DESIGN, SYNTHESIS, AND DEPOSITION FROM SINGLE SOURCE PRECURSORS By NATHANIEL ELBA RICHEY A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2018 © 2018 Nathaniel Elba Richey To grokking in fullness ACKNOWLEDGMENTS First and foremost, I would like to thank my advisor, Professor McElwee-White for her guidance and support throughout graduate school. Her guidance has helped me grow into an independent and critical thinker and her rigorous edits of my documents has greatly improved my scientific writing. I will greatly miss the group potlucks at her home. I would also like to thank the rest of my committee for their time and feedback on my projects. I would also like to thank my external collaborators and others who I have worked with. I would like to particularly Professor David Wei and his previous student Dr. Jingjing Qiu for their hard work on the SPMCSD of copper. I would also like to thank Dr. Eric Lambers for training me on X-ray photoelectron spectroscopy and assisting me with interpreting the data from it. I would like to thank Professor Daniel Talham and his student Sinha Khushboo for assistance in using their atomic force microscope. Finally, I would like to thank Katrina Pangilinan at the University of Tennessee Knoxville for performing the thermogravimetric analysis coupled to mass spectrometry on several of my compounds. I must also thank my many excellent group members, both past and present, for their continuous support. I would like to thank Dr. Kelsea Johnson for training me when I first joined in the summer of 2013. I would also like to acknowledge Alina Kilbert, who worked with over a summer while she was still in high school and was my first mentee as a graduate student. I would also like to thank Kevin Hamlin, Jessica Tami, and Chandler Haines for being awesome undergraduates. Duane Bock, Michelle Nolan, and Nathan Ou have greatly supported my research by helping to characterize my deposits by SEM, XRD, and Raman spectroscopy, respectively. I was privileged to work with Michelle Nolan and Alex Touchton on the deposition of tungsten carbonitride from a precursor they synthesized. I would also like to acknowledge Zahra Ali who I worked with for six months while she was visiting from Pakistan, whose high 4 energy was an invigorating change of pace. Nathan Ou has been a great help in modifying our inhouse AACVD reactor into a conventional CVD reactor. Finally, I would like to thank Will Carden, Chris Brewer, and Scot Matsuda for their stimulating discussions in lab and for simply being awesome lab mates. I must also thank all of the other friends I have made while at UF, both those inside and outside of the chemistry department. They have provided a constant route to relaxing and enjoying life outside of the lab. Last, but not least, I thank my family who have been, and continue to be, the most supportive group of people. 5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ...............................................................................................................4 LIST OF TABLES ...........................................................................................................................8 LIST OF FIGURES .......................................................................................................................10 LIST OF ABBREVIATIONS ........................................................................................................13 ABSTRACT ...................................................................................................................................14 CHAPTER 1 INTRODUCTION ..................................................................................................................16 Nanoscale Fabrication ............................................................................................................16 Precursors for Chemical Depositions .....................................................................................19 Chemical Vapor Deposition ...................................................................................................21 Surface Plasmon Mediated Chemical Solution Deposition ....................................................25 Importance of Precursor Design .............................................................................................32 2 SURFACE PLASMON MEDIATED CHEMICAL SOLUTION DEPOSITION OF COPPER .................................................................................................................................33 Copper Uses and Deposition ..................................................................................................33 SPMCSD from Adduct Stabilized Copper β-diketonates .......................................................36 SPMCSD from Copper Borohydrides ....................................................................................43 Summary of Copper Deposition from SPMCSD ....................................................................57 3 AEROSOL ASSISTED CHEMICAL VAPOR DEPOSITION OF TUNGSTEN DISULFIDE ............................................................................................................................59 Transition Metal Dichalcogenides ..........................................................................................59 Tungsten Dithiocarbamate Precursor .....................................................................................63 Dithiolene Precursors ..............................................................................................................70 Tungsten Disulfide Monolayers .............................................................................................76 Summary of WS2 Deposition..................................................................................................81 4 INTRAGROUP COLLABORATIONS .................................................................................83 Preface ....................................................................................................................................83 N,N-Disubstituted-N-acylthioureas for the Deposition of Metal Sulfides .............................83 Deposition of WCxNy using Aerosol Assisted Chemical Vapor Deposition ..........................94 Chemical Vapor Deposition of WOx from Volatile Single Source Precursors ....................101 Summary ........................................................................................................................106 6 5 EXPERIMENTAL PROCEDURES .....................................................................................107 General Considerations .........................................................................................................107 Copper Precursors .................................................................................................................108 Tungsten Sulfide Precursors .................................................................................................112 N,N-disubstituted-Nʹ-acylthiourea Ligands and Precursors .................................................113 Tungsten Carbonitride Precursor ..........................................................................................116 Deposition Procedures ..........................................................................................................117 APPENDIX A COMPOUND STRUCTURES, FORMULAS, AND NUMBERS ......................................120 B FULL X-RAY CRYSTAL STRUCTURES .........................................................................123 C FULL X-RAY TABLES.......................................................................................................125 X-ray Tables of 20 ................................................................................................................125 X-ray Tables of 22 ................................................................................................................131 X-ray Tables of 23 ................................................................................................................143 X-ray Tables of 24·NCCH3 ..................................................................................................155 D FULL TANDEM MASS SPECTRUM ................................................................................166 LIST OF REFERENCES .............................................................................................................167 BIOGRAPHICAL SKETCH .......................................................................................................183 7 LIST OF TABLES Table page 2-1 Solid-state and solution phase decomposition temperatures of the synthesized copper borohydrides ...........................................................................................................................51 4-1 Fragments from the MS-MS of 20 ..........................................................................................88 4-2 Selected X-ray crystallographic data for 20, 22, 23, 24 ..........................................................90 4-3 Selected bond distances (Å) for 20, 22, 23, 24 ........................................................................91 4-4 Selected bond angles (degrees) for 20, 22, 23, 24 ...................................................................91 4-5 Elemental composition of the deposits from 29 as determined by XPS