Clemson University TigerPrints All Dissertations Dissertations 3-2010 A SOLUTION-BASED APPROACH TO THE FABRICATION OF NOVEL CHALCOGENIDE GLASS MATERIALS AND STRUCTURES Nathan Carlie Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Part of the Condensed Matter Physics Commons Recommended Citation Carlie, Nathan, "A SOLUTION-BASED APPROACH TO THE FABRICATION OF NOVEL CHALCOGENIDE GLASS MATERIALS AND STRUCTURES" (2010). All Dissertations. 554. https://tigerprints.clemson.edu/all_dissertations/554 This Dissertation is brought to you for free and open access by the Dissertations at TigerPrints. It has been accepted for inclusion in All Dissertations by an authorized administrator of TigerPrints. For more information, please contact [email protected]. A SOLUTION-BASED APPROACH TO THE FABRICATION OF NOVEL CHALCOGENIDE GLASS MATERIALS AND STRUCTURES A Dissertation Presented to the Graduate School of Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Materials Science and Engineering by Nathan A. Carlie March 29, 2010 Accepted by: Dr. Kathleen Richardson, Committee Chair Dr. Igor Luzinov Dr. Jian Luo Dr. Konstantin Kornev Mr. Norm C. Anheier i ABSTRACT Chalcogenide glasses (ChGs) are well known for their large optical nonlinearities and high infrared transparency, and are candidate materials for next-generation thin film- based planar infrared (IR) optical applications. They are also known, however, to possess low thermal and mechanical stability as compared to oxide glasses. Traditional physical vapor deposition (PVD) methods used for the deposition of these materials as thin films often suffer from low deposition rates, deviation from stoichiometry, and cannot coat over complex surfaces. In order to retain the attractive optical properties of ChGs while enabling new fabrication routes and hybrid and composite material systems, we have developed a novel technique for the deposition of ChG-based materials through dissolution of bulk glasses in organic solvents. Utilization of the solution phase allows for new deposition routes such and spin-coating and direct fabrication of ChG optical structures in a single step using micro-stamping techniques. Solution-derived thin films in the As-Ge-Sb-S system are shown to possess similar molecular structure to the parent bulk glass, and vacuum heat treatment allows the preservation of IR transparency through the removal of residual organics. Additionally it is shown that glass-polymer hybrid materials may be created through the incorporation of compatible polymers in the co- solution phase. It was shown that it is possible to tune the optical and mechanical properties of these coatings by tailoring the glass chemistry/polymer content over a broad range, important for applications in IR optical coatings and as interfacial materials where thermal and mechanical property matching is critical. This technique was shown to be a promising route towards the preparation of novel IR optical materials and structures. ii DEDICATION Above all, this work is dedicated to my forgiving wife Alison and my beautiful daughter Charlotte , who put up with all the late nights, busy weekends and general stress which result from trying to address all the myriad details that always seem to pop-up. Thank you so much for being such a great “single mom” while I’ve been lost in my work. To my parents, grandparents, and my family as whole - thank you for being by my side. Naturally, none of this would have been possible without the guidance and support of my advisor Kathleen Richardson, who has given me the opportunity to see fascinating places around the world, work with some terrific collaborators, and to choose a research topic that has been both challenging and rewarding. Dr. Laeticia Petit has worked with me as a mentor for nearly 6 years now and who, more recently with Dr. J. David Musgraves , has kept keep me focused, organized, and motivated. Without you I would have been lost long ago. Thanks to you all for keeping me on the path. Finally, I would like to thank all those who I’ve worked with over the years, at the University of Central Florida, the University of Bordeaux, the Massachusetts Institute of Technology, Pacific Northwest National Lab, my teammates and committee members and the faculty and staff of the School of Materials Science and Engineering at Clemson University. There is no such thing as a truly individual effort, and all of your contributions are appreciated. Thanks so much! iii ACKNOWLEDGMENTS I would like to acknowledge the United States Department of Energy (DoE) for partial funding of this research, which was conducted under project #DE-FG52- 06NA27502 entitled “Novel Material and Manufacturing Technology Development for a High Sensitivity, Target-Specific Planar Optical-Microsensor-Array for Remote Sensing of Chemical Species”. This project was conducted as part of a multi-university effort between Clemson University, MIT, and the University of Central Florida, and much of the work on bulk glass characterization and solution-derived glass coating development was performed as part of this project. I would also like to thank my collaborators on other aspects of this work, Dr. Georges Boudebs, at the University of Angers II in France, for performing the nonlinear optical property measurements and Norm Anheier at Pacific Northwest National Lab (PNNL) for providing the training and laboratory access to make the infrared prism coupling measurements. The novel instrument used to generate these data in this dissertation was developed during a three month internship at PNNL, and housing and laboratory space was provided during the duration. Prof. Lionel Kimerling at the MIT Microphotonics Laboratory and Dr. Michael Drews at the Clemson Conservation Center provided micro-Raman spectroscopy measurements. Finally, I would like to acknowledge the many contributions of Dr. Dave Musgraves, Dr. Bogdan Zdyrko, and especially Dr. Laeticia Petit who acted as my mentor throughout this research, and without whom it would not have been possible. iv TABLE OF CONTENTS Page TITLE PAGE .................................................................................................................... i ABSTRACT ..................................................................................................................... ii DEDICATION ................................................................................................................ iii ACKNOWLEDGMENTS .............................................................................................. iv LIST OF TABLES ......................................................................................................... vii LIST OF FIGURES ...................................................................................................... viii CHAPTER 1. Introduction .................................................................................................... 1 Motivation ................................................................................................ 1 Theoretical Background ........................................................................... 2 Potential applications ............................................................................. 11 2. Experimental ................................................................................................ 15 Sample preparation ............................................................................... 15 Physical property measurements ............................................................ 18 Thermal property measurements ............................................................ 25 Optical property measurements ............................................................. 29 Structural analysis .................................................................................. 38 3. Compositional dependence of bulk glass properties ................................... 43 Physical and thermal properties ............................................................. 44 Optical properties ................................................................................... 45 Structural characterization ..................................................................... 48 Bulk glass structure-property relationships ........................................... 59 Summary of findings.............................................................................. 63 4. Optimization of glass coating processing conditions .................................. 65 Bulk glass dissolution ........................................................................... 66 Optimization of dissolution conditions ................................................. 93 v Optimization of spin-coating conditions ............................................... 96 Optimization of the heat treatment conditions ..................................... 107 Bulk-film structural comparison .......................................................... 114 Summary of findings............................................................................ 123 5. Evaluation of novel solution-derived materials ......................................... 125 Chalcogenide glass / polymer hybrid coatings .................................... 125 Capillary force lithography .................................................................. 144 Waveguide over-cladding ...................................................................