anwendung des Satzes vom Virial in der kinetischen Theorie der Gase
journal, January 1881


Cylindrical molecular brushes: Synthesis, characterization, and properties
journal, July 2008


Thermally Tunable Metallodielectric Photonic Crystals from the Self-Assembly of Brush Block Copolymers and Gold Nanoparticles
journal, April 2015

  • Song, Dong-Po; Li, Cheng; Colella, Nicholas S.
  • Advanced Optical Materials, Vol. 3, Issue 9
  • DOI: 10.1002/adom.201500116

Assembly and organization of poly(3-hexylthiophene) brushes and their potential use as novel anode buffer layers for organic photovoltaics
journal, January 2013

  • Alonzo, José; Kochemba, W. Michael; Pickel, Deanna L.
  • Nanoscale, Vol. 5, Issue 19
  • DOI: 10.1039/c3nr02226a

Nanoporous Poly(3-alkylthiophene) Thin Films Generated from Block Copolymer Templates
journal, January 2008

  • Boudouris, Bryan W.; Frisbie, C. Daniel; Hillmyer, Marc A.
  • Macromolecules, Vol. 41, Issue 1
  • DOI: 10.1021/ma071626d

Exploring the synthesis and impact of end-functional poly(3-hexylthiophene)
journal, February 2015

  • Handa, Nisha V.; Serrano, Abigail V.; Robb, Maxwell J.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 7
  • DOI: 10.1002/pola.27522

Cylindrical nanocapsules from photo-cross-linkable core–shell bottlebrush copolymers
journal, January 2015

  • Onbulak, Sebla; Rzayev, Javid
  • Polymer Chemistry, Vol. 6, Issue 5
  • DOI: 10.1039/C4PY01215A

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


VORO++ : A three-dimensional Voronoi cell library in C++
journal, December 2009

  • Rycroft, Chris H.
  • Chaos: An Interdisciplinary Journal of Nonlinear Science, Vol. 19, Issue 4
  • DOI: 10.1063/1.3215722

In Situ Formation of Pyridyl-Functionalized Poly(3-hexylthiophene)s via Quenching of the Grignard Metathesis Polymerization: Toward Ligands for Semiconductor Quantum Dots
journal, November 2012

  • Kochemba, W. Michael; Pickel, Deanna L.; Sumpter, Bobby G.
  • Chemistry of Materials, Vol. 24, Issue 22
  • DOI: 10.1021/cm302915h

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications
journal, March 2009

  • Mishra, Amaresh; Ma, Chang-Qi; Bäuerle, Peter
  • Chemical Reviews, Vol. 109, Issue 3
  • DOI: 10.1021/cr8004229

Kumada Catalyst-Transfer Polycondensation: Mechanism, Opportunities, and Challenges
journal, July 2011

  • Kiriy, Anton; Senkovskyy, Volodymyr; Sommer, Michael
  • Macromolecular Rapid Communications, Vol. 32, Issue 19
  • DOI: 10.1002/marc.201100316

Transformation of Step-Growth Polymerization into Living Chain-Growth Polymerization
journal, November 2015


Stimuli-responsive molecular brushes
journal, January 2010


Bottlebrush Polymer Synthesis by Ring-Opening Metathesis Polymerization: The Significance of the Anchor Group
journal, May 2016

  • Radzinski, Scott C.; Foster, Jeffrey C.; Chapleski, Robert C.
  • Journal of the American Chemical Society, Vol. 138, Issue 22
  • DOI: 10.1021/jacs.5b13317

Interplay between Liquid Crystalline Order and Microphase Segregation on the Self-Assembly of Side-Chain Liquid Crystalline Brush Block Copolymers
journal, October 2013

  • Deshmukh, Prashant; Ahn, Suk-kyun; Geelhand de Merxem, Ludovic
  • Macromolecules, Vol. 46, Issue 20
  • DOI: 10.1021/ma401448j

Thiophene based hyperbranched polymers with tunable branching using direct arylation methods
journal, January 2013

  • Okamoto, Ken; Housekeeper, Jeremy B.; Michael, Forrest E.
  • Polymer Chemistry, Vol. 4, Issue 12
  • DOI: 10.1039/c3py00412k

Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation
journal, July 2013

  • Ahn, Suk-kyun; Pickel, Deanna L.; Kochemba, W. Michael
  • ACS Macro Letters, Vol. 2, Issue 8
  • DOI: 10.1021/mz4003563

Grignard metathesis (GRIM) polymerization for the synthesis of conjugated block copolymers containing regioregular poly(3-hexylthiophene)
journal, January 2012

  • Stefan, Mihaela C.; Bhatt, Mahesh P.; Sista, Prakash
  • Polym. Chem., Vol. 3, Issue 7
  • DOI: 10.1039/C1PY00453K

Rapid self-assembly of brush block copolymers to photonic crystals
journal, August 2012

  • Sveinbjornsson, B. R.; Weitekamp, R. A.; Miyake, G. M.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 36, p. 14332-14336
  • DOI: 10.1073/pnas.1213055109

Star-Shaped Oligo( p -phenylenevinylene) Substituted Hexaarylbenzene:  Purity, Stability, and Chiral Self-assembly
journal, December 2007

  • Tomović, Željko; van Dongen, Joost; George, Subi J.
  • Journal of the American Chemical Society, Vol. 129, Issue 51
  • DOI: 10.1021/ja0765417

Macrocyclic regioregular poly(3-hexylthiophene): from controlled synthesis to nanotubular assemblies
journal, January 2013

  • Coulembier, Olivier; Deshayes, Gaëlle; Surin, Mathieu
  • Polym. Chem., Vol. 4, Issue 2
  • DOI: 10.1039/C2PY20647A

Thin Film Phase Behavior of Bottlebrush/Linear Polymer Blends
journal, July 2014

  • Mitra, Indranil; Li, Xianyu; Pesek, Stacy L.
  • Macromolecules, Vol. 47, Issue 15
  • DOI: 10.1021/ma501070w

Poly(3-Hexylthiophene) Nanostructured Materials for Organic Electronics Applications
journal, February 2014

  • Bhatt, M. P.; Magurudeniya, H. D.; Rainbolt, E. A.
  • Journal of Nanoscience and Nanotechnology, Vol. 14, Issue 2
  • DOI: 10.1166/jnn.2014.8892

Precisely Tunable Photonic Crystals From Rapidly Self-Assembling Brush Block Copolymer Blends
journal, September 2012

  • Miyake, Garret M.; Piunova, Victoria A.; Weitekamp, Raymond A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 45, p. 11246-11248
  • DOI: 10.1002/anie.201205743

Cylindrical polymer brushes
journal, January 2005

  • Zhang, Mingfu; Müller, Axel H. E.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 16, p. 3461-3481
  • DOI: 10.1002/pola.20900

Branched Terthiophenes in Organic Electronics: From Small Molecules to Polymers
journal, November 2014

  • Scheuble, Martin; Goll, Miriam; Ludwigs, Sabine
  • Macromolecular Rapid Communications, Vol. 36, Issue 2
  • DOI: 10.1002/marc.201400525

On the Self-Assembly of Brush Block Copolymers in Thin Films
journal, October 2013

  • Hong, Sung Woo; Gu, Weiyin; Huh, June
  • ACS Nano, Vol. 7, Issue 11
  • DOI: 10.1021/nn402639g

Advances in Photofunctional Dendrimers for Solar Energy Conversion
journal, June 2014

  • Zhang, Xiaohui; Zeng, Yi; Yu, Tianjun
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5007862

Design of Well-Defined Monofunctionalized Poly(3-hexylthiophene)s: Toward the Synthesis of Semiconducting Graft Copolymers
journal, February 2012

  • Mougnier, Sébastien-Jun; Brochon, Cyril; Cloutet, Eric
  • Macromolecular Rapid Communications, Vol. 33, Issue 8
  • DOI: 10.1002/marc.201100703

Phase Diagram of P3HT/PCBM Blends and Its Implication for the Stability of Morphology
journal, February 2009

  • Zhao, Jun; Swinnen, Ann; Van Assche, Guy
  • The Journal of Physical Chemistry B, Vol. 113, Issue 6, p. 1587-1591
  • DOI: 10.1021/jp804151a

Minimizing Lateral Domain Collapse in Etched Poly(3-hexylthiophene)- block -Polylactide Thin Films for Improved Optoelectronic Performance
journal, June 2010

  • Botiz, Ioan; Martinson, Alex B. F.; Darling, Seth B.
  • Langmuir, Vol. 26, Issue 11
  • DOI: 10.1021/la904515z

Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011

  • Brown, W. Michael; Wang, Peng; Plimpton, Steven J.
  • Computer Physics Communications, Vol. 182, Issue 4
  • DOI: 10.1016/j.cpc.2010.12.021

Dynamically confined crystallization in a soft lamellar space constituted by alternating polymer co-brushes
journal, September 2011


Exciton diffusion in organic photovoltaic cells
journal, January 2014

  • Menke, S. Matthew; Holmes, Russell J.
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE42444H

Aqueous Self-Assembly of Giant Bottlebrush Block Copolymer Surfactants as Shape-Tunable Building Blocks
journal, May 2014

  • Fenyves, Ryan; Schmutz, Marc; Horner, Ian J.
  • Journal of the American Chemical Society, Vol. 136, Issue 21
  • DOI: 10.1021/ja503283r

End-group composition of poly(3-hexylthiophene)s prepared by in situ quenching of the grignard metathesis polymerization: Influence of additives and reaction conditions
journal, April 2012

  • Kochemba, W. Michael; Kilbey, S. Michael; Pickel, Deanna L.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, Issue 14
  • DOI: 10.1002/pola.26057

Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement
journal, December 2009

  • Xia, Yan; Olsen, Bradley D.; Kornfield, Julia A.
  • Journal of the American Chemical Society, Vol. 131, Issue 51, p. 18525-18532
  • DOI: 10.1021/ja908379q

Architecturally Complex Polymers with Controlled Heterogeneity
journal, August 2011


Structural Evolution of Polylactide Molecular Bottlebrushes: Kinetics Study by Size Exclusion Chromatography, Small Angle Neutron Scattering, and Simulations
journal, August 2014

  • Ahn, Suk-kyun; Carrillo, Jan-Michael Y.; Han, Youngkyu
  • ACS Macro Letters, Vol. 3, Issue 9
  • DOI: 10.1021/mz5003454

Molecular Design of “Graft” Assembly for Ordered Microphase Separation of P3HT-Based Rod–Coil Copolymers
journal, October 2013

  • Kim, Hyeong Jun; Paek, Kwanyeol; Yang, Hyunseung
  • Macromolecules, Vol. 46, Issue 21
  • DOI: 10.1021/ma401530q

Conducting Block Copolymers of Regioregular Poly(3-hexylthiophene) and Poly(methacrylates): Electronic Materials with Variable Conductivities and Degrees of Interfibrillar Order
journal, September 2007

  • Iovu, Mihaela C.; Zhang, Rui; Cooper, Jessica R.
  • Macromolecular Rapid Communications, Vol. 28, Issue 17
  • DOI: 10.1002/marc.200700401

Cyclic polymers: Synthetic strategies and physical properties
journal, January 2010

  • Kricheldorf, Hans R.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 48, Issue 2
  • DOI: 10.1002/pola.23755

Designing π-conjugated polymers for organic electronics
journal, December 2013


Constructing Regioregular Star Poly(3-hexylthiophene) via Externally Initiated Kumada Catalyst-Transfer Polycondensation
journal, February 2012

  • Yuan, Mingjian; Okamoto, Ken; Bronstein, Hugo A.
  • ACS Macro Letters, Vol. 1, Issue 3
  • DOI: 10.1021/mz3000368

Poly(3-hexylthiophene): synthetic methodologies and properties in bulk heterojunction solar cells
journal, January 2012

  • Marrocchi, Assunta; Lanari, Daniela; Facchetti, Antonio
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee22129b

Directing Self-Assembly of Nanoscopic Cylindrical Diblock Brush Terpolymers into Films with Desired Spatial Orientations: Expansion of Chemical Composition Scope
journal, December 2013

  • Cho, Sangho; Yang, Fan; Sun, Guorong
  • Macromolecular Rapid Communications, Vol. 35, Issue 4
  • DOI: 10.1002/marc.201300845

Bioinspired Bottle-Brush Polymer Exhibits Low Friction and Amontons-like Behavior
journal, April 2014

  • Banquy, Xavier; Burdyńska, Joanna; Lee, Dong Woog
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja501770y

Advances in Star-Shaped π-Conjugated Systems: Properties and Applications
journal, April 2014

  • Jarosz, Tomasz; Lapkowski, Mieczyslaw; Ledwon, Przemyslaw
  • Macromolecular Rapid Communications, Vol. 35, Issue 11
  • DOI: 10.1002/marc.201400061

Crystallization of Molecular Brushes with Block Copolymer Side Chains
journal, November 2009

  • Yu-Su, Sherryl Y.; Sheiko, Sergei S.; Lee, Hyung-il
  • Macromolecules, Vol. 42, Issue 22
  • DOI: 10.1021/ma901432v

Cyclic polymers as a building block for cyclic brush polymers and gels
journal, July 2014


Structure, function, self-assembly, and applications of bottlebrush copolymers
journal, January 2015

  • Verduzco, Rafael; Li, Xianyu; Pesek, Stacy L.
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00329B

Macromolecular architectures for organic photovoltaics
journal, January 2012

  • Popere, Bhooshan C.; Pelle, Andrea M. Della; Poe, Ambata
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 12
  • DOI: 10.1039/c2cp23422j

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