Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Masud, Ali; Wu, Wenjie; Singh, Maninderjeet; Tonny, Wafa; Ammar, Ali; Sharma, Kshitij; Strzalka, Joseph W.; Terlier, Tanguy; Douglas, Jack F.; Karim, Alamgir

doi:10.1021/acs.macromol.1c01305

Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Journal Article · Fri Sep 17 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c01305· OSTI ID:1840574

^[1]; Wu, Wenjie ^[1]; ^[1]; Tonny, Wafa ^[1]; Ammar, Ali ^[1]; Sharma, Kshitij ^[1]; ^[2]; Terlier, Tanguy ^[3]; ^[4]; ^[1]

Univ. of Houston, TX (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Rice Univ., Houston, TX (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Rapid and reliable processing methods for forming ordered block copolymer (BCP) materials with low defect density in a thin film geometry are required for many nanotechnology applications. Vertically aligned BCP structures, in particular, have applications ranging from nanolithography for electronics and photonics to nanoporous membranes for water remediation and novel batteries for flexible electronics. However, the attainment of nearly complete vertical orientational order of the BCP ordered phase remains challenging. Solvent-based techniques, such as direct immersion annealing (DIA) and solvent vapor annealing (SVA), have immense potential for these applications of BCP films, as it allows for tuning of their thermodynamic, structural, and chain mobility driven kinetic properties. We first demonstrate that DIA, using a judicious choice of binary solvent mixtures along with a relatively hydrophobic ionic liquid (IL), induces the rapid vertical ordering in polystyrene-b-polymethylmethacrylate (PS-PMMA) block copolymer in lamellar films. The IL establishes synergy to the binary solvent mixture of toluene and heptane to 1 create a near-neutral solvent environment for attaining the vertical microstructure of the BCP. Next, we show that IL can suppress the de-wetting of the PS-PMMA films to achieve long-range order using SVA in cylindrical films for long annealing times. Both vertical and horizontal morphology is attained in these films by selecting different solvent environments. Furthermore, attaining enhanced vertical and horizontal BCP structure with long-range defect-free order by tuning solvent quality and using additives like IL can render them useful for many nanotech applications.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840574

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 18 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Thermal Approaches to Perpendicular Block Copolymer Microdomains in Thin Films: A Review and Appraisal Wang, Hyun Suk; Kim, Ki Hyun; Bang, Joona Macromolecular Rapid Communications, Vol. 40, Issue 4 https://doi.org/10.1002/marc.201800728	journal	November 2018
The morphology and structure of PS-b-P4VP block copolymer films by solvent annealing: effect of the solvent parameter O'Driscoll, Sheena; Demirel, G.; Farrell, Richard A. Polymers for Advanced Technologies, Vol. 22, Issue 6 https://doi.org/10.1002/pat.1596	journal	November 2009
Solvent vapor induced dewetting in diblock copolymer thin films Peng, Juan; Xuan, Yu; Wang, Hanfu Polymer, Vol. 46, Issue 15 https://doi.org/10.1016/j.polymer.2005.05.042	journal	July 2005
Effect of solvent selectivity on supramolecular assemblies of block copolymer by solvent-vapor annealing Kim, Eunhye; Park, Sungmin; Han, Young-Soo Polymer, Vol. 150 https://doi.org/10.1016/j.polymer.2018.07.039	journal	August 2018
Rectangular Patterns Using Block Copolymer Directed Assembly for High Bit Aspect Ratio Patterned Media Ruiz, Ricardo; Dobisz, Elizabeth; Albrecht, Thomas R. ACS Nano, Vol. 5, Issue 1 https://doi.org/10.1021/Nn101561p	journal	December 2010
Ultra-Fast Vertical Ordering of Lamellar Block Copolymer Films on Unmodified Substrates Singh, Maninderjeet; Wu, Wenjie; Basutkar, Monali N. Macromolecules, Vol. 54, Issue 3 https://doi.org/10.1021/acs.macromol.0c01782	journal	January 2021
Ionic Liquid Enhanced Parallel Lamellar Ordering in Block Copolymer Films Masud, Ali; Longanecker, Melanie; Bhadauriya, Sonal Macromolecules, Vol. 54, Issue 10 https://doi.org/10.1021/acs.macromol.0c02546	journal	May 2021
Extending Dynamic Range of Block Copolymer Ordering with Rotational Cold Zone Annealing (RCZA) and Ionic Liquids Ye, Changhuai; Sun, Yan; Karim, Alamgir Macromolecules, Vol. 48, Issue 20 https://doi.org/10.1021/acs.macromol.5b02128	journal	October 2015
Ordering Pathway of Block Copolymers under Dynamic Thermal Gradients Studied by in Situ GISAXS Samant, Saumil; Strzalka, Joseph; Yager, Kevin G. Macromolecules, Vol. 49, Issue 22 https://doi.org/10.1021/acs.macromol.6b01555	journal	October 2016
Reduced Domain Size and Interfacial Width in Fast Ordering Nanofilled Block Copolymer Films by Direct Immersion Annealing Longanecker, Melanie; Modi, Arvind; Dobrynin, Andrey Macromolecules, Vol. 49, Issue 22 https://doi.org/10.1021/acs.macromol.6b01690	journal	November 2016
Observation of General Entropy–Enthalpy Compensation Effect in the Relaxation of Wrinkled Polymer Nanocomposite Films Bhadauriya, Sonal; Wang, Xiaoteng; Nallapaneni, Asritha Nano Letters, Vol. 21, Issue 3 https://doi.org/10.1021/acs.nanolett.0c02817	journal	February 2021
Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer Zhang, Jieqian; Clark, Michael B.; Wu, Chunyi Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04602	journal	December 2015
Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing Basutkar, Monali N.; Samant, Saumil; Strzalka, Joseph Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b04028	journal	November 2017
Direct Immersion Annealing of Thin Block Copolymer Films Modi, Arvind; Bhaway, Sarang M.; Vogt, Bryan D. ACS Applied Materials & Interfaces, Vol. 7, Issue 39 https://doi.org/10.1021/acsami.5b06259	journal	September 2015
Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim ACS Applied Materials & Interfaces, Vol. 8, Issue 12 https://doi.org/10.1021/acsami.5b11851	journal	March 2016
Ionic Liquids as Additives to Polystyrene- Block -Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features Chen, Xuanxuan; Zhou, Chun; Chen, Shuang-Jun ACS Applied Materials & Interfaces, Vol. 10, Issue 19 https://doi.org/10.1021/acsami.8b02990	journal	April 2018
Effect of Molecular Weight and Layer Thickness on the Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films Samant, Saumil; Basutkar, Monali; Singh, Maninderjeet ACS Applied Polymer Materials, Vol. 2, Issue 8 https://doi.org/10.1021/acsapm.0c00127	journal	June 2020
Nanosized Organo-Silica Particles with “Built-In” Surface-Initiated Atom Transfer Radical Polymerization Capability as a Platform for Brush Particle Synthesis Han, Jin; Zhai, Yue; Wang, Zongyu ACS Macro Letters, Vol. 9, Issue 9 https://doi.org/10.1021/acsmacrolett.0c00502	journal	August 2020
High χ–Low N Block Polymers: How Far Can We Go? Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00472	journal	September 2015
Control of Phase Morphology of Binary Polymer Grafted Nanoparticle Blend Films via Direct Immersion Annealing Wu, Wenjie; Singh, Maninderjeet; Masud, Ali ACS Nano, Vol. 15, Issue 7 https://doi.org/10.1021/acsnano.1c03357	journal	July 2021
Structure, Stability, and Reorganization of 0.5 L ₀ Topography in Block Copolymer Thin Films Maher, Michael J.; Self, Jeffrey L.; Stasiak, Pawel ACS Nano, Vol. 10, Issue 11 https://doi.org/10.1021/acsnano.6b05390	journal	November 2016
Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends Doerk, Gregory S.; Yager, Kevin G. ACS Nano, Vol. 11, Issue 12 https://doi.org/10.1021/acsnano.7b06154	journal	October 2016
Interfacial Design for Block Copolymer Thin Films Maher, Michael J.; Bates, Christopher M.; Blachut, Gregory Chemistry of Materials, Vol. 26, Issue 3 https://doi.org/10.1021/cm403813q	journal	January 2014
Hexagonal-to-Cubic Phase Transformation in Composite Thin Films Induced by FePt Nanoparticles Located at PS/PEO Interfaces Aissou, Karim; Fleury, Guillaume; Pecastaings, Gilles Langmuir, Vol. 27, Issue 23 https://doi.org/10.1021/la2036983	journal	December 2011
Dissolution of Symmetric Diblock Copolymers with Neutral Solvents, a Selective Solvent, a Nonsolvent, and Mixtures of a Solvent and Nonsolvent Monitored by FT-IR Imaging Koenig, Jack L. Macromolecules, Vol. 36, Issue 13 https://doi.org/10.1021/ma0215363	journal	July 2003
Surface Morphology of Annealed Polystyrene and Poly(methyl methacrylate) Thin Film Blends and Bilayers Harris, Mark; Appel, Guenter; Ade, Harald Macromolecules, Vol. 36, Issue 9 https://doi.org/10.1021/ma0257043	journal	May 2003
Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films Xu, Ting; Hawker, Craig J.; Russell, Thomas P. Macromolecules, Vol. 38, Issue 7 https://doi.org/10.1021/ma048005u	journal	April 2005
Anisotropic Self-Diffusion in Block Copolymer Cylinders Cavicchi, Kevin A.; Lodge, Timothy P. Macromolecules, Vol. 37, Issue 16 https://doi.org/10.1021/ma0495339	journal	July 2004
Electric Field Alignment of Asymmetric Diblock Copolymer Thin Films Xu, T.; Zvelindovsky, A. V.; Sevink, G. J. A. Macromolecules, Vol. 38, Issue 26 https://doi.org/10.1021/ma050521c	journal	December 2005
Ionic Conductivity, Capacitance, and Viscoelastic Properties of Block Copolymer-Based Ion Gels Zhang, Sipei; Lee, Keun Hyung; Frisbie, C. Daniel Macromolecules, Vol. 44, Issue 4 https://doi.org/10.1021/ma102435a	journal	February 2011
Effect of Concentration on the Glass Transition and Viscoelastic Properties of Poly(methyl methacrylate)/Ionic Liquid Solutions Mok, Michelle M.; Liu, Xingcheng; Bai, Zhifeng Macromolecules, Vol. 44, Issue 4 https://doi.org/10.1021/ma102503j	journal	January 2011
Effect of Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers Weber, Ryan L.; Ye, Yuesheng; Schmitt, Andrew L. Macromolecules, Vol. 44, Issue 14 https://doi.org/10.1021/ma201067h	journal	July 2011
Controlling the Orientation of Block Copolymer Thin Films using Thermally-Stable Gold Nanoparticles with Tuned Surface Chemistry Yoo, Misang; Kim, Seyong; Jang, Se Gyu Macromolecules, Vol. 44, Issue 23 https://doi.org/10.1021/ma2019254	journal	December 2011
Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing Singh, Gurpreet; Yager, Kevin G.; Smilgies, Detlef-M. Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma301004j	journal	August 2012
Solvent Vapor Annealing of Block Polymer Thin Films Sinturel, Christophe; Vayer, Marylène; Morris, Michael Macromolecules, Vol. 46, Issue 14 https://doi.org/10.1021/ma400735a	journal	June 2013
Effect of the Solvent on Polymer Incompatibility in Solution Zeman, L.; Patterson, D. Macromolecules, Vol. 5, Issue 4 https://doi.org/10.1021/ma60028a030	journal	July 1972
Cylindrical Microdomain Orientation of PS- b -PMMA on the Balanced Interfacial Interactions: Composition Effect of Block Copolymers Ryu, Du Yeol; Ham, Sujin; Kim, Eunhye Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma900110w	journal	July 2009
Self-Consistent Calculations of Block Copolymer Solution Phase Behavior Huang, Ching-I; Lodge, Timothy P. Macromolecules, Vol. 31, Issue 11 https://doi.org/10.1021/ma980007p	journal	June 1998
Neutrality Conditions for Block Copolymer Systems on Random Copolymer Brush Surfaces Huang, E.; Pruzinsky, S.; Russell, T. P. Macromolecules, Vol. 32, Issue 16 https://doi.org/10.1021/ma990483v	journal	August 1999
Diffusion of Triblock Copolymers in a Spherical Domain Structure Yokoyama, Hideaki; Kramer, Edward J. Macromolecules, Vol. 33, Issue 3 https://doi.org/10.1021/ma991202m	journal	February 2000
Highly Aligned Block Copolymer Thin Films by Synergistic Coupling of Static Graphoepitaxy and Dynamic Thermal Annealing Fields Berry, Brian C.; Singh, Gurpreet; Kim, Ho-Cheol ACS Macro Letters, Vol. 2, Issue 4 https://doi.org/10.1021/mz400054y	journal	March 2013
Deep-Nanoscale Pattern Engineering by Immersion-Induced Self-Assembly Park, Woon Ik; Kim, Jong Min; Jeong, Jae Won ACS Nano, Vol. 8, Issue 10 https://doi.org/10.1021/nn504995c	journal	October 2014
Ionic liquid polymer electrolytes Ye, Yun-Sheng; Rick, John; Hwang, Bing-Joe J. Mater. Chem. A, Vol. 1, Issue 8 https://doi.org/10.1039/C2TA00126H	journal	January 2013
Enhanced vertical ordering of block copolymer films by tuning molecular mass Zhang, Xiaohua; Douglas, Jack F.; Satija, Sushil RSC Advances, Vol. 5, Issue 41 https://doi.org/10.1039/C5RA02047F	journal	January 2015
Enhanced resistance to decay of imprinted nanopatterns in thin films by bare nanoparticles compared to polymer-grafted nanoparticles Bhadauriya, Sonal; Nallapaneni, Asritha; Wang, Xiaoteng Nanoscale Advances, Vol. 3, Issue 18 https://doi.org/10.1039/D1NA00206F	journal	January 2021
Rapid structural reorganization in thin films of block copolymer self-assembly Gong, Jinsam; Ahn, Hyungju; Kim, Eunhye Soft Matter, Vol. 8, Issue 13 https://doi.org/10.1039/c2sm07262a	journal	January 2012
Lamellar and liquid crystal ordering in solvent-annealed all-conjugated block copolymers Lin, Yen-Hao; Yager, Kevin G.; Stewart, Bridget Soft Matter, Vol. 10, Issue 21 https://doi.org/10.1039/c3sm53090f	journal	January 2014
Controlled solvent vapor annealing of a high χ block copolymer thin film Lundy, Ross; Flynn, Shauna P.; Cummins, Cian Physical Chemistry Chemical Physics, Vol. 19, Issue 4 https://doi.org/10.1039/c6cp07633e	journal	January 2017
Theory of the Interface between Immiscible Polymers. II Helfand, Eugene; Tagami, Yukiko The Journal of Chemical Physics, Vol. 56, Issue 7 https://doi.org/10.1063/1.1677735	journal	April 1972
Controlling the size of nanostructures in thin films via blending of block copolymers and homopolymers Peng, Juan; Gao, Xiang; Wei, Yuhan The Journal of Chemical Physics, Vol. 122, Issue 11 https://doi.org/10.1063/1.1858854	journal	March 2005
Morphologies in solvent-annealed thin films of symmetric diblock copolymer Peng, Juan; Kim, Dong Ha; Knoll, Wolfgang The Journal of Chemical Physics, Vol. 125, Issue 6 https://doi.org/10.1063/1.2219446	journal	August 2006
Reversible morphology control of three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates Chu, Chiang-Jui; Cheng, Ming-Hsiang; Chung, Pei-Yun International Journal of Polymeric Materials and Polymeric Biomaterials, Vol. 65, Issue 13 https://doi.org/10.1080/00914037.2016.1157801	journal	May 2016
Nanoscale Strategies to Enhance the Energy Storage Capacity of Polymeric Dielectric Capacitors: Review of Recent Advances Singh, Maninderjeet; Apata, Ikeoluwa E.; Samant, Saumil Polymer Reviews https://doi.org/10.1080/15583724.2021.1917609	journal	May 2021
GIXSGUI : a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films Jiang, Zhang Journal of Applied Crystallography, Vol. 48, Issue 3 https://doi.org/10.1107/S1600576715004434	journal	April 2015
Can ionic liquid additives be used to extend the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self-assembly? Bennett, Thomas M.; Pei, Kevin; Cheng, Han-Hao Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 13, Issue 3 https://doi.org/10.1117/1.JMM.13.3.031304	journal	July 2014
Formation of sub-7 nm feature size PS-b-P4VP block copolymer structures by solvent vapour process Chaudhari, Atul; Ghoshal, Tandra; Shaw, Matthew T. SPIE Advanced Lithography, SPIE Proceedings https://doi.org/10.1117/12.2046044	conference	March 2014
Extending the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self-assembly Bennett, Thomas; Pei, Kevin; Cheng, Han-Hao SPIE Advanced Lithography, SPIE Proceedings https://doi.org/10.1117/12.2046296	conference	March 2014
Block Copolymer Thermodynamics: Theory and Experiment Bates, Frank S.; Fredrickson, Glenn H. Annual Review of Physical Chemistry, Vol. 41, Issue 1 https://doi.org/10.1146/annurev.pc.41.100190.002521	journal	October 1990
Polymer self assembly in semiconductor microelectronics Black, C. T.; Ruiz, R.; Breyta, G. IBM Journal of Research and Development, Vol. 51, Issue 5 https://doi.org/10.1147/rd.515.0605	journal	September 2007

Similar Records

Direct Immersion Annealing of Thin Block Copolymer Films

Journal Article · Wed Sep 09 00:00:00 EDT 2015 · ACS Applied Materials and Interfaces · OSTI ID:1354329

Ultra-Fast Vertical Ordering of Lamellar Block Copolymer Films on Unmodified Substrates

Journal Article · Tue Jan 19 19:00:00 EST 2021 · Macromolecules · OSTI ID:1774155

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aromatic compounds
block copolymer
chemical structure
directed assembly
enhanced kinetics
enhanced stability
grazing incidence small angle scattering
ionic liquids
long-range order
order
solvent annealing
solvents
vertical orientation

Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Citation Formats

References (59)

Similar Records

Related Subjects