ABSTRACT Title of Dissertation: NITROGEN-VACANCY COUPLING IN NANODIAMOND HYBRID NANOSTRUCTURES Nathaniel Steinsultz, Doctor of Philosophy, 2017 Dissertation directed by: Associate Professor, Min Ouyang, Department of Physics Nitrogen-vacancy centers (NVs) are an atomic defect in diamond which possess remarkable fluorescence and spin properties which can be used for multiple metrological applications, particularly when the NV is hosted in nanodiamond, which can be easily integrated with a variety of nanoscale systems. A new class of nanodiamond hybrid nanostructures was developed using bottom-up synthesis methods. In this work, coupling between NV centers and plasmonic, excitonic and magnetic nanoparticles in these nanodiamond hybrid nanostructures is investigated using fluorescence lifetime measurements, spin relaxometry measurements and modeled using finite element method (FEM) and Monte Carlo simulations. This work not only characterizes the properties of these nanodiamond-hybrid nanostructures but also facilitates design guidelines for future hybrid structures with enhanced metrological and imaging capabilities. NITROGEN-VACANCY COUPLING IN NANODIAMOND HYBRID NANOSTRUCTURES by Nathaniel Steinsultz Dissertation submitted to the Faculty of the Graduate School of the University of Maryland, College Park, in partial fulfillment of the requirements for the degree of Doctor of Philosophy 2017 Advisory Committee: Professor Min Ouyang, Chair Professor Steven Anlage Professor Luis Orozco Professor Chris Lobb Professor John Cumings, Dean’s Representative © Copyright by Nathaniel Steinsultz 2017 Dedication All praises to The Grey Fox, who has given us life and seed in these dreary lands, under the shadow of the shadow of the mountain which devours all warmths ii Acknowledgements There are many people who I would like to thank for their academic and personal support throughout my graduate career. I’d also like to acknowledge the University of Maryland and the National Science Foundation for the financial support which made this work possible. I’d like to thank my advisor Min Ouyang for his guidance and support and providing me with the real opportunity to tackle challenging research problems. I also owe a great deal of gratitude to the members of the Ouyang group: Shangjie Yu, Geng Li, Pengpeng Wang and, particularly, Jinxiao Gong. Without her work in material synthesis and TEM characterization, none of this research would have been possible. I’d also like to thank all the members of my dissertation committee for contributing their time to review this thesis. One of the wonders of the University of Maryland is the large physics community and I have been fortunate to work with many great people. I’d like to thank Bob Anderson and Steve Anlage for loaning equipment and expertise in magnetic coil and microwave design, respectively. I appreciate all the support I have received in navigating university bureaucracies from Mary Sutton, Jane Hessing and Jessica Crosby. I have grown up considerably, both academically and personally, since beginning graduate school, and I owe that growth to a great many people who I have met while in Maryland. Thank you to Rich Knoche, Young Ho Shin, Ryan Maunu, Jack Wimberly and Chris Schroeder who helped me navigate that first year of grad school and beyond. Thank you to Jimmy Juno, Liz Friedman and Zach Eldredge for their superior iii contributions while I served on graduate committee. Thank you to Jeff, Joe, George and Neil for indulging my musical obsessions. Thanks to my solemate, Emmelia, and everyone else from MUUSA who have given me the necessary energy to carry forward when the work felt too heavy. There is no way that I could have survived the challenges of graduate school without the support and friendship from George, Joe, Kevin, Kiersten, Ginny, Neil, Meredith, Alireza and Rachel in everything over the past few years including Physics House, CCCP, RJUVC, Aul Graeve and beyond. Thank you for all the food, pickles, parties, trips and more. When I first started at UMD, I was certain I’d only live with you temporarily but now I can’t imagine what my life would have been like without you. I owe everything to my partner, Meredith, who has been incredibly supportive and who grounds me when I get too carried away. She has been there for me for most my life and I would not be the person I am now without her support. Finally, I would like to thank my mom and dad who have always supported me and provided me with the opportunities to learn and grow that made graduate school possible. iv Table of Contents Dedication .......................................................................................................... ii Acknowledgements .................................................................................................... iii Table of Contents .........................................................................................................v List of Tables ........................................................................................................ vii List of Figures ....................................................................................................... viii List of Abbreviations ............................................................................................... xvi Chapter 1 Nitrogen-Vacancy Centers: Properties and Applications ...........1 1.1 Introduction ...................................................................................... 1 1.2 NV Properties ................................................................................... 2 1.3 NV Spin Coherence .......................................................................... 8 1.4 NV Magnetometry .......................................................................... 11 1.5 NV as a Quantum Emitter .............................................................. 17 1.6 NV Based Hybrid Structures .......................................................... 20 1.7 Thesis Overview and Structure ...................................................... 23 Chapter 2 Experimental Apparatus and Nanodiamond Spin Characterization ............................................................................27 2.1 Laser Scanning Confocal Microscopy ........................................... 29 2.2 Time Correlated Single Photon Counting ...................................... 34 2.3 Fluorescence Lifetime Measurements ............................................ 37 2.4 Microwave Source and Antenna .................................................... 41 2.5 Sample Stage and External Magnetic Field ................................... 45 2.6 Optically Detected Magnetic Resonance ....................................... 47 2.7 Pulsed Magnetometry Techniques ................................................. 48 2.8 Conclusion ...................................................................................... 62 Chapter 3 Plasmonic Modification of the Fluorescence Lifetime in Nanodiamond Based Hybrid Nanostructures .............................63 3.1 Introduction .................................................................................... 63 3.2 Effects of Local Surface Plasmon Resonance on Fluorescence Decay Rates .................................................................................... 65 3.3 Synthesis of ND based hybrid nanostructures ................................ 67 3.4 Fluorescence modification in ND based hybrid nanostructures. .... 73 3.5 Aggregated Lifetime Measurements of Metal Nanoparticle- Nanodiamond Hybrid Structures .................................................... 82 3.6 Conclusion ...................................................................................... 86 Chapter 4 Modeling and Simulations of Nanodiamond-Based Hybrid Nanostructures ...............................................................................88 4.1 Introduction .................................................................................... 88 v 4.2 Nanodiamond Properties ................................................................ 91 4.3 Finite Element Method Modelling of Plasmonic Fluorescence Modification ................................................................................... 95 4.4 Monte Carlo Simulations of Aggregate Fluorescence Behavior .. 108 4.5 Förster Resonant Energy Transfer Between NV Centers and Quantum Dots ............................................................................... 113 4.6 Conclusion .................................................................................... 119 Chapter 5 Magnetic Noise Spectroscopy of Superparamagnetic Nanoparticles ...............................................................................121 5.1 Superparamagnetic Iron Oxide Nanoparticles ............................. 121 5.2 NV Center Based Quantum Noise Spectroscopy ......................... 128 5.3 Investigating Magnetic Noise with Nanodiamond-SPION Hybrid Nanostructures .............................................................................. 135 5.4 Directions for Future Investigation .............................................. 149 5.5 Conclusion .................................................................................... 152 Chapter 6 Conclusion and Outlook .............................................................153 Appendix A: FEM Results .................................................................................157 Bibliography .......................................................................................................164