University of Central Florida STARS Electronic Theses and Dissertations, 2004-2019 2016 Design of surface chemical reactivity and optical properties in glasses Antoine Lepicard University of Central Florida Part of the Engineering Science and Materials Commons Find similar works at: https://stars.library.ucf.edu/etd University of Central Florida Libraries http://library.ucf.edu This Doctoral Dissertation (Open Access) is brought to you for free and open access by STARS. It has been accepted for inclusion in Electronic Theses and Dissertations, 2004-2019 by an authorized administrator of STARS. For more information, please contact [email protected]. STARS Citation Lepicard, Antoine, "Design of surface chemical reactivity and optical properties in glasses" (2016). Electronic Theses and Dissertations, 2004-2019. 5264. https://stars.library.ucf.edu/etd/5264 DESIGN OF SURFACE CHEMICAL REACTIVITY AND OPTICAL PROPERTIES IN GLASSES by ANTOINE M.J. LEPICARD M.S. ENSCI, FRANCE, 2013 A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Materials Science and Engineering in the College of Engineering and Computer Science at the University of Central Florida Orlando, Florida Fall Term 2016 Major Professor: Kathleen A. Richardson ABSTRACT Thermal poling is a technique which involves the application of a strong DC electric field to a glass substrate heated below its glass transition temperature (Tg). Following the treatment, a static electric field is frozen inside the glass matrix, effectively breaking its centrosymmetry. Historically, this treatment has been used as a way to gain access to second order non-linear optical properties in glasses. However, recent efforts have shown that the treatment was responsible for structural changes as well as surface property modifications. Our study was focused on using this technique to tailor surface properties in oxide (borosilicate and niobium borophosphate) and chalcogenide glasses. A strong emphasis was put on trying to control all changes at the micrometric scale. After poling, property changes were assessed using a set of characterization tools: the Maker fringes technique (a Second Harmonic Generation ellipsometry technique), micro-Second Harmonic Generation (µ-SHG), vibrational spectroscopy and Secondary Ion Mass Spectroscopy (SIMS). Surface reactivity in borosilicate glasses was effectively changed while in niobium borophosphate and chalcogenide glasses, the optical properties were controlled linearly and non- linearly. Finally, property changes were effectively controlled at the micrometric scale. This opens up new applications of thermal poling as a mean to design glass substrate for integrated photonics and lab-on-a-chip devices. ii ACKNOWLEDGMENTS This work has been done through a co-tutelle program between France and the USA. I would first like to thank my advisors Dr. Marc Dussauze, Dr. Kathleen Richardson and Dr. Vincent Rodriguez who have given me this opportunity. I thank you for your availability and for all of your advice over these three years. I would also like to thank all of my collaborators in France and in the USA, especially Dr. Thierry Cardinal at ICMCB Bordeaux for welcoming me in his group for the preparation of some of my glasses and who has shared his knowledge of glass science with me. Mikhail Klimov at UCF for the time he has spent for SIMS measurements on my samples. I would also like to thank all of the members of the Molecular Spectroscopy Group in Bordeaux. It was a real pleasure to work with you during this PhD. Especially, I would like to thank Frédéric Adamietz, without whom lots of the results presented in this dissertation would have been hard to obtain. I wish to also thank Flavie Bondu with whom I have liked working on thermal poling. I thank Matthieu Chafer, former intern with Marc Dussauze, who has contributed to the work on BPN glasses. I would also like to thank all members or former members of the GPCL group in UCF, Benn, James, Andy, Charmayne, Jason, Devon, Erick, Laura, Karima, Spencer, Becca and all the others. I have liked working with you and I thank you for showing me the American way of life! I would like to thank my parents, brother and sisters for their continuous support during my time shared between two continents. Finally, I would like to especially thank Elise who has supported me and made my life easier during these years of PhD. Now is time for new adventures! iii TABLE OF CONTENTS LIST OF FIGURES ..................................................................................................................... viii LIST OF TABLES ....................................................................................................................... xiii CHAPTER 1: INTRODUCTION ................................................................................................... 1 1.1 How to break a glass’s centrosymmetry? .............................................................................. 4 1.1.1 Optical poling ................................................................................................................. 5 1.1.2 Corona poling ................................................................................................................. 6 1.1.3 Thermal poling ............................................................................................................... 6 1.2 Introduction to second order nonlinear optics ....................................................................... 8 1.2.1 Light to matter interaction and the concept of polarization ............................................ 8 1.2.2 The effect of symmetry on the χ(2) tensor ..................................................................... 13 1.2.3 Origin of the induced SONL properties in poled glasses ............................................. 14 1.2.4 Phase matching conditions ........................................................................................... 15 1.3 Second Harmonic Generation in Silica glass ...................................................................... 18 1.4 Thermal poling of alkali-rich glasses .................................................................................. 21 1.5 Second Harmonic Generation in chalcogenide glasses ....................................................... 26 1.6 Applications of thermal poling ............................................................................................ 30 1.6.1 Microelectronics: the first use of thermal poling.......................................................... 31 1.6.2 Electro-optics ................................................................................................................ 32 1.6.3 Thermal poling as an imprinting process ..................................................................... 37 1.6.4 Use of the electric field to enhance chemical properties .............................................. 38 1.7 References ........................................................................................................................... 41 CHAPTER 2: INSTRUMENTS AND EXPERIMENTAL TECHNIQUES ................................ 51 2.1 Glass synthesis .................................................................................................................... 51 2.1.1 Borosilicate glasses....................................................................................................... 51 2.1.2 Chalcogenide glasses .................................................................................................... 51 2.2 Differential Scanning calorimetry ....................................................................................... 53 iv 2.3 Density measurements......................................................................................................... 54 2.4 Measurements of the refractive index using Brewster’s angle and the M-lines ................. 55 2.5 Thermal poling of the glass sample: description of the poling cell .................................... 58 2.6 Structuring electrodes for thermal poling............................................................................ 60 2.7 Measurements of the SHG response by mean of the Maker fringes ................................... 60 2.8 Optical spectroscopy ........................................................................................................... 65 2.8.1 Infrared spectroscopy ................................................................................................... 66 2.8.2 Ultraviolet-visible spectroscopy ................................................................................... 69 2.8.3 Raman spectroscopy and correlative μ-SHG mapping ................................................. 70 2.9 Atomic Force Microscopy ................................................................................................... 73 2.10 Electron Microprobe Analysis .......................................................................................... 76 2.11 Secondary Ion Mass Spectrometry .................................................................................... 77 2.12 References ......................................................................................................................... 79 CHAPTER 3: MICRO-POLING OF A NIOBIUM BOROPHOSPHATE GLASS: A WAY TO CONTROL THE 2ND ORDER NONLINEAR OPTICAL PROPERTIES AT THE MICROMETRIC SCALE ............................................................................................................