Polycyclic aromatic hydrocarbons: exploring new processes and materials for electronics

252 Pages·2013·7.01 MB·English

POLYCYCLIC AROMATIC HYDROCARBONS:
EXPLORING NEW PROCESSES AND MATERIALS FOR
ELECTRONICS

A Thesis
Presented to
The Academic Faculty

by

Jose Baltazar

In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy in the
School of Chemical and Biomolecular Engineering

Georgia Institute of Technology
May 2014

COPYRIGHT 2014 BY JOSE BALTAZAR
POLYCYCLIC AROMATIC HYDROCARBONS:
EXPLORING NEW PROCESSES AND MATERIALS FOR
ELECTRONICS

Approved by:

Dr. Clifford L. Henderson, Advisor Dr. Elsa Reichmanis
School of Chemical and Biomolecular School of Chemical and Biomolecular
Engineering Engineering
Georgia Institute of Technology Georgia Institute of Technology

Dr. Laren M. Tolbert Dr. Samuel Graham
School of Chemistry and Biochemistry School of Mechanical Engineering
Georgia Institute of Technology Georgia Institute of Technology

Dr. Dennis W. Hess
School of Chemical and Biomolecular
Engineering
Georgia Institute of Technology

Date Approved:[December 13, 2013]
To all, whom I am lucky to have as “My Family”.
Muito Obrigado!
ACKNOWLEDGEMENTS

I would like to thank everyone looking from above, blessing me, providing me with
the extra and essential pieces of the puzzle that life is. I must/have to thank all my family
members (my uncles, aunts, grandmothers, cousins, etc) for not being able to see me for
many years, their patience, unconditional love puts to shame whoever said “far from the
eyes, far from the heart”. I especially would like to thank my mother Filomena ( Tia Mena)
for being “my heart”, My father Jose Baltazar (Papa, taking care of me from above) for
being “my head”: I can’t put into words what both of you mean to me and I know that you
will always take care of me. I would like to thank my sister Osualda Palanca (Yaya), whose
courage and determination never stops to impress me, if I had half of your heart I would
be able to achieve the imaginable, never change my dear sister. I would like to thank my
other siblings, even though we were apart, we grew stronger: Edson, Sandra, Lucy, Vado,
Breno, Lueji, Emmanuel and Ariel.
I want to thank the many people that directly or indirectly made this dissertation
possible, without whom none of this would have been possible. Firstly, I would like to
thank my advisor Professor Cliff Henderson for his advisement, encouragement and
guidance during the course of this research; the freedom he provided while conducting
research and his valuable opinions and insights, allowed me to expand my ideas and move
in the right direction, promoting scientific growth and maturity. I would also like to extend
my gratitude to Professor Laren M. Tolbert, my second advisor, for all his unlimited help,
knowledge, opinions and support during my time at Georgia Tech, that were essential for
my success.
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I would also like to thank my committee members, Professor Dennis W. Hess,
Professor Samuel Graham and Professor Elsa Reichmanis for their patience, input, advice
and feedback on my work.
I would also like to thank my colleagues, co-authors whom I have worked very
closely to complete this thesis: Dr. Hua-Wei Chu, Dr Janusz Kowalik, Dr Hossein Sojoudi,
Boyi Fu, Dr Sergio Paniagua, Dr Wei-Ming Yeh, Dr Jing Chen, Dr Nathan Jarnagin, Dr
Juan Vargas, Mason Risley, Siyuan Zhang, Dr Richard Lawson, Andrew Peters and Caleb
Breaux. I spent countless nights and weekends working, shared not only experimental data
but also friendship. I hope success to all of your endeavors, and that we can continue our
friendship for years to come.
Last but not least, I would like to acknowledge, from the bottom of my heart all of
my friends (which are now part of my family), in no particular order, who provided a nice
environment during this past 4.5 years: we shared many discussion, problems set, soccer
games, meals, movies etc. I am appreciative the unconditional friendship that made us
closer each and every day: Deepraj, Nitesh, Carine, Frank, Christine, Wilmarie, Andac,
Sandeep, Michael, Lina, Loice. Florencia, Fabian, Ben, Boris, Diapa, Ponion, Norbert,
Nick, Roma FC, Vahi FC, Namory, Rodrigue, Avi, Prashant, Pramod, Messi, Ronaldo, Oli.
Emmanuel, Anthony, Trudy, Chi-Chi, Shirae, Eno, Bruna and Arine and many more
friends that I hold dear in my heart.
I would like to thank NSF and Intel for funding. I appreciate the help I received
from the management and staff members at the Georgia institute of Technology, the
Microelectronics Research Center (MiRC), the ChBE graduate office and all the other
member of the Georgia Tech family: Thank you!
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TABLE OF CONTENTS

Page

ACKNOWLEDGEMENTS iv
LIST OF TABLES x
LIST OF FIGURES xi
LIST OF SYMBOLS xviii
SUMMARY xxiii
CHAPTER 1
INTRODUCTION AND BACKGROUND 1
1.1 Overview 1
1.2 Graphene and Its Properties 6
1.3 Graphene Synthesis Methods 9
1.4 Graphene: Applications, Devices and Doping 11
1.5 Research Objective 16
1.6 Organization of Thesis 17
1.7 References 20

CHAPTER 2
FACILE FORMATION OF GRAPHENE P-N JUNCTIONS USING APTES 27
2.1 Introduction 28
2.2 Experimental Section 31
2.3 Results and Discussion 33
2.4 Conclusions 50
2.5 References 51
vi
CHAPTER 3
CREATING GRAPHENE P-N JUNCTIONS USING SELF-ASSEMBLED
MONOLAYERS 56
3.1 Introduction 57
3.2 Experimental Section 59
3.3 Results and Discussion 60
3.4 Conclusions 70
3.5 References 71

CHAPTER 4
PHOTOCHEMICAL DOPING AND TUNING OF THE WORK FUNCTION AND
DIRAC POINT IN GRAPHENE USING PHOTOACID AND PHOTOBASE
GENERATORS 74
4.1 Introduction 75
4.2 Experimental Section 78
4.2.1 Graphene Growth 78
4.2.2 Device fabrication, doping procedure and electrical measurements 79
4.2.3 Surface Characterization and UV/Visible Spectroscopy 81
4.3 Results and Discussion 82
4.4 Conclusions 106
4.5 References 107

CHAPTER 5
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EXFOLIATION OF GRAPHENE SHEETS BY AN ELECTRON DONOR
SURFACTANT 113
5.1 Introduction 114
5.2 Experimental Section 119
5.3 Results and Discussion 123
5.4 Conclusions 138
5.5 References 139

CHAPTER 6
EXPLORING SURFACE DIELS-ALDER ADDUCTS ON SILICA AS A
CONTROLLABLE CARBON PRECURSOR FOR PRISTINE GRAPHENE 145
6.1 Introduction 146
6.2 Experimental Section 147
6.3 Results and Discussion 152
6.4 Conclusions 160
6.5 References 161

CHAPTER 7
TOWARDS A LOW TEMPERATURE GRAPHENE GROWTH USING NON-
FLAMMABLE PRECURSORS 165
7.1 Introduction 166
7.2 Experimental Section 168
7.3 Results and Discussion 172
7.4 Conclusions 181
7.5 References 182
viii
CHAPTER 8
SYNTHESIS OF GRAPHITIC NANORIBBONS (GNRS) VIA ENCAPSULATION IN
SINGLE-WALLED ALUMINOSILICATE NANOTUBES 184
8.1 Introduction 185
8.2 Experimental Section 187
8.3 Results and Discussion 189
8.4 Conclusions 199
8.5 References 200

CHAPTER 9
CONCLUSIONS AND RECOMMENDATIONS 203
9.1 Conclusions 203
9.2 Recommendations for Future Work 207
9.2.1 Doping of Graphene 207
9.2.2 Graphene Growth 213
9.3 References 215
APPENDIX 1: SUPPORTING INFORMATION FOR EXPLORING SURFACE DIELS-
ALDER ADDUCTS ON SILICA AS A CONTROLLABLE CARBON PRECURSOR
FOR PRISTINE GRAPHENE 217

ix
LIST OF TABLES

Page

Table 1.1 Comparison of Common Graphene Production Methods................................. 10

Table 6.1. C/N ratio expected and obtained experimental via XPS analyses for: MPES,
A-MPES and B-MPES .................................................................................................... 155

Table 7-1 Single layer graphene grown on copper foil at different pressures and from
different carbon sources. ................................................................................................. 174

Table 7.2 Results from experiments of graphene growth on copper foil at 600 oC at
different pressures and from different carbon sources. ................................................... 179

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