Ordering of lamellar block copolymers on oxidized silane coatings

Mahadevapuram, Nikhila; Mitra, Indranil; Sridhar, Shyam; Strzalka, Joseph; Stein, Gila E.

doi:10.1016/j.eurpolymj.2016.01.010

Title: Ordering of lamellar block copolymers on oxidized silane coatings

Journal Article · Sat Jan 02 00:00:00 EST 2016 · European Polymer Journal

DOI:https://doi.org/10.1016/j.eurpolymj.2016.01.010· OSTI ID:1338963

Mahadevapuram, Nikhila ^[1]; Mitra, Indranil ^[1]; Sridhar, Shyam ^[1]; Strzalka, Joseph ^[2]; Stein, Gila E. ^[1]

Univ. of Houston, Houston, TX (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Thin films of lamellar poly(styrene-b-methyl methacrylate) (PS-PMMA) block copolymers are widely investigated for surface patterning. These materials can generate dense arrays of nanoscale lines when the lamellar domains are oriented perpendicular to the substrate. To stabilize this preferred domain orientation, we tuned the substrate surface energy using oxidation of hydrophobic silane coatings. This simple approach is effective for a broad range of PS-PMMA film thicknesses when the oxidation time is optimized, which demonstrates that the substrate coating is energetically neutral with respect to PS and PMMA segments. The lamellar films are characterized by high densities of defects that exhibit a strong dependence on film thickness: in-plane topological defects disrupt the lateral order in ultrathin films, while lamellar domains in thick films can bend and tilt to large misorientation angles. As a result, the types and densities of these defects are similar to those observed with other classes of neutral substrate coatings, such as random copolymer brushes, which demonstrates that oxidized silanes can be used to control PS-PMMA self assembly in thin films.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; DMR-1151468

OSTI ID:: 1338963

Alternate ID(s):: OSTI ID: 1341127

Journal Information:: European Polymer Journal, Vol. 75, Issue C; ISSN 0014-3057

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

References (43)

Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement Diederichsen, Kyle M.; Brow, Ryan R.; Stoykovich, Mark P. ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/acsnano.5b01321	journal	February 2015
A Highly Efficient Sensor Platform Using Simply Manufactured Nanodot Patterned Substrates Rasappa, Sozaraj; Ghoshal, Tandra; Borah, Dipu Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep13270	journal	August 2015
Block Copolymer Lithography Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W. Macromolecules, Vol. 47, Issue 1, p. 2-12 https://doi.org/10.1021/ma401762n	journal	November 2013
Directed self-assembly of block copolymers for nanocircuitry fabrication Morris, M. A. Microelectronic Engineering, Vol. 132 https://doi.org/10.1016/j.mee.2014.08.009	journal	January 2015
Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns Bang, Joona; Jeong, Unyong; Ryu, Du Yeol Advanced Materials, Vol. 21, Issue 47, p. 4769-4792 https://doi.org/10.1002/adma.200803302	journal	July 2009
Polarity-Switching Top Coats Enable Orientation of Sub-10-nm Block Copolymer Domains Bates, C. M.; Seshimo, T.; Maher, M. J. Science, Vol. 338, Issue 6108 https://doi.org/10.1126/science.1226046	journal	November 2012
Consequences of Surface Neutralization in Diblock Copolymer Thin Films Kim, Sangwon; Bates, Christopher M.; Thio, Anthony ACS Nano, Vol. 7, Issue 11 https://doi.org/10.1021/nn403616r	journal	October 2013
A Generalized Approach to the Modification of Solid Surfaces Ryu, D. Y. Science, Vol. 308, Issue 5719 https://doi.org/10.1126/science.1106604	journal	April 2005
Controlling Polymer-Surface Interactions with Random Copolymer Brushes Mansky, P.; Liu, Y.; Huang, E. Science, Vol. 275, Issue 5305, p. 1458-1460 https://doi.org/10.1126/science.275.5305.1458	journal	March 1997
Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains Han, Eungnak; Stuen, Karl O.; La, Young-Hye Macromolecules, Vol. 41, Issue 23 https://doi.org/10.1021/ma8018393	journal	December 2008
Interplay of surface chemical composition and film thickness on graphoepitaxial assembly of asymmetric block copolymers Kim, Myungwoong; Han, Eungnak; Sweat, Daniel P. Soft Matter, Vol. 9, Issue 26 https://doi.org/10.1039/c3sm50307k	journal	January 2013
Ultrathin Random Copolymer-Grafted Layers for Block Copolymer Self-Assembly Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina ACS Applied Materials & Interfaces, Vol. 7, Issue 20 https://doi.org/10.1021/acsami.5b02201	journal	May 2015
Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers Vu, Thai; Mahadevapuram, Nikhila; Perera, Ginusha M. Macromolecules, Vol. 44, Issue 15 https://doi.org/10.1021/ma2009222	journal	August 2011
Perpendicular orientation of microdomains in PS-b-PMMA thin films on the PS brushed substrates Guo, Rui; Kim, Eunhye; Gong, Jinsam Soft Matter, Vol. 7, Issue 15 https://doi.org/10.1039/c1sm05562c	journal	January 2011
Engineering Silicon Oxide Surfaces Using Self-Assembled Monolayers Onclin, Steffen; Ravoo, Bart Jan; Reinhoudt, David N. Angewandte Chemie International Edition, Vol. 44, Issue 39 https://doi.org/10.1002/anie.200500633	journal	October 2005
Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies Albert, Julie N. L.; Baney, Michael J.; Stafford, Christopher M. ACS Nano, Vol. 3, Issue 12 https://doi.org/10.1021/nn900750w	journal	November 2009
Controlled vapor deposition approach to generating substrate surface energy/chemistry gradients Albert, Julie N. L.; Kim, Joey D.; Stafford, Christopher M. Review of Scientific Instruments, Vol. 82, Issue 6 https://doi.org/10.1063/1.3594104	journal	June 2011
Manipulating Nanoscale Morphologies in Cylinder-Forming Poly(styrene- b -isoprene- b -styrene) Thin Films Using Film Thickness and Substrate Surface Chemistry Gradients Luo, Ming; Seppala, Jonathan E.; Albert, Julie N. L. Macromolecules, Vol. 46, Issue 5 https://doi.org/10.1021/ma302410q	journal	February 2013
Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates Ouk Kim, Sang; Solak, Harun H.; Stoykovich, Mark P. Nature, Vol. 424, Issue 6947, p. 411-414 https://doi.org/10.1038/nature01775	journal	July 2003
Easy Orientation of Diblock Copolymers on Self-Assembled Monolayers Using UV Irradiation Liu, Pang-Hung; Thébault, Pascal; Guenoun, Patrick Macromolecules, Vol. 42, Issue 24 https://doi.org/10.1021/ma9021357	journal	November 2009
SAXS Analysis of the Order−Disorder Transition and the Interaction Parameter of Polystyrene- block -poly(methyl methacrylate) Zhao, Yue; Sivaniah, Easan; Hashimoto, Takeji Macromolecules, Vol. 41, Issue 24 https://doi.org/10.1021/ma8013004	journal	December 2008
Calculation of interfacial tension in polymer systems Wu, Souheng Journal of Polymer Science Part C: Polymer Symposia, Vol. 34, Issue 1 https://doi.org/10.1002/polc.5070340105	journal	January 1971
Polar and Nonpolar Interactions in Adhesion Wu, Souheng The Journal of Adhesion, Vol. 5, Issue 1 https://doi.org/10.1080/00218467308078437	journal	January 1973
Surface and interfacial tensions of polymer melts. II. Poly(methyl methacrylate), poly(n-butyl methacrylate), and polystyrene Wu, Souheng The Journal of Physical Chemistry, Vol. 74, Issue 3 https://doi.org/10.1021/j100698a026	journal	February 1970
Forces involved in the adhesive process Dann, J. R. Journal of Colloid and Interface Science, Vol. 32, Issue 2 https://doi.org/10.1016/0021-9797(70)90054-8	journal	February 1970
Interfacial Segregation in Disordered Block Copolymers: Effect of Tunable Surface Potentials Mansky, P.; Russell, T. P.; Hawker, C. J. Physical Review Letters, Vol. 79, Issue 2 https://doi.org/10.1103/PhysRevLett.79.237	journal	July 1997
Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions Han, Eungnak; Stuen, Karl O.; Leolukman, Melvina Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma9002903	journal	July 2009
Polymer surface modification by plasmas and photons Chan, C.-M.; Ko, T.-M.; Hiraoka, H. Surface Science Reports, Vol. 24, Issue 1-2, p. 1-54 https://doi.org/10.1016/0167-5729(96)80003-3	journal	May 1996
Interface and surface effects on the glass-transition temperature in thin polymer films Keddie, Joseph L.; Jones, Richard A. L.; Cory, Rachel A. Faraday Discussions, Vol. 98 https://doi.org/10.1039/fd9949800219	journal	January 1994
Dependence of the Glass Transition Temperature of Polymer Films on Interfacial Energy and Thickness Fryer, David S.; Peters, Richard D.; Kim, Eui Jun Macromolecules, Vol. 34, Issue 16 https://doi.org/10.1021/ma001932q	journal	July 2001
Extraordinary elevation of the glass transition temperature of thin polymer films grafted to silicon oxide substrates Tate, Ranjeet S.; Fryer, David S.; Pasqualini, Silvia The Journal of Chemical Physics, Vol. 115, Issue 21 https://doi.org/10.1063/1.1415497	journal	December 2001
Mechanisms of Ordering in Striped Patterns Harrison, C. Science, Vol. 290, Issue 5496 https://doi.org/10.1126/science.290.5496.1558	journal	November 2000
Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers Hammond, Matthew R.; Cochran, Eric; Fredrickson, Glenn H. Macromolecules, Vol. 38, Issue 15 https://doi.org/10.1021/ma050479l	journal	July 2005
Observation of surface corrugation-induced alignment of lamellar microdomains in PS-b-PMMA thin films Park, Sang-Min; Berry, Brian C.; Dobisz, Elizabeth Soft Matter, Vol. 5, Issue 5 https://doi.org/10.1039/b813749h	journal	January 2009
Symmetric Diblock Copolymer Thin Films on Rough Substrates. Kinetics and Structure Formation in Pure Block Copolymer Thin Films Sivaniah, E.; Hayashi, Y.; Matsubara, S. Macromolecules, Vol. 38, Issue 5 https://doi.org/10.1021/ma0482157	journal	March 2005
Processing Approaches for the Defect Engineering of Lamellar-Forming Block Copolymers in Thin Films Campbell, Ian P.; Hirokawa, Soichi; Stoykovich, Mark P. Macromolecules, Vol. 46, Issue 24 https://doi.org/10.1021/ma401704m	journal	December 2013
Probing surface and interface morphology with Grazing Incidence Small Angle X-Ray Scattering Renaud, Gilles; Lazzari, Rémi; Leroy, Frédéric Surface Science Reports, Vol. 64, Issue 8 https://doi.org/10.1016/j.surfrep.2009.07.002	journal	August 2009
Layering Transitions in Thin Films of Spherical-Domain Block Copolymers Stein, Gila E.; Kramer, Edward J.; Li, Xuefa Macromolecules, Vol. 40, Issue 7 https://doi.org/10.1021/ma0625509	journal	April 2007
Impact of Film Thickness on the Morphology of Mesoporous Carbon Films Using Organic−Organic Self-Assembly Vogt, Bryan D.; Chavez, Vicki L.; Dai, Mingzhi Langmuir, Vol. 27, Issue 9 https://doi.org/10.1021/la200475d	journal	May 2011
Surface versus Confinement Induced Morphology Transition in Triblock Copolymer Films: A Grazing Incidence Small Angle Neutron Scattering Investigation Müller-Buschbaum, P.; Maurer, E.; Bauer, E. Langmuir, Vol. 22, Issue 22 https://doi.org/10.1021/la061455q	journal	October 2006
Impact of Out-of-Plane Translational Order in Block Copolymer Lithography Bosworth, Joan K.; Dobisz, Elizabeth A.; Hellwig, Olav Macromolecules, Vol. 44, Issue 23 https://doi.org/10.1021/ma201967a	journal	December 2011
Directed Self-Assembly of Lamellar Copolymers: Effects of Interfacial Interactions on Domain Shape Perera, Ginusha M.; Wang, Chengqing; Doxastakis, Manolis ACS Macro Letters, Vol. 1, Issue 11 https://doi.org/10.1021/mz300331k	journal	October 2012
Controlling interfacial interactions for directed self assembly of block copolymers Stein, Gila E.; Mahadevapuram, Nikhila; Mitra, Indranil Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 2, p. 96-102 https://doi.org/10.1002/polb.23502	journal	May 2014

Cited By (1)

Rapid ordering of block copolymer thin films Majewski, Pawel W.; Yager, Kevin G. Journal of Physics: Condensed Matter, Vol. 28, Issue 40 https://doi.org/10.1088/0953-8984/28/40/403002	journal	August 2016

Similar Records

In-plane and out-of-plane defectivity in thin films of lamellar block copolymers

Journal Article · Thu Oct 29 00:00:00 EDT 2015 · Journal of Polymer Science. Part B, Polymer Physics · OSTI ID:1338963

Mahadevapuram, Nikhila; Mitra, Indranil; Bozhchenko, Alona; +2 more

Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing [Thru-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing]

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Nano Letters · OSTI ID:1338963

Basutkar, Monali N.; Samant, Saumil; Strzalka, Joseph; +3 more

Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers

Journal Article · Thu Mar 15 00:00:00 EDT 2012 · Macromolecules · OSTI ID:1338963

Vu, Thai; Mahadevapuram, Nikhila; Perera, Ginusha M; +1 more

Related Subjects

36 MATERIALS SCIENCE
block copolymer
GISAXS
lithography
patterning
silane
thin film

Title: Ordering of lamellar block copolymers on oxidized silane coatings

Citation Formats

References (43)

Cited By (1)

Similar Records

Related Subjects