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Title: In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

Abstract

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing under vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.

Authors:
ORCiD logo [1];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1337655
Alternate Identifier(s):
OSTI ID: 1359790
Report Number(s):
BNL-113318-2016-JA
Journal ID: ISSN 0032-3861; R&D Project: 32452; KC0403020
Grant/Contract Number:  
SC00112704; SC0012704; DMR1419807
Resource Type:
Accepted Manuscript
Journal Name:
Polymer
Additional Journal Information:
Journal Volume: 101; Journal Issue: C; Journal ID: ISSN 0032-3861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; block copolymer; self-assembly; ordering; Center for Functional Nanomaterials; in situ

Citation Formats

Bai, W., Yager, K. G., and Ross, C. A. In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition. United States: N. p., 2016. Web. doi:10.1016/j.polymer.2016.08.055.
Bai, W., Yager, K. G., & Ross, C. A. In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition. United States. https://doi.org/10.1016/j.polymer.2016.08.055
Bai, W., Yager, K. G., and Ross, C. A. Fri . "In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition". United States. https://doi.org/10.1016/j.polymer.2016.08.055. https://www.osti.gov/servlets/purl/1337655.
@article{osti_1337655,
title = {In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition},
author = {Bai, W. and Yager, K. G. and Ross, C. A.},
abstractNote = {The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing under vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.},
doi = {10.1016/j.polymer.2016.08.055},
journal = {Polymer},
number = C,
volume = 101,
place = {United States},
year = {Fri Aug 19 00:00:00 EDT 2016},
month = {Fri Aug 19 00:00:00 EDT 2016}
}

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Cited by: 9 works
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Works referenced in this record:

Composite mesostructures by nano-confinement
journal, October 2004

  • Wu, Yiying; Cheng, Guosheng; Katsov, Kirill
  • Nature Materials, Vol. 3, Issue 11
  • DOI: 10.1038/nmat1230

Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An in Situ GISAXS Study
journal, May 2010

  • Paik, Marvin Y.; Bosworth, Joan K.; Smilges, Detlef-M.
  • Macromolecules, Vol. 43, Issue 9
  • DOI: 10.1021/ma902646t

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents
journal, April 2015

  • Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.
  • Advanced Functional Materials, Vol. 25, Issue 20
  • DOI: 10.1002/adfm.201404053

Thin Film Morphologies of Bulk-Gyroid Polystyrene- block -polydimethylsiloxane under Solvent Vapor Annealing
journal, August 2014

  • Bai, Wubin; Hannon, Adam F.; Gotrik, Kevin W.
  • Macromolecules, Vol. 47, Issue 17
  • DOI: 10.1021/ma501293n

Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns
journal, June 2009


A Top Coat with Solvent Annealing Enables Perpendicular Orientation of Sub-10 nm Microdomains in Si-Containing Block Copolymer Thin Films
journal, September 2014

  • Kim, Eunjin; Kim, Wonjung; Lee, Kwang Hee
  • Advanced Functional Materials, Vol. 24, Issue 44
  • DOI: 10.1002/adfm.201401678

Solvent Vapor Annealing of Block Polymer Thin Films
journal, June 2013

  • Sinturel, Christophe; Vayer, Marylène; Morris, Michael
  • Macromolecules, Vol. 46, Issue 14
  • DOI: 10.1021/ma400735a

An In Situ Grazing Incidence X-Ray Scattering Study of Block Copolymer Thin Films During Solvent Vapor Annealing
journal, November 2013

  • Gu, Xiaodan; Gunkel, Ilja; Hexemer, Alexander
  • Advanced Materials, Vol. 26, Issue 2
  • DOI: 10.1002/adma.201302562

Magnetic field alignment of block copolymers and polymer nanocomposites: Scalable microstructure control in functional soft materials
journal, October 2011

  • Majewski, Pawel W.; Gopinadhan, Manesh; Osuji, Chinedum O.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 1
  • DOI: 10.1002/polb.22382

Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures
journal, June 2005

  • Stoykovich, Mark P.; Müller, Marcus; Kim, Sang Ouk
  • Science, Vol. 308, Issue 5727, p. 1442-1446
  • DOI: 10.1126/science.1111041

3D TEM Tomography of Templated Bilayer Films of Block Copolymers
journal, October 2014

  • Gotrik, Kevin W.; Lam, Thomas; Hannon, Adam F.
  • Advanced Functional Materials, Vol. 24, Issue 48
  • DOI: 10.1002/adfm.201402457

Perpendicular Block Copolymer Microdomains in High Aspect Ratio Templates
journal, September 2015


Self-assembly of block copolymer thin films
journal, June 2010


High-Aspect-Ratio Perpendicular Orientation of PS- b -PDMS Thin Films under Solvent Annealing
journal, October 2012

  • Son, Jeong Gon; Gotrik, Kevin W.; Ross, C. A.
  • ACS Macro Letters, Vol. 1, Issue 11
  • DOI: 10.1021/mz300475g

The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity
journal, June 2002

  • Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J.
  • Macromolecules, Vol. 35, Issue 12
  • DOI: 10.1021/ma0200975

Phase Behavior of Block Copolymers in a Neutral Solvent
journal, February 2003

  • Lodge, Timothy P.; Hanley, Kenneth J.; Pudil, Bryant
  • Macromolecules, Vol. 36, Issue 3
  • DOI: 10.1021/ma0209601

Phase Behavior of a Block Copolymer in Solvents of Varying Selectivity
journal, August 2000

  • Hanley, Kenneth J.; Lodge, Timothy P.; Huang, Ching-I
  • Macromolecules, Vol. 33, Issue 16
  • DOI: 10.1021/ma000318b

Morphology Control in Block Copolymer Films Using Mixed Solvent Vapors
journal, August 2012

  • Gotrik, Kevin W.; Hannon, Adam F.; Son, Jeong Gon
  • ACS Nano, Vol. 6, Issue 9
  • DOI: 10.1021/nn302641z

Morphology-Controlled Kinetics of Solvent Uptake by Block Copolymer Films in Nonselective Solvent Vapors
journal, August 2014

  • Stenbock-Fermor, Anja; Rudov, Andrey A.; Gumerov, Rustam A.
  • ACS Macro Letters, Vol. 3, Issue 8
  • DOI: 10.1021/mz500347n

Effect of dilution on a block copolymer in the complex phase window
journal, December 1998


An in situ GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in-plane sphere order upon deswelling
journal, October 2015

  • Gunkel, Ilja; Gu, Xiaodan; Sun, Zhiwei
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 2
  • DOI: 10.1002/polb.23933

Structural Rearrangements in a Lamellar Diblock Copolymer Thin Film during Treatment with Saturated Solvent Vapor
journal, January 2010

  • Di, Zhenyu; Posselt, Dorthe; Smilgies, Detlef-M.
  • Macromolecules, Vol. 43, Issue 1
  • DOI: 10.1021/ma9017795

In Situ GISAXS Study on Solvent Vapour Induced Orientation Switching in PS- b -P4VP Block Copolymer Thin Films
journal, November 2010

  • Gowd, E. Bhoje; Böhme, Marcus; Stamm, Manfred
  • IOP Conference Series: Materials Science and Engineering, Vol. 14
  • DOI: 10.1088/1757-899X/14/1/012015

Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute
journal, June 2014

  • Kao, Joseph; Thorkelsson, Kari; Bai, Peter
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5053

Cylinder Orientation Mechanism in Block Copolymer Thin Films Upon Solvent Evaporation
journal, September 2010

  • Phillip, William A.; Hillmyer, Marc A.; Cussler, E. L.
  • Macromolecules, Vol. 43, Issue 18
  • DOI: 10.1021/ma1012946

Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering
journal, May 2005

  • Lee, Byeongdu; Park, Insun; Yoon, Jinhwan
  • Macromolecules, Vol. 38, Issue 10
  • DOI: 10.1021/ma047562d

A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator
journal, October 2010


Depth-Dependent Structural Changes in PS- b -P2VP Thin Films Induced by Annealing
journal, August 2014

  • Wernecke, Jan; Okuda, Hiroshi; Ogawa, Hiroki
  • Macromolecules, Vol. 47, Issue 16
  • DOI: 10.1021/ma500642d

Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS: Different Behavior of Parallel and Perpendicular Lamellae
journal, August 2014

  • Zhang, Jianqi; Posselt, Dorthe; Smilgies, Detlef-M.
  • Macromolecules, Vol. 47, Issue 16
  • DOI: 10.1021/ma500633b

Controlling Domain Spacing and Grain Size in Cylindrical Block Copolymer Thin Films by Means of Thermal and Solvent Vapor Annealing
journal, April 2016


Solvent vapor annealing of block copolymer thin films: removal of processing history
journal, June 2014

  • Gu, Xiaodan; Gunkel, Ilja; Hexemer, Alexander
  • Colloid and Polymer Science, Vol. 292, Issue 8
  • DOI: 10.1007/s00396-014-3286-9

Block Copolymer Self Assembly during Rapid Solvent Evaporation: Insights into Cylinder Growth and Stability
journal, December 2013

  • Paradiso, Sean P.; Delaney, Kris T.; García-Cervera, Carlos J.
  • ACS Macro Letters, Vol. 3, Issue 1
  • DOI: 10.1021/mz400572r

Structural Transitions in Asymmetric Poly(styrene)- block -Poly(lactide) Thin Films Induced by Solvent Vapor Exposure
journal, July 2014

  • Sinturel, Christophe; Grosso, David; Boudot, Mickael
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 15
  • DOI: 10.1021/am504086x

Coexistence curves of polystyrene/ poly(dimethylsiloxane) blends
journal, January 1995


Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography
journal, February 2014

  • Kennemur, Justin G.; Yao, Li; Bates, Frank S.
  • Macromolecules, Vol. 47, Issue 4
  • DOI: 10.1021/ma4020164

Universal pattern transfer methods for metal nanostructures by block copolymer lithography
journal, August 2015


Eliminating the Trade-Off between the Throughput and Pattern Quality of Sub-15 nm Directed Self-Assembly via Warm Solvent Annealing
journal, November 2014

  • Kim, Jong Min; Kim, YongJoo; Park, Woon Ik
  • Advanced Functional Materials, Vol. 25, Issue 2
  • DOI: 10.1002/adfm.201401529

Simulation methods for solvent vapor annealing of block copolymer thin films
journal, January 2015

  • Hannon, A. F.; Bai, W.; Alexander-Katz, A.
  • Soft Matter, Vol. 11, Issue 19
  • DOI: 10.1039/C5SM00324E

Topcoat-Assisted Perpendicular and Straightly Parallel Coexisting Orientations of Block Copolymer Films
journal, April 2015

  • Jeong, Jiyoung; Ha, Jeong Sook; Lee, Sang-Soo
  • Macromolecular Rapid Communications, Vol. 36, Issue 13
  • DOI: 10.1002/marc.201500088

Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation
journal, February 2004

  • Kim, S. H.; Misner, M. J.; Xu, T.
  • Advanced Materials, Vol. 16, Issue 3, p. 226-231
  • DOI: 10.1002/adma.200304906

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990


Failure of the dilution approximation in block copolymer solutions
journal, November 1995

  • Lodge, T. P.; Pan, C.; Jin, X.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 16
  • DOI: 10.1002/polb.1995.090331614

Works referencing / citing this record:

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures
journal, March 2018

  • Berezkin, Anatoly V.; Jung, Florian; Posselt, Dorthe
  • Advanced Functional Materials, Vol. 28, Issue 19
  • DOI: 10.1002/adfm.201706226

UV-solvent annealing of PDMS-majority and PS-majority PS- b -PDMS block copolymer films
journal, October 2016