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Alkaline Earth Metal Fluxes for the Growth of Single Crystal Oxides

Title: Alkaline Earth Metal Fluxes for the Growth of Single Crystal Oxides.
Name(s): Ramirez, Daniel, author
Siegrist, Theo M., professor directing thesis
Hellstrom, Eric, committee member
Liang, Zhiyong Richard, committee member
Florida State University, degree granting institution
Graduate School, degree granting college
Program in Materials Science, degree granting department
Type of Resource: text
Genre: Text
Issuance: monographic
Date Issued: 2016
Publisher: Florida State University
Florida State University
Place of Publication: Tallahassee, Florida
Physical Form: computer
online resource
Extent: 1 online resource (71 pages)
Language(s): English
Abstract/Description: Oxide ceramics are materials with a wide range of properties. Insulators are most common, however semiconductors, strongly correlated electron materials, and even superconductors are all relevant oxide materials. Here we seek to synthesize novel oxide single crystal phases and study their properties using an alkaline earth metal flux technique. The specific flux techniques are new, and we will seek to understand the capabilities of these fluxes as a novel synthesis tool. The use of a barium metal flux to grow single crystal oxides is rather counterintuitive, but is exemplified further with the growth of europium monoxide (Fm3 #225, Z = 4). Eu₁₋xBaxO single crystals (x = 0.01 – 0.25) are grown and studied for their ferromagnetic properties. A new oxide phase Ba₂Eu₂P₂O (P4/mbm #127, Z = 2) has also been synthesized from the same method, and may potentially be studied as a ferromagnetic semiconductor based on preliminary observations. Other examples of single crystal oxide phases grown from barium metal flux includes Ba₂TeO (P4/nmm #129, Z = 2), BaLn₂O₄(Ln = La – Lu) (Pnma #62, Z = 4), and Ba₃Yb₂O₅Te (P4/mmm #123 Z = 1). The new crystal phases Ba₃Ln₂O₅Cl₂ (Ln = Sm – Lu, Y) are synthesized using a reactive barium metal flux. Single crystal x-ray diffraction is used to determine their structures with space group (I4/mmm #139, Z = 2) related to the Ruddlesden-Popper structure type. The unit cell dimensions range from a = 4.46(6) Å and c = 24.87(6) Å for Ba₃Gd₂O₅Cl₂ to a = 4.35(6) Å and c = 24.57(6) Å for Ba₃Lu₂O₅Cl₂ with the dimensions following the expected lanthanide contraction trends. The magnetic properties of these materials are studied and related to their structures. The use of alkaline earth fluxes such as magnesium or calcium based fluxes are also briefly considered for their capabilities to produce novel mixed anion phases. A calcium flux is shown to produce the novel semimetals Ca₄TeOH₄ and Ca₃Ca₁₋xEuxTeOH₄ (I4/mmm #139, Z = 2), and highly reducing magnesium fluxes are shown to produce the divalent samarium Zintl phases SmMg₂Bi₂ and SmMg₂Sb₂ (P3m1 #163, Z = 1).
Identifier: FSU_2016SU_Ramirez_fsu_0071N_13312 (IID)
Submitted Note: A Thesis submitted to the Program in Materials Science and Engineering in partial fulfillment of the requirements for the degree of Master of Science.
Degree Awarded: Spring Semester 2016.
Date of Defense: April 21, 2016.
Bibliography Note: Includes bibliographical references.
Advisory Committee: Theo M. Siegrist, Professor Directing Thesis; Eric Hellstrom, Committee Member; Zhiyong (Richard) Liang, Committee Member.
Subject(s): Materials science
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Host Institution: FSU

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Ramirez, D. (2016). Alkaline Earth Metal Fluxes for the Growth of Single Crystal Oxides. Retrieved from