skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS

Abstract

Dynamic thermal gradient-based processes for directed self-assembly of block copolymer (BCP) thin films such as cold zone annealing (CZA) have demonstrated much potential for rapidly fabricating highly ordered patterns of BCP domains with facile orientation control. As a demonstration, hexagonally packed predominantly vertical cylindrical morphology, technologically relevant for applications such as membranes and lithography, was achieved in 1 μm thick cylinder-forming PS-b-PMMA (cBCP) films by applying sharp thermal gradients (CZA-Sharp) at optimum sample sweep rates. A thorough understanding of the molecular level mechanisms and pathways of the BCP ordering that occur during this CZA-S process is presented, useful to fully exploit the potential of CZA-S for large-scale BCP-based device fabrication. To that end, we developed a customized CZA-S assembly to probe the dynamic structure evolution and ordering of the PS-b-PMMA cBCP film in situ as it undergoes the CZA-S process using the grazing incidence small-angle X-ray scattering (GISAXS) technique. Four distinct regimes of BCP ordering were observed within the gradient that include microphase separation from an “as cast” unordered state (Regime I), evolution of vertical cylinders under a thermally imposed strain gradient (Regime II), reorientation of a fraction of cylinders due to preferential substrate interactions (Regime III), and finally grain-coarseningmore » on the cooling edge (Regime IV). The ordering pathway in the different regimes is further described within the framework of an energy landscape. A novel aspect of this study is the identification of a grain-coarsening regime on the cooling edge of the gradient, previously obscure in zone annealing studies of BCPs. In conclusion, such insights into the development of highly ordered BCP nanostructures under template-free thermal gradient fields can potentially have important ramifications in the field of BCP-directed self-assembly and self-assembling polymer systems more broadly.« less

Authors:
 [1];  [2];  [3];  [3];  [1];  [1];  [1];  [1];  [4];  [1]
  1. Univ. of Akron, Akron, OH (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Arkansas, Little Rock, AR (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1337643
Alternate Identifier(s):
OSTI ID: 1339647
Report Number(s):
BNL-113293-2016-JA
Journal ID: ISSN 0024-9297; KC0403020
Grant/Contract Number:  
SC00112704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 22; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; block copolymer; self-assembly; GISAXS; cold zone annealing; Center for Functional Nanomaterials; in-situ; orientation correlation length; 36 MATERIALS SCIENCE

Citation Formats

Samant, Saumil, Strzalka, Joseph, Yager, Kevin G., Kisslinger, Kim, Grolman, Danielle, Basutkar, Monali, Salunke, Namrata, Singh, Gurpreet, Berry, Brian, and Karim, Alamgir. Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.macromol.6b01555.
Samant, Saumil, Strzalka, Joseph, Yager, Kevin G., Kisslinger, Kim, Grolman, Danielle, Basutkar, Monali, Salunke, Namrata, Singh, Gurpreet, Berry, Brian, & Karim, Alamgir. Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS. United States. https://doi.org/10.1021/acs.macromol.6b01555
Samant, Saumil, Strzalka, Joseph, Yager, Kevin G., Kisslinger, Kim, Grolman, Danielle, Basutkar, Monali, Salunke, Namrata, Singh, Gurpreet, Berry, Brian, and Karim, Alamgir. Mon . "Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS". United States. https://doi.org/10.1021/acs.macromol.6b01555. https://www.osti.gov/servlets/purl/1337643.
@article{osti_1337643,
title = {Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS},
author = {Samant, Saumil and Strzalka, Joseph and Yager, Kevin G. and Kisslinger, Kim and Grolman, Danielle and Basutkar, Monali and Salunke, Namrata and Singh, Gurpreet and Berry, Brian and Karim, Alamgir},
abstractNote = {Dynamic thermal gradient-based processes for directed self-assembly of block copolymer (BCP) thin films such as cold zone annealing (CZA) have demonstrated much potential for rapidly fabricating highly ordered patterns of BCP domains with facile orientation control. As a demonstration, hexagonally packed predominantly vertical cylindrical morphology, technologically relevant for applications such as membranes and lithography, was achieved in 1 μm thick cylinder-forming PS-b-PMMA (cBCP) films by applying sharp thermal gradients (CZA-Sharp) at optimum sample sweep rates. A thorough understanding of the molecular level mechanisms and pathways of the BCP ordering that occur during this CZA-S process is presented, useful to fully exploit the potential of CZA-S for large-scale BCP-based device fabrication. To that end, we developed a customized CZA-S assembly to probe the dynamic structure evolution and ordering of the PS-b-PMMA cBCP film in situ as it undergoes the CZA-S process using the grazing incidence small-angle X-ray scattering (GISAXS) technique. Four distinct regimes of BCP ordering were observed within the gradient that include microphase separation from an “as cast” unordered state (Regime I), evolution of vertical cylinders under a thermally imposed strain gradient (Regime II), reorientation of a fraction of cylinders due to preferential substrate interactions (Regime III), and finally grain-coarsening on the cooling edge (Regime IV). The ordering pathway in the different regimes is further described within the framework of an energy landscape. A novel aspect of this study is the identification of a grain-coarsening regime on the cooling edge of the gradient, previously obscure in zone annealing studies of BCPs. In conclusion, such insights into the development of highly ordered BCP nanostructures under template-free thermal gradient fields can potentially have important ramifications in the field of BCP-directed self-assembly and self-assembling polymer systems more broadly.},
doi = {10.1021/acs.macromol.6b01555},
journal = {Macromolecules},
number = 22,
volume = 49,
place = {United States},
year = {2016},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors
journal, March 2016

  • Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 12
  • DOI: 10.1021/acsami.5b11851

Broad-wavelength-range chemically tunable block-copolymer photonic gels
journal, October 2007

  • Kang, Youngjong; Walish, Joseph J.; Gorishnyy, Taras
  • Nature Materials, Vol. 6, Issue 12
  • DOI: 10.1038/nmat2032

Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes
journal, February 2010

  • Phillip, William A.; O’Neill, Brandon; Rodwogin, Marc
  • ACS Applied Materials & Interfaces, Vol. 2, Issue 3
  • DOI: 10.1021/am900882t

Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes
journal, December 2005

  • Hawker, Craig J.; Russell, Thomas P.
  • MRS Bulletin, Vol. 30, Issue 12, p. 952-966
  • DOI: 10.1557/mrs2005.249

Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly
journal, August 2008


Orientational Order in Block Copolymer Films Zone Annealed below the Order−Disorder Transition Temperature
journal, September 2007

  • Berry, Brian C.; Bosse, August W.; Douglas, Jack F.
  • Nano Letters, Vol. 7, Issue 9
  • DOI: 10.1021/nl071354s

Domain Orientation and Grain Coarsening in Cylinder-Forming Poly(styrene- b -methyl methacrylate) Films
journal, June 2011

  • Ji, Shengxiang; Liu, Chi-Chun; Liao, Wen
  • Macromolecules, Vol. 44, Issue 11
  • DOI: 10.1021/ma2005734

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

Direct Immersion Annealing of Thin Block Copolymer Films
journal, September 2015

  • Modi, Arvind; Bhaway, Sarang M.; Vogt, Bryan D.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 39
  • DOI: 10.1021/acsami.5b06259

Large Scale Domain Alignment of a Block Copolymer from Solution Using Electric Fields
journal, February 2002

  • Böker, Alexander; Knoll, Armin; Elbs, Hubert
  • Macromolecules, Vol. 35, Issue 4
  • DOI: 10.1021/ma0108113

Pathways toward Electric Field Induced Alignment of Block Copolymers
journal, October 2002

  • Thurn-Albrecht, Thomas; DeRouchey, Jason; Russell, Thomas P.
  • Macromolecules, Vol. 35, Issue 21
  • DOI: 10.1021/ma020567v

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

Order-Disorder Transition and Alignment Dynamics of a Block Copolymer Under High Magnetic Fields by In Situ X-Ray Scattering
journal, February 2013


Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films
journal, October 2012

  • Singh, Gurpreet; Yager, Kevin G.; Berry, Brian
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn304266f

Pathways to Macroscale Order in Nanostructured Block Copolymers
journal, August 1997


Macroscopic Orientation of Block Copolymer Cylinders in Single-Layer Films by Shearing
journal, October 2004

  • Angelescu, D. E.; Waller, J. H.; Adamson, D. H.
  • Advanced Materials, Vol. 16, Issue 19
  • DOI: 10.1002/adma.200400643

Nanostructure engineering by templated self-assembly of block copolymers
journal, October 2004

  • Cheng, Joy Y.; Mayes, Anne M.; Ross, Caroline A.
  • Nature Materials, Vol. 3, Issue 11
  • DOI: 10.1038/nmat1211

Precise Control over Molecular Dimensions of Block-Copolymer Domains Using the Interfacial Energy of Chemically Nanopatterned Substrates
journal, August 2004

  • Edwards, E. W.; Montague, M. F.; Solak, H. H.
  • Advanced Materials, Vol. 16, Issue 15
  • DOI: 10.1002/adma.200400763

Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing
journal, August 2012

  • Singh, Gurpreet; Yager, Kevin G.; Smilgies, Detlef-M.
  • Macromolecules, Vol. 45, Issue 17
  • DOI: 10.1021/ma301004j

Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films
journal, May 2013

  • Singh, Gurpreet; Batra, Saurabh; Zhang, Ren
  • ACS Nano, Vol. 7, Issue 6
  • DOI: 10.1021/nn401094s

Orientation control in nanoparticle filled block copolymer cold zone annealed films
journal, March 2015

  • Samant, Saumil; Hailu, Shimelis T.; Al-Enizi, Abdullah M.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 8
  • DOI: 10.1002/polb.23684

Extending Dynamic Range of Block Copolymer Ordering with Rotational Cold Zone Annealing (RCZA) and Ionic Liquids
journal, October 2015


Millisecond Ordering of Block Copolymer Films via Photothermal Gradients
journal, February 2015

  • Majewski, Pawel W.; Yager, Kevin G.
  • ACS Nano, Vol. 9, Issue 4
  • DOI: 10.1021/nn5071827

Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films
journal, July 2015


Block Copolymer Response to Photothermal Stress Fields
journal, June 2015


Arbitrary lattice symmetries via block copolymer nanomeshes
journal, June 2015

  • Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8448

The Morphology of Directionally Solidified Poly(ethylene oxide) Spherulites
journal, March 1976


Single-Grain Lamellar Microdomain from a Diblock Copolymer
journal, March 1999

  • Bodycomb, Jeffrey; Funaki, Yoshinori; Kimishima, Kohtaro
  • Macromolecules, Vol. 32, Issue 6
  • DOI: 10.1021/ma981538g

Cylindrical Domains of Block Copolymers Developed via Ordering under Moving Temperature Gradient
journal, August 2007

  • Mita, Kazuki; Tanaka, Hirokazu; Saijo, Kenji
  • Macromolecules, Vol. 40, Issue 16
  • DOI: 10.1021/ma070404c

Evolution of block-copolymer order through a moving thermal zone
journal, January 2010

  • Yager, Kevin G.; Fredin, Nathaniel J.; Zhang, Xiaohua
  • Soft Matter, Vol. 6, Issue 1
  • DOI: 10.1039/B916200C

Highly Aligned Block Copolymer Thin Films by Synergistic Coupling of Static Graphoepitaxy and Dynamic Thermal Annealing Fields
journal, March 2013

  • Berry, Brian C.; Singh, Gurpreet; Kim, Ho-Cheol
  • ACS Macro Letters, Vol. 2, Issue 4
  • DOI: 10.1021/mz400054y

Block-Copolymer Ordering with a Spatiotemporally Heterogeneous Mobility
journal, November 2007


Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing
journal, March 2016

  • Cong, Zhinan; Zhang, Liangshun; Wang, Liquan
  • The Journal of Chemical Physics, Vol. 144, Issue 11
  • DOI: 10.1063/1.4943864

Grazing incidence small-angle X-ray scattering: an advanced scattering technique for the investigation of nanostructured polymer films
journal, March 2003


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

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

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

Generating thickness gradients of thin polymer films via flow coating
journal, February 2006

  • Stafford, Christopher M.; Roskov, Kristen E.; Epps, Thomas H.
  • Review of Scientific Instruments, Vol. 77, Issue 2
  • DOI: 10.1063/1.2173072

The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source
journal, June 2012

  • Jiang, Zhang; Li, Xuefa; Strzalka, Joseph
  • Journal of Synchrotron Radiation, Vol. 19, Issue 4
  • DOI: 10.1107/S0909049512022017

Rapid structural reorganization in thin films of block copolymer self-assembly
journal, January 2012

  • Gong, Jinsam; Ahn, Hyungju; Kim, Eunhye
  • Soft Matter, Vol. 8, Issue 13
  • DOI: 10.1039/c2sm07262a

Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate)
journal, May 1990

  • Russell, Thomas P.; Hjelm, Rex P.; Seeger, Phil A.
  • Macromolecules, Vol. 23, Issue 3
  • DOI: 10.1021/ma00205a033

Block copolymer microstructures in the intermediate-segregation regime
journal, February 1997

  • Matsen, M. W.; Bates, F. S.
  • The Journal of Chemical Physics, Vol. 106, Issue 6
  • DOI: 10.1063/1.473153

Long-Range Ordering of Block Copolymer Cylinders Driven by Combining Thermal Annealing and Substrate Functionalization
journal, March 2013

  • She, Ming-Shiuan; Lo, Ting-Ya; Ho, Rong-Ming
  • ACS Nano, Vol. 7, Issue 3
  • DOI: 10.1021/nn305725q

Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions
journal, July 2009

  • Han, Eungnak; Stuen, Karl O.; Leolukman, Melvina
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma9002903

High Aspect Ratio PS- b -PMMA Block Copolymer Masks for Lithographic Applications
journal, November 2014

  • Ferrarese Lupi, F.; Giammaria, T. J.; Volpe, F. G.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 23
  • DOI: 10.1021/am506391n

Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors
journal, October 2009


Relaxation of polymer thin films in isothermal temperature-jump measurements
journal, January 2000


Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films
journal, April 2005

  • Xu, Ting; Hawker, Craig J.; Russell, Thomas P.
  • Macromolecules, Vol. 38, Issue 7
  • DOI: 10.1021/ma048005u

Effect of structural anisotropy on the coarsening kinetics of diblock copolymer striped patterns
journal, February 2008


Structural evolution of cylindrical-phase diblock copolymer thin films
journal, January 2004

  • Black, C. T.; Guarini, K. W.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 8
  • DOI: 10.1002/pola.10977

    Works referencing / citing this record:

    Micellar‐Mediated Block Copolymer Ordering Dynamics Revealed by In Situ Grazing Incidence Small‐Angle X‐Ray Scattering during Spin Coating
    journal, March 2019

    • Fleury, Guillaume; Hermida‐Merino, Daniel; Jingjin, Dong
    • Advanced Functional Materials, Vol. 29, Issue 10
    • DOI: 10.1002/adfm.201806741

    Evolution of Microstructure in Block Copolymer Thin Films during Zone Annealing
    journal, November 2018