University of Groningen
Magnetic order from molecular oxygen anions
Riyadi, Syarif
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2012
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Riyadi, S. (2012). Magnetic order from molecular oxygen anions Groningen: s.n.
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Magnetic Order from Molecular Oxygen Anions
Cover: Illustration of the dioxygen dumbbells (front) and Molecular orbital diagram
of dioxygen species (back)
Cover design by Syarif Riyadi
The work described in this thesis was performed in the group Solid State Materials for Electronics (part of the Zernike Institute for Advanced Materials) of
the University of Groningen, The Netherlands, and is supported partly by VIDI
fellowship from the Dutch National Organization (NWO).
c
Copyright ⃝2011
S. Riyadi. All rights reserved.
Printed by: Offpage, Amsterdam. www.offpage.nl
Zernike Institute for Advanced Materials PhD thesis series 2012-10
ISSN 1570-1530
ISBN: 978-90-367-5450-7 (paper version)
ISBN: 978-90-367-5451-4 (electronic version)
RIJKSUNIVERSITEIT GRONINGEN
Magnetic Order from Molecular Oxygen Anions
Proefschrift
ter verkrijging van het doctoraat in de
Wiskunde en Natuurwetenschappen
aan de Rijksuniversiteit Groningen
op gezag van de
Rector Magnificus, dr. E. Sterken,
in het openbaar te verdedigen op
vrijdag 4 mei 2012
om 11.00 uur
door
Syarif Riyadi
geboren op 21 december 1980
te Bandung, Indonesië
Promotores:
Prof. dr. T.T.M. Palstra
Prof. dr. R.A. de Groot
Copromotor:
Dr. G.R. Blake
Beoordelingscommissie:
Prof. dr. ir. P.H.M. van Loosdrecht
Prof. dr. A. Damascelli
Prof. dr. C. Felser
Untuk
Mama & Papa
ii
Contents
1 Introduction
1.1 General Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Alkali Metal Oxides and their Properties . . . . . . . . . . . . . . .
1.2.1 Molecular Oxygen Species and Alkali Metal Oxide Compounds
1.2.2 Phase Transitions in Alkali Metal Superoxides . . . . . . .
1.3 Magnetic Interactions and Magnetic Order in Solids . . . . . . . .
1.3.1 Spin Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.2 Low-Dimensional Magnets . . . . . . . . . . . . . . . . . . .
1.4 Magnetic Properties of Alkali Metal Oxides . . . . . . . . . . . . .
1.4.1 Magnetic Exchange Interactions in Alkali Metal Superoxides
1.4.2 Magnetogyration . . . . . . . . . . . . . . . . . . . . . . . .
1.4.3 Field-induced Transitions . . . . . . . . . . . . . . . . . . .
1.5 Motivation and Outline of the Thesis . . . . . . . . . . . . . . . . .
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Bibliography
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2 Synthesis and Characterization
2.1 Sample Handling and Preparations . . . . . . . . . . . . . . . . . .
2.1.1 Oxidation of Alkali Metal-Liquid Ammonia Solution . . . .
2.1.2 Direct Oxidation of Alkali Metals . . . . . . . . . . . . . . .
2.1.3 Thermal Decomposition . . . . . . . . . . . . . . . . . . . .
2.2 Phase Analysis and Structural Characterization . . . . . . . . . . .
2.2.1 X-Ray Powder Diffraction . . . . . . . . . . . . . . . . . . .
2.2.2 Neutron Diffraction . . . . . . . . . . . . . . . . . . . . . .
2.3 Physical and Chemical Properties . . . . . . . . . . . . . . . . . . .
2.3.1 Magnetization Measurements . . . . . . . . . . . . . . . . .
2.3.2 Differential Scanning Calorimetry-Thermogravimetric Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.3 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . .
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Contents
2.4
Thin Film Deposition . . . . . . . . . . . . . . . . . . . . . . . . .
Bibliography
33
3 Rubidium Oxides: Phase Diagram and Cooling-rate Effect
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Rubidium Oxide Phases . . . . . . . . . . . . . . . . . . . . .
3.3.1 Rubidium Superoxide (RbO2 ) . . . . . . . . . . . . . .
3.3.2 RbO2−δ . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.3 Incorporating Peroxide Anions (RbO2−δ ; δ > 0.5) . . .
3.4 Discussion on the Phase Diagram of RbOx . . . . . . . . . . .
3.5 Cooling Rate Effect in RbOx . . . . . . . . . . . . . . . . . .
3.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Bibliography
4 Ferromagnetic Order from p-Electrons
4.1 Introduction . . . . . . . . . . . . . . .
4.2 Experiment . . . . . . . . . . . . . . .
4.3 Results . . . . . . . . . . . . . . . . . .
4.3.1 Chemical Composition . . . . .
4.3.2 Crystal Structure . . . . . . . .
4.3.3 Magnetic Properties . . . . . .
4.4 Discussion . . . . . . . . . . . . . . . .
4.5 Conclusions . . . . . . . . . . . . . . .
Bibliography
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Rubidium Oxide
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5 Isotropic S = 1/2 Antiferromagnetic Chain in p-Electron System 91
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2 Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.3 Structure and Chemical Composition . . . . . . . . . . . . . . . . . 94
5.4 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.4.1 One-Dimensional Spin Chain . . . . . . . . . . . . . . . . . 96
5.4.2 Field Dependence of Magnetization . . . . . . . . . . . . . . 100
5.5 Low-Temperature Crystal Structure . . . . . . . . . . . . . . . . . 101
5.6 Low Temperature Raman Spectroscopy . . . . . . . . . . . . . . . 104
5.7 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Bibliography
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Contents
6 Thin Film Rubidium Oxides and Investigation of Cesium
Potassium Oxides
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2 Thin Film Rubidium Oxides . . . . . . . . . . . . . . . . . . . .
6.3 Cesium Oxides (CsO2−x ) . . . . . . . . . . . . . . . . . . . . .
6.4 Potassium Oxides (KO2−x ) . . . . . . . . . . . . . . . . . . . .
6.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Bibliography
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Summary
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Samenvatting
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Acknowledgments
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Contents