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Clemson University TigerPrints All Dissertations Dissertations 12-2015 TOWARDS A GREATER UNDERSTANDING OF HYDROTHERMALLY GROWN GARNETS AND SESQUIOXIDE CRYSTALS FOR LASER APPLICATIONS Cheryl Moore Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Part of the Chemistry Commons Recommended Citation Moore, Cheryl, "TOWARDS A GREATER UNDERSTANDING OF HYDROTHERMALLY GROWN GARNETS AND SESQUIOXIDE CRYSTALS FOR LASER APPLICATIONS" (2015). All Dissertations. 1604. https://tigerprints.clemson.edu/all_dissertations/1604 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]. TOWARDS A GREATER UNDERSTANDING OF HYDROTHERMALLY GROWN GARNETS AND SESQUIOXIDE CRYSTALS FOR LASER APPLICATIONS A Dissertation Presented to the Graduate School of Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Chemistry by Cheryl Ann Moore December 2015 Accepted by: Joseph W. Kolis, Committee Chair John Ballato William T. Pennington Andrew G. Tennyson ABSTRACT The hydrothermal method of crystal growth offers many benefits over traditional melt-based techniques such as lower temperature requirements relieving detrimental high temperature effects such as stress fracturing and a closed-environment, which limits impurities. The continued study of this type of growth including hydrothermal epitaxy is crucial in our world of constant miniaturization. Presented in this thesis is the hydrothermal growth of crystals of LuAG and Lu 2O3 doped with a variety of dopants. Their room-temperature and cryogenic absorption spectra are also presented. Much like Nature uses heat, pressure, water and a nutrient-rich feedstock we have used this hydrothermal technique to produce synthetic crystals of grossular, Ca 3Al 2(SiO 4)3, a naturally occurring garnet as well as other aluminosilicates related to grossular, including a new type of vesuvianite. Other garnets important to the laser industry have also been grown using the hydrothermal technique, such as yttrium aluminum garnet (YAG), lutetium aluminum garnet (LuAG) and the related sesquioxide Lu 2O3, (lutetia). The growth and characteristics of Yb-doped lutetia and LuAG, Nd-doped lutetia, and Dy-doped lutetia and YAG are presented herein. These laser crystals have been analyzed by high-resolution absorption spectroscopy at room temperature as well as 250K, 200K, 150K and 80K and absorption coefficients are presented. A coprecipitation technique common in the ceramics field has been adapted for use creating precursors for hydrothermal crystal growth, including phase-pure ii polycrystalline anorthite and phase-pure gehlenite. Coprecipitation has also been utilized to gain greater control of dopants to create pre-doped feedstocks used for the growth of laser crystal. The versatility of the hydrothermal growth method is also highlighted in a novel epitaxial technique, core growth, which coats the internal surfaces of a seed crystal as well as external surfaces. This can result in multifunctional, layered crystals with no additional size, suitable for applications in need of constant miniaturization demanded by today’s industries. iii DEDICATION I would like to dedicate this work to the memory of Georgia Louise Thomas Jackley and Kenneth Rudolph Thomas. We did it! iv ACKNOWLEDGMENTS While writing a dissertation can be an extremely personal experience, to stop there would be to overlook so many people integral to the process and, without whom, this manuscript would not exist. First and foremost I must thank Clemson University, the Department of Chemistry, and specifically the Kolis research group for offering me the opportunity to study here. Chance may have ultimately landed me here, but I call it luck. Thank you to Dr. David C. Brown and everybody at Snake Creek Lasers, L.L.C. for taking me in and allowing me to walk beside you for this short time; you are some of the most amazing people I’ve ever met. Thank you especially to Lisa Vitali for helping me find my sanity when I almost lost it. I would like to extend my deepest gratitude to the following people for their part in this work either directly or indirectly. To Kyle Fulle for being my right hand and sometimes my left hand, too. To Dr. Duminda Sanjeewa for opening to me a whole new world of lutetia and who has grown some of the most beautiful SN crystals I have seen. To Barbara Lewis for encouraging me when I was so ready to quit. You will never know what your kind words meant and mean to me still. To Craig Goodman for our countless hours of brainstorming. Ideas always seem to make more sense after they bounce off of you. To Dr. Colin D. McMillen. You taught me everything I know about crystal growth and reminded me of the importance of family when I really needed it. But most of all I’d like to thank Dr. Joseph Kolis for, among other things, guiding and supporting me when I v needed it most and giving me the latitude to stray from the beaten path occasionally. Who knows where in the world I would be without you. Literally. vi TABLE OF CONTENTS Page TITLE PAGE .................................................................................................................... i ABSTRACT ..................................................................................................................... ii DEDICATION ................................................................................................................ iv ACKNOWLEDGMENTS ............................................................................................... v LIST OF TABLES .......................................................................................................... xi LIST OF FIGURES ...................................................................................................... xiii CHAPTER I. CRYSTALS, CRYSTAL GROWTH, AND LASERS .................................. 1 Methods of crystal growth ....................................................................... 2 Hydrothermal Crystal Growth ................................................................. 9 Growth by spontaneously nucleation ..................................................... 10 Hydrothermal epitaxial growth .............................................................. 13 Interaction of light with matter .............................................................. 14 Lasers and Laser Crystals ...................................................................... 17 Garnets as hosts...................................................................................... 19 Sesquioxides as hosts ............................................................................. 22 Laser active ions .................................................................................... 23 II. EXPERIMENTAL METHODS AND TECHNIQUES OF ANALYSIS .... 28 Growth by spontaneous nucleation ........................................................ 28 Hydrothermal epitaxial growth .............................................................. 28 SN of Doped Lutetia Crystals ................................................................ 30 Transport Growth and Epitaxy............................................................... 31 Pre-doping feedstock for greater control of dopant ............................... 38 Powder pattern matching ....................................................................... 39 Lattice parameter matching .................................................................... 42 Elemental analysis by Energy Dispersive X-ray ................................... 47 Index matching by single-crystal diffractometry (XRD) ....................... 50 vii Table of Contents (Continued) Chapter Page III. LuAG ........................................................................................................... 51 Hydrothermal crystal growth ................................................................. 52 Growth of Ga:LuAG .............................................................................. 55 Nd:LuAG ............................................................................................... 57 Yb:LuAG ............................................................................................... 61 Ho:LuAG ............................................................................................... 65 Tm:LuAG ............................................................................................... 67 Er:LuAG ................................................................................................ 69 Pr:LuAG ................................................................................................. 71 Ce:LuAG ................................................................................................ 73 Sm:LuAG ............................................................................................... 75 IV. EXPLORATION OF NATURAL GARNET .............................................. 78 Grossular Garnet .................................................................................... 78 Crystal Growth ....................................................................................... 80 Attempted synthesis of grossular from components .............................. 81 Synthesis of dellaite single-crystals ......................................................
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