From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

Meirav Oded; Stephen T. Kelly; Mary K. Gilles; Axel H.E. Müller; Roy Shenhar

doi:10.1016/j.polymer.2016.07.016

From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

Meirav Oded, Stephen T. Kelly, Mary K. Gilles, Axel H.E. Müller, Roy Shenhar^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. These insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.

Original language	American English
Pages (from-to)	406-414
Number of pages	9
Journal	Polymer
Volume	107
DOIs	https://doi.org/10.1016/j.polymer.2016.07.016
State	Published - 19 Dec 2016

Bibliographical note

Funding Information:
M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program , and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 . M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements.

Funding Information:
M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program, and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements.

Publisher Copyright:
© 2016 Elsevier Ltd

Keywords

Block copolymers
Layer-by-layer deposition
Patterning
Polyelectrolytes
Self-assembly

Access to Document

10.1016/j.polymer.2016.07.016

Cite this

@article{67f179d3fbd34093920a326fef49cd1c,

title = "From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates",

abstract = "The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. These insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.",

keywords = "Block copolymers, Layer-by-layer deposition, Patterning, Polyelectrolytes, Self-assembly",

author = "Meirav Oded and Kelly, {Stephen T.} and Gilles, {Mary K.} and M{\"u}ller, {Axel H.E.} and Roy Shenhar",

note = "Funding Information: M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program , and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 . M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements. Funding Information: M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program, and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements. Publisher Copyright: {\textcopyright} 2016 Elsevier Ltd",

year = "2016",

month = dec,

day = "19",

doi = "10.1016/j.polymer.2016.07.016",

language = "American English",

volume = "107",

pages = "406--414",

journal = "Polymer",

issn = "0032-3861",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - From dots to doughnuts

T2 - Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

AU - Oded, Meirav

AU - Kelly, Stephen T.

AU - Gilles, Mary K.

AU - Müller, Axel H.E.

AU - Shenhar, Roy

N1 - Funding Information: M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program , and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 . M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements. Funding Information: M.O. thanks the Harry and Sylvia Hoffman Leadership and Responsibility Program, and the Dalia and Dan Maydan Fellowship for financial support. The Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. M.K.G., S.T.K and Beamline 11.0.2 were supported by the same contract as well as the Condensed Phase and Interfacial Molecular Sciences Program of the U.S. Department of Energy. The authors thank Dr. Vitaly Gutkin for assistance with the XPS measurements. Publisher Copyright: © 2016 Elsevier Ltd

PY - 2016/12/19

Y1 - 2016/12/19

N2 - The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. These insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.

AB - The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. These insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.

KW - Block copolymers

KW - Layer-by-layer deposition

KW - Patterning

KW - Polyelectrolytes

KW - Self-assembly

UR - http://www.scopus.com/inward/record.url?scp=85002891899&partnerID=8YFLogxK

U2 - 10.1016/j.polymer.2016.07.016

DO - 10.1016/j.polymer.2016.07.016

M3 - Article

AN - SCOPUS:85002891899

SN - 0032-3861

VL - 107

SP - 406

EP - 414

JO - Polymer

JF - Polymer

ER -

From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Fingerprint

Cite this