List of Contributors ........................................... XI
Foreword ....................................................... XV
M. Rosseinsky
1 Introduction to the Series "Progress in Fluorine Science" .... 1
A. Tressaud
Part One. Synthesis ............................................. 5
2 Elaboration of Nanofluorides and Ceramics for Optical and
Laser Applications ........................................... 7
P.P. Fedorov, S.V. Kuznetsov, V.V. Osiko
1 Introduction .............................................. 7
2 Phase Formation in Nanofluoride Systems ................... 8
3 Luminescence ............................................. 15
4 Laser and Scintillating Ceramics ......................... 22
5 Self-Fluorinating Agents ................................. 22
6 Conclusion ............................................... 25
Acknowledgments ............................................. 25
References .................................................. 25
Part Two. Optical Properties .................................. 33
3 Upconversion Phenomena in Nanofluorides ..................... 35
G. Ledoux, M.F. Joubert, S. Mishra
1 Introduction ............................................. 35
2 The Components of the Upconverting Nanoparticles:
Dopants and Hosts ........................................ 38
3 Synthetic Strategies ..................................... 39
4 Upconversion in Rare Earth—Doped Nanofluorides ........... 50
5 Conclusion ............................................... 53
References .................................................. 54
4 Optical Properties of Fluoride Transparent Ceramics ......... 65
P. Gredin, M. Mortier
1 Introduction ............................................. 65
2 Fluoride Transparent Ceramic Preparation Processes ....... 68
3 Structural and Optical Properties of Fluoride
Transparent Ceramics ..................................... 69
4 Conclusion—Future for Fluoride Transparent Ceramics ...... 82
References .................................................. 84
5 Synthesis and Characterization of F-Doped Zinc Oxides,
Al-Doped Zinc Hydroxyfluoride, and Oxide—Fluoride
Composites for Transparent Visible/Infrared Absorbers ....... 89
M. Gaudon, H. Serier-Brault, I. Trenque, A. Demourgues
1 Introduction ............................................. 89
2 F-Doped Transparent Conductive Oxides: A State of the
Art ...................................................... 91
3 Al3+-Doped Zn(OH,F)2 Compounds/Al3+-Doped ZnF2
Compounds ................................................ 94
4 Zinc Oxyfluoride "Composites" ........................... 103
5 Conclusion .............................................. 109
References ................................................. 109
6 Fluorine-Containing Beryllium Borates as Nonlinear Optical
Crystals for Deep-Ultraviolet Laser Generation ............. 113
C. Chen, L. Liu, X. Wang
1 Introduction ............................................ 114
2 КВегВОзРг Family Crystals ............................... 115
3 RBBF .................................................... 129
4 CBBF .................................................... 133
5 Conclusions ............................................. 133
References ................................................. 134
7 Fluorescence in Nanostructured Oxyfluoride Glasses Doped
vfith Rare Earth Ions .................................. 139
J. Heo, C. Liu
1 Introduction ............................................ 139
2 Preparation and Characterization of Rare Earth—Doped
Oxyfluoride Glass-Ceramics .............................. 141
3 Nd3+ and Tm3+ Ions in Oxyfluoride Glass-Ceramics ........ 142
4 Electron Energy Loss Spectroscopic Analysis on the
Preferential Incorporation of Rare Earth Ions into
Nanocrystals ............................................ 147
5 Distribution of Rare Earth Ions Inside the Fluoride
Nanocrystals ............................................ 148
6 YF3 Codoping on the Emission of Er3+ in Oxyfluoride
Glass-Ceramics .......................................... 150
7 Summary ................................................. 154
References ................................................. 155
8 Fluorinated Nematic Liquid Crystals: Design, Synthesis,
and Properties ............................................. 159
P. Kirsch
1 Introduction: Liquid Crystals, Fluorine Chemistry, and
Liquid Crystal Display Technology ....................... 159
2 "Nematic Fluorine" and ortho-Metalation Technology ...... 160
3 Fluorine in Polar Terminal and Lateral Groups ........... 162
4 Sulfur-Based Ruorinated Polar Groups .................... 166
5 Fluorinated Bridge Structures ........................... 167
6 Computational Methods for Molecular Design .............. 171
7 The Future of Huorinated Liquid Crystals ................ 174
References ................................................. 174
9 Molecular Engineering of F-Based Iridium(in) Complexes as
a Phosphorescent Emitter ................................... 177
Y. Takahira, E. Murotani
1 Introduction ............................................ 177
2 Molecular Engineering of F-Based Iridium(III) Complexes
as a Phosphorescent Emitter ............................. 182
3 Conclusion .............................................. 192
References ................................................. 192
10 Zinc Hydroxyfluoride (ZnOHF) Nanostructure as
Photoelectrode of Quantum Dot-Sensitized Solar Cells ....... 199
H. Chen, L. Zhu, H. Liu, W. Li
1 Introduction to Zinc Hydroxyfluoride .................... 199
2 Introduction to QDSCs ................................... 200
3 Physical and Chemical Properties of Zinc Hydroxyfluoride 202
4 Synthesis of Zinc Hydroxyfluoride Nanostructures ........ 204
5 Zinc Hydroxyfluoride Nanostructure-Based QDSCs .......... 204
6 Conclusions and Outlooks ................................ 208
Acknowledgment ............................................. 208
References ................................................. 208
Part Three. Magnetic Properties ............................... 211
11 Molecular Fluoride-Bridged 3d-4f Complexes and Their Magnetic
Properties ................................................. 213
K.S. Pedersen, J. Bendix
1 Introduction ........................................... 213
2 Robust CrIII Complexes as Synthons ...................... 214
3 Magnetic Interactions ................................... 219
4 Improving Magnetic Coolers .............................. 225
5 Outlook and Conclusions ................................. 228
Acknowledgments ............................................ 229
References ................................................. 229
12 Unique Silver(II) Fluorides: The Emerging Electronic and
Magnetic Materials ......................................... 231
Z. Mazej, D. Kurzydłowski, W. Grochala
1 Introduction ............................................ 232
2 The Jahn-Teller Effect .................................. 232
3 The Collective Jahn-Teller Effect ....................... 235
4 General Magnetic and Electronic Properties of
Fluoroargentates(II) .................................... 237
5 Silver(II) Fluoride (AgF2)-Precursor Toward
Fluoroargentates(II) .................................... 241
6 Crystal Structures and Magnetic Properties of B2AgF4 .... 244
7 BAgF3 Systems ........................................... 252
8 Summary and Outlook ..................................... 255
Acknowledgments ............................................ 257
References ................................................. 257
13 Magnetic Properties of Transition Metal Fluoride
Perovskites ................................................. 261
L. Clark, P. Lightfoot
1 Introduction ............................................ 261
2 Cubic Perovskites ....................................... 262
3 Distorted Perovskite Derivatives ........................ 264
4 Layered Perovskites ..................................... 271
5 Hexagonal Perovskites ................................... 279
References ................................................. 281
14 Multiferroism in Fluorides ................................. 285
G. Calestani, F. Mezzadri
1 Introduction ............................................ 285
2 The BaMF4 Family ........................................ 286
3 Fluorides With Tetragonal Tungsten Bronze Structure ..... 290
4 Conclusions ............................................. 303
References ................................................. 305
Part Four Non-linear Properties ........................... 309
15 Frequency-Doubling Oxide Fluorides, Borate Fluorides, and
Fluorooxoborates ........................................... 311
S. Pan, Y. Wang, K.R. Poeppelmeier
1 Introduction ............................................ 312
2 Fundamentals of Borate Fluorides and Fluorooxoborates:
Synthesis and Structural Chemistry ...................... 313
3 Borate Fluorides as Frequency-DoubUng Materials ......... 317
4 Fluorooxoborates as Frequency-Doubling Materials ........ 342
5 Summary and Outlook ..................................... 348
References ................................................. 348
16 Ferroelastic and Ferroelectric Phase Transitions in Fluoro-
and Oxyfluorometallates .................................... 355
I.N. Flerov, M.V. Gorev, M.S. Molokeev, N.M. Laptash
1 Introduction ............................................ 355
2 Mechanism of Structural Phase Transitions in Fluorides
and Oxide-Fluorides ..................................... 357
3 Nature of Phase Transitions ............................. 367
4 Sensitivity to Pressure ................................. 370
5 Conclusions ............................................. 376
Acknowledgments ............................................ 377
References ................................................. 377
17 Group Theoretical Approach on Possible Magnetoelectric
Fluorides .................................................. 383
G. Nénert
1 Introduction ............................................ 383
2 The BaMIIIF5 Family ...................................... 384
3 Na2SiF6-Related Family: AMM'Fg Materials (A = Na, Li; M,
M' = Mn, Cr, Ga, Fe) .................................... 390
4 Weberite ................................................ 393
5 Conclusion .............................................. 396
References ................................................. 397
Part Five Superconductor Properties .......................... 399
18 Modification of Magnetic and Electronic Properties, in
Particular Superconductivity, by Low Temperature Insertion
of Fluorine into Oxides .................................... 401
P. Slater, L. Driscoll
1 Introduction ............................................ 401
2 Initial Studies of the Fluorination of Cuprates With F2,
NF3 Gas, and Electrochemical Fluorination ............... 403
3 Fluorination of Cuprates With Solid-State Fluorinating
Agents (CuF2, ZnF2, NiF2, AgF2, XeF2, NH4F, PVDF, PTFE) .. 408
4 Extension of Low-Temperature Fluorination Routes to Other
Transition Metal—Containing Systems ..................... 410
5 Conclusions and Future Directions ....................... 415
References ................................................. 417
19 Superconductivity in Iron Oxypnictide Induced by F-Doping .. 423
Y. Kamihara, H. Hosono
1 Background and Recent Progress in Layered Oxypnictides .. 423
2 Electronic Phase and Superconducting Mechanism in Layered
Oxypnictides ............................................ 428
3 Synthesis Procedures and Applications ................... 436
4 Conclusions ............................................. 440
References ................................................. 440
Part Six. Ionic Conductors .................................... 447
20 Ionic Conductivity of Nanocrystalline Metal Fluorides ...... 449
M.A. Reddy, M. Fichtner
1 Introduction ............................................ 449
2 Ionic Conduction in Solids .............................. 450
3 Fluoride Ion Conductors ................................. 454
4 Summary ................................................. 462
References ................................................. 462
21 Nonstoichiometric Single Crystals M1-xRxF2+x and
R1-уМуF3-у (M = Ca, Sr, Ba: R = Rare Earth Elements) as
Fluorine-Ionic Conductive Solid Electrolytes ............... 465
B.P. Sobolev, N.I. Sorokin, N.B. Bolotina
1 Introduction ............................................ 466
2 Nonstoichiometric Phases With Fluorite- and Tysonite-
Type Structures ......................................... 467
3 Fluorine-Ion Transport in Nonstoichiometric Fluorides
With CaF2- and LaF3-Structures .......................... 468
4 The Search for Fluoride Systems Involving FCSEs ......... 468
5 Defect Structures of Nonstoichiometric M1-xRxF2+x
and R1-yMyF3-y, Crystals ................................. 469
6 Chemical Engineering Aspects of Research on Ruorine-
Ionic Conductivity in M1-xRxF2+x and R1-yMyF3-y
Crystals ................................................ 472
7 Techniques of σdc Measurements in M1-xRxF2+x and
R1-yMyF3-y Crystals ...................................... 473
8 Experimental Studies of σdc in Fluorite-Like
М1-xRxF2+x: Single Crystals .............................. 475
9 Experimental Studies of σdc in Tysonite-Like R1-yMyF3-y
Single Crystals ......................................... 482
10 Conclusions ............................................. 487
References ................................................. 487
Index ......................................................... 493
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