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University of Oklahoma UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE Structural and Optical Properties of All-Inorganic and Hybrid Organic-Inorganic Metal (M = Zn, Cd, Hg, Cu) Halides A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY In partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY By RACHEL ROCCANOVA Norman, Oklahoma 2019 STRUCTURAL AND OPTICAL PROPERTIES OF ALL-INORGANIC AND HYBRID ORGANIC-INORGANIC METAL (M = ZN, CD, HG, CU) HALIDES A DISSERTATION APPROVED FOR THE DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY BY Dr. Bayram Saparov, Chair Dr. Daniel T. Glatzhofer Dr. George Richter-Addo Dr. Robert White Dr. Ian Sellers © Copyright by RACHEL ROCCANOVA 2019 All Rights Reserved. ACKNOWLEDGEMENTS None of this work would have been possible had it not been firstly for my advisor and mentor Dr. Bayram Saparov. Without his many ideas, enthusiasm and knowledge of solid-state chemistry I would have never had the chance to learn about, grow, and study these amazing materials. The opportunities that he has provided for me throughout this process to not only grow as a scientist but as a person, is something I will be forever grateful for. A portion of this work also would have never happened had it not been for Dr. Daniel Glatzhofer providing some of his many organic molecules and willing students to assist in creating some of these wonderful materials. Secondly, I would like to thank my friends and lab family that I gained from moving all the way to Oklahoma. Without them, especially Dr. Kellye Cupp-Sutton and Dr. Matthew Houck, completing this work and program would have never been possible. Their continued support in both good and bad times always will be of great solace to me. I will also forever be grateful for my undergraduate research mentees Simon Avery Vigil, Dillon Doss, Gavin Hettler, and Max McWhorter. Thank you all for the time that you spent learning about and making new compounds with me and of course, for all the time we spent having fun in the process. Lastly, I would like to thank my parents and my husband—without whom I would not be here or have been able to complete this work. Moving half way across the country was hard for all of us, but without their continued support and encouragement none of this would have been possible. I would especially like to thank my husband, Scott, who provided the support and encouragement from the beginning to the end of this arduous journey. iv ABSTRACT All-inorganic and hybrid organic-inorganic metal halide materials, especially halide perovskites, have sparked the interest of the materials research community due to their excellent optoelectronic properties and their diverse tunable crystal structures and chemical compositions. APbX3 (A = Cs, CH3NH3; X = Cl, Br, I) perovskites prepared decades ago are today’s shining stars with CH3NH3PbI3 attracting attention as a solar cell material, and CsPbX3 and Cs4PbX6 as materials for radiation detector, display and lighting technology applications. Despite these notable achievements in the field, Pb-based perovskites suffer from lead toxicity and poor thermal, air and moisture stability which ultimately hamper their overall incorporation into marketable devices. This dissertation largely focuses on non-Pb metal halide systems that have been underexplored in literature, primarily those based on group 11 and 12 metals (Cu, Zn, Cd and Hg). Thus, in Chapter 2, a summary of the results of investigations into the structural and optical properties of the (CH3NH3)2CdX4 (X = Cl, Br, I) family is provided in which we conclude that contrary to our expectations room temperature luminescence could not be achieved in this low- dimensional family. A summary of the studies on the (C5H7N2)2MBr4 (X = Zn, Hg) family is also presented in Chapter 2, where we found that by substituting a known emissive organic cation, we could obtain materials that demonstrate room-temperature luminescence resulting from simultaneous emission from both organic and inorganic units. In Chapter 3, the incorporation of a large bulky cation in the R-M-X (R = C15H26N; M = Zn, Cd; X = Br, I) family is reported. As a result, room temperature luminescence with quantum efficiency values up to XXX was achieved. Interestingly, light emission in this family was found to originate mostly from the organic cations. In Chapter 4, we show that the concept of dimensional reduction can also be applied to all- inorganic halides with the preparation and characterization of compounds in the CsX-CuX (X = v Cl, Br, I) systems. Notable, the obtained materials include Cs3Cu2I5 that demonstrates a near-unity quantum efficiency blue emission at room temperature. Finally, the dissertation is concluded in Chapter 5 with a discussion of possible future directions. vi Table of Contents Chapter 1: Introduction to Luminescent Low-Dimensional Metal Halides.................................... 1 1.1 Introduction ...................................................................................................................... 1 1.2 Crystal Structures of Low-Dimensional Halides ............................................................. 5 1.2.1 Three-Dimensional Parent Structure ......................................................................... 5 1.2.2 Lower-Dimensional Perovskite-Derived Structures ................................................. 9 1.2.2.1 Two-Dimensional Perovskite Derivative Structures ............................................. 10 1.2.2.2 One- and Zero-Dimensional Perovskite Derivative Structures ............................. 13 1.3 Optical Properties of Low-Dimensional Metal Halides ................................................. 15 1.3.1 Electronic Band Structures ..................................................................................... 15 1.3.2 Electronic Density of States and Quantum Confinement ....................................... 18 1.3.3 Luminescence in Low-Dimensional Metal Halides ................................................ 22 1.3.3.1 Band-to-Band Absorption and the Concept of an Exciton .................................... 22 1.3.3.2 Elementary Excitons and the Effects of Quantum Confinement ........................... 23 1.3.3.2.1 Wannier-Mott and Frenkel Excitons ....................................................................... 23 1.3.4 Photoluminescence of Low-Dimensional Halides ................................................. 27 1.3.4.1 Self-trapped Excitons ............................................................................................. 29 1.4 Applications of Luminescence Metal Halides ............................................................... 34 1.4.1 Phosphors ................................................................................................................ 37 1.4.2 Light Emitting Diodes (LEDs)................................................................................ 40 1.4.3 Scintillators ............................................................................................................. 42 1.5 Beyond Lead Halide Perovskites ................................................................................... 45 1.5.1 Bismuth and Antimony Based Metal Halides ......................................................... 46 1.5.2 Alternative Non-Pb Metal Halides .......................................................................... 47 Chapter 2: Size Effects in Hybrid Group 12 Metal Halides ......................................................... 53 2.1 Methylammonium Cadmium Halides MA2CdX4 (X = Cl, Br, I) ....................................... 54 2.1.1 Introduction ............................................................................................................. 54 2.1.2 Synthesis and Methods of MA2CdX4 (MA = CH3NH3; X = Cl, Br, I) ................... 57 2.1.2.1 Reactants ................................................................................................................ 57 2.1.2.2 MABr and MAI Synthesis ..................................................................................... 57 2.1.2.3 MA2CdX4 Synthesis and Single Crystal Growth .................................................. 57 vii 2.1.2.4 Powder X-ray diffraction ....................................................................................... 58 2.1.2.5 Single Crystal X-ray diffraction............................................................................. 59 2.1.2.6 UV-vis Absorbance Measurements ....................................................................... 60 2.1.2.7 Variable Temperature Photoluminescence Measurements .................................... 60 2.1.2.8 Electronic Structure Calculations .......................................................................... 61 2.1.3 Room Temperature Crystal Structures ......................................................................... 61 2.1.4 Variable Temperature X-ray Diffraction Studies ................................................... 66 2.1.4.1 MA2CdCl4 .............................................................................................................. 67 2.1.4.2 MA2CdBr4 and MA2CdI4 ....................................................................................... 68 2.1.5 Air and Moisture Stability ...................................................................................... 70 2.1.6 Optical Property Measurements .............................................................................. 73 2.1.7 Band Structure Calculations ..................................................................................
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