Novel Block Copolymer Architectures for Lithography-Relevant Self-Assembly

150 Pages·2016·5.26 MB·English

UUnniivveerrssiittyy ooff SSoouutthh CCaarroolliinnaa
SScchhoollaarr CCoommmmoonnss
Theses and Dissertations
12-14-2015
NNoovveell BBlloocckk CCooppoollyymmeerr AArrcchhiitteeccttuurreess ffoorr LLiitthhooggrraapphhyy--RReelleevvaanntt
SSeellff--AAsssseemmbbllyy
Jeffery Hakim Hayat
University of South Carolina - Columbia
Follow this and additional works at: https://scholarcommons.sc.edu/etd
Part of the Chemistry Commons
RReeccoommmmeennddeedd CCiittaattiioonn
Hayat, J. H.(2015). Novel Block Copolymer Architectures for Lithography-Relevant Self-Assembly.
(Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/3244
This Open Access Dissertation is brought to you by Scholar Commons. It has been accepted for inclusion in
Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please
contact [email protected].
NOVEL BLOCK COPOLYMER ARCHITECTURES FOR LITHOGRAPHY-RELEVANT
SELF-ASSEMBLY

by

Jeffery Hakim Hayat

Bachelor of Science
University of Pittsburgh at Greensburg, 2011

Submitted in Partial Fulfillment of the Requirements

For the Degree of Doctor of Philosophy in

Chemistry

College of Arts and Sciences

University of South Carolina

2015

Accepted by:

Chuanbing Tang, Major Professor

Brian Benicewicz, Committee Member

Hui Wang, Committee Member

Ehsan Jabbarzadeh, Committee Member

Lacy Ford, Senior Vice Provost and Dean of Graduate Studies
© Copyright by Jeffery Hakim Hayat, 2015
All Rights Reserved
ii
DEDICATION
To my wife, my family, and all my friends, without their support and
encouragement, none of my accomplishments would be possible.

iii
ACKNOWLEDGEMENTS
First, I would like to show my sincerest gratitude to my advisor, Dr. Chuanbing
Tang, who gave me the opportunity to work in his research group, and offered endless
support and guidance on my research projects. I feel very fortunate to have the
opportunity to learn from such an enthusiastic and knowledgeable person and it has
proved invaluable in my development as a scientist. His enthusiasm for polymer science
has influenced me a great deal and I am thankful for the foundation he has created for me
and only hope to learn more from him in the future.
I would also like to thank my research committee Dr. Brian Benicewicz, Dr. Hui
Wang, and Dr. Ehsan Jabbarzadeh for their advice, encouragement, and valuable
suggestions on my research during graduate school. Further, I would like to
acknowledge the research collaborations formed with Dr. Gila Stein’s research group
from the University of Houston and Dr. Morgan Stefik’s research group from USC as
they were instrumental in the research presented herein.
I am very appreciative of the experiences shared and friendships formed with
other graduate students and post-docs at USC. Members of Tang group, Dr. Christopher
Hardy, Dr. Kejian Yao, Dr. Perry Wilbon, Dr. Jiuyang Zhang, Dr. Yali Qiao, Dr. Yi Yan,
Dr. Alper Nese, Dr. Xiaodong Yin, Dr. Zhongkai Wang, Mitra Ganewatta, Liang Yuan,
Nathan Trenor, Paras Pageni, Anis Rahman, Pabel Kabir, Meghan Lamm, and many
great others. It was a great pleasure to work with all of you and learn from you. I would
iv
also like to thank Mike, Tony, Mohammad, Amrita, Andrew, and Zach for your help both
within and outside of lab.
Further, I would like especially like to thank Kayley Fishel-Hayat for her constant
support, listening, and help throughout my academic career, as it allowed me to reach this
stage. Holly and Benji-thank you for always being there for mom so she could be there
for me. Thank you very much!
Finally, I would like to acknowledge all the funding supports from the University
of South Carolina, the SRC, and the ACS Petroleum Research Fund.
v
ABSTRACT
This dissertation is focused on the synthesis, characterization, self-assembly, and
materials processing of various functionalized block copolymer systems. A variety of
monomers were prepared and polymerized through various polymerization techniques
including atom transfer radical polymerization, reversible addition-fragmentation chain
transfer polymerization, and ring-opening metathesis polymerization. Self-assembly of
the functionalized block copolymers led to well-defined nanostructures in bulk and thin
films. These materials have the capability to be utilized in various applications including
ordered catalysts and templates for nanolithography.
In Chapter 1, the overall background of diblock and triblock copolymers and their
preparation methods is in this dissertation. Major research objectives of my doctoral work
are described.
Chapter 2 focuses on the reduction of annealing time and use of industrially
compatible solvents in high-humidity solvent annealing with poly(ethylene oxide)-block-
poly(styrene). Chapters 3-5 describe the design, synthesis, and characterization of various
diblock and triblock polymeric architectures and their self-assembly in both bulk and
thin-films. Incorporating desirable functional groups into block copolymer systems can
lead to confinement of the functional group to a specific domain upon microphase
vi
separation of block copolymers. The resulting materials display desirable characteristics
of the functional group in a well-ordered nanostructure.
Finally, chapter 6 provides a summary of the work described herein, and provides
an outlook into future research with these block copolymer systems.

vii
TABLE OF CONTENTS
DEDICATION ....................................................................................................................... iii
ACKNOWLEDGEMENTS ........................................................................................................ iv
ABSTRACT .......................................................................................................................... vi
LIST OF TABLES .................................................................................................................. xi
LIST OF FIGURES ................................................................................................................ xii
LIST OF SYMBOLS ...............................................................................................................xv
LIST OF ABBREVIATIONS ................................................................................................... xvi
CHAPTER 1: INTRODUCTION ..................................................................................................1
1.1 BACKGROUND .......................................................................................................2
1.2 DIBLOCK COPOLYMERS .........................................................................................2
1.3 TRIBLOCK COPOLYMERS ........................................................................................4
1.4 POLYMERIZATION TECHNIQUES AND “CLICK” CHEMISTRY ...................................5
1.5 DISSERTATION OUTLINE ........................................................................................9
1.6 REFERENCES ........................................................................................................10
CHAPTER 2: IMPROVING HUMIDITY-CONTROLLED SOLVENT ANNEALING PROCESSES FOR
BLOCK COPOLYMER POLY(ETHYLENE OXIDE)-B-POLYSTYRENE .......................................15

2.1 ABSTRACT ...........................................................................................................16
2.2 INTRODUCTION ....................................................................................................16
2.3 EXPERIMENTAL SECTION .....................................................................................20
2.4 RESULTS AND DISCUSSION ..................................................................................22
viii
2.5 CONCLUSION .......................................................................................................47
2.6 REFERENCES ........................................................................................................47
CHAPTER 3: HIGH QUALITY FILMS WITH SUB-10 NM FEATURE SIZES UTILIZING NOVEL
GRAFTED AND STAR BLOCK COPOLYMERS ........................................................................52

3.1 ABSTRACT ...........................................................................................................53
3.2 INTRODUCTION ....................................................................................................53
3.3 EXPERIMENTAL SECTION .....................................................................................57
3.4 RESULTS AND DISCUSSION ..................................................................................65
3.5 CONCLUSION .......................................................................................................74
3.6 REFERENCES ........................................................................................................74
CHAPTER 4: SYMMETRIC POLY(2-VINYLPYRIDINE-B-STYRENE-B-ISOPRENE) TRIBLOCK
COPOLYMERS: SYNTHESIS, CHARACTERIZATION, AND SELF-ASSEMBLY IN BULK AND THIN
FILMS ..................................................................................................................................78

4.1 ABSTRACT ...........................................................................................................79
4.2 INTRODUCTION ....................................................................................................79
4.3 EXPERIMENTAL SECTION .....................................................................................82
4.4 RESULTS AND DISCUSSION ..................................................................................88
4.5 CONCLUSION .......................................................................................................98
4.6 REFERENCES ........................................................................................................99
CHAPTER 5: GRAFTED BLOCK COPOLYMER PNB-G-(PS-B-PMMA) ................................104

5.1 ABSTRACT .........................................................................................................105
5.2 INTRODUCTION ..................................................................................................105
5.3 EXPERIMENTAL SECTION ...................................................................................108
5.4 RESULTS AND DISCUSSION ................................................................................113
5.5 CONCLUSION .....................................................................................................122
ix