Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2011 Application of Scanning Probe Microscopy for New Physical Measurements and Studies of Surface Chemical Reactions of Materials at the Molecular Level Stephanie Loletha Daniels Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Daniels, Stephanie Loletha, "Application of Scanning Probe Microscopy for New Physical Measurements and Studies of Surface Chemical Reactions of Materials at the Molecular Level" (2011). LSU Doctoral Dissertations. 4028. https://digitalcommons.lsu.edu/gradschool_dissertations/4028 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. APPLICATION OF SCANNING PROBE MICROSCOPY FOR NEW PHYSICAL MEASUREMENTS AND STUDIES OF SURFACE CHEMICAL REACTIONS OF MATERIALS AT THE MOLECULAR LEVEL A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Stephanie Loletha Daniels B.S., Jackson State University, 2004 M.S., Jackson State University, 2006 May 2011 DEDICATION This dissertation is dedicated to my mother, Delois Daniels, my sister, Melanie Daniels, nephew Darian Hearn, and to my family and friends who have been on this incredible journey with me. I sincerely thank you for your love and support. ii ACKNOWLEDGEMENTS This dissertation would not have been possible without the support, love and encouragement of many people. I thank GOD for giving me the strength to endure and see my dreams come true. To my mother, Delois and my sister, Melanie, I cannot express my gratitude enough for your unwavering love, patience and support throughout this process. This work would not have been possible without you and for that reason; I am forever indebted to my family. Thank you for your encouraging words when I needed them most. Most of all, thank you for always believing in me. I would like to thank my research advisor and mentor, Dr. Jayne C. Garno, for her guidance, patience, words of encouragement and belief in my abilities throughout my studies at Louisiana State University. I am grateful for the opportunity to have worked in your research group. Your mentorship has helped to shape me into the scientist I am today. I appreciate the valuable feedback and discussions with my committee members, Dr. Kermit K. Murray, Dr. Isiah Warner, Dr. Les Butler, and Dr. Georgios Veronis. I am thankful to Dr. Darren Lytle, my supervisor at the U.S. Environmental Protection Agency in Cincinnati, OH. I appreciate your guidance during and after my internship. I would also like to acknowledge the staff and my colleagues at the EPA for making me feel at home while in Cincinnati. Finally, I thank my colleagues in the Garno Research group, past and present. To Dr. Johnpeter Ngunjiri, Wilson Serem, Kathie Lusker and Dr. Zorabelle LeJeune, I greatly appreciate your friendship and I will always remember and cherish the great times we spent with each other. iii TABLE OF CONTENTS DEDICATION ................................................................................................................................ ii ACKNOWLEDGEMENTS ........................................................................................................... iii LIST OF TABLES ........................................................................................................................ vii LIST OF FIGURES ..................................................................................................................... viii LIST OF ABBREVIATIONS ........................................................................................................ xi ABSTRACT ................................................................................................................................. xiii CHAPTER 1. INTRODUCTION ...................................................................................................1 1.1 Scanning Probe Microscopy ...............................................................................................1 1.2 Ferritin as a Model System for Scanning Probe Microscopy Characterizations ................................................................................................................2 1.3 A New Magnetic AFM Mode for Detecting the Vibrational Response of Nanomaterials .....................................................................................................................3 1.4 Characterization of the Superparamagnetic Properties of Ferritin Microstructures by Contact-mode AFM Combined with MSM-AFM ..............................3 1.5 Fabrication of Patterned Surfaces with Particle Lithography .............................................4 1.6 Studying Copper Corrosion Phenomena at the Nanoscale with AFM ...............................4 1.7 Summary and Future Prospectus ........................................................................................6 CHAPTER 2. EXPERIMENTAL APPROACH: IMAGING PRINCIPLES AND MODES OF SCANNING PROBE MICROSCOPY (SPM) ................................................................................7 2.1 History of Scanning Probe Microscopy ..............................................................................7 2.2 Basic Imaging Principle for SPM .......................................................................................8 2.3 Contact and Lateral Force Modes of AFM ........................................................................10 2.3.1 Force Distance Measurements .....................................................................................13 2.4 Tapping Mode and Phase Imaging AFM ...........................................................................15 2.5 Current Sensing AFM and I-V Measurements ..................................................................17 2.6 Magnetic Sample Modulation AFM ..................................................................................18 2.7 SPM Imaging Modes Used for Dissertation Research ......................................................19 CHAPTER 3. FERRITIN AS A MODEL NANOMATERIAL: NANOLITHOGRAPHY AND SCANNING PROBE MICROSCOPY STUDIES ..........................................................................................................................21 3.1 Introduction .......................................................................................................................21 3.2 Molecularly Resolved Characterizations of Ferritin and Apoferritin ...............................21 3.2.1 Electron Microscopy Studies.. .....................................................................................22 3.2.2 Scanning Probe Microscopy Studies of Ferritin at the Molecular Level .....................23 3.3 Lithography Approaches for Controlling the Surface Arrangement of Ferritin ..............................................................................................................................26 iv 3.3.1 Applications of Scanning Probe Lithography to Produce Nanopatterns of Ferritin .....................................................................................................................27 3.3.2 Nanostructures of Ferritin Produced by Surface Selectivity ........................................29 3.3.3 Patterning of Ferritin Using Particle Lithography .......................................................31 3.4 Physical Properties of Ferritin Investigated with AFM ....................................................32 3.4.1 Mechanical Properties-Force Spectroscopy Studies with AFM ................................32 3.4.2 Conductive Probe Studies with Ferritin .......................................................................34 3.4.3 Magnetic Measurements of Ferritin Using SPM .........................................................35 3.5 Ferritin as a Vessel for Biomineralization ........................................................................38 3.6 Future Technologies Based on Ferritin-Derived Nanostructures .....................................39 3.7 Conclusion and Prospectus ...............................................................................................40 CHAPTER 4. CHARACTERIZATION OF FERRITIN MICROSTRUCTURES WITH MAGNETIC SAMPLE MODULATION AFM ...................................................41 4.1 Introduction .......................................................................................................................41 4.2 Experimental Approach ....................................................................................................42 4.2.1 Materials and Reagents ................................................................................................42 4.2.2 Procedure for Micropatterning Ferritin by Capillary Filling of PDMS Molds ..........................................................................................................................43 4.2.3 Atomic Force Microscopy ...........................................................................................43 4.2.4 Basic Principle