Spectroscopic Properties of Rare Earths in Optical Materials

Contents......Page 8
1.1 Introduction......Page 18
1.2.1 Central Field Approximation......Page 21
1.2.2 LS Coupling and Intermediate Coupling......Page 24
1.3.1 Coulomb Interaction......Page 28
1.3.2 Spin-orbit Interaction......Page 31
1.3.3 Corrections to Free-ion Hamiltonian......Page 32
1.3.4 Reduced Matrices and Free-ion State Representation......Page 34
1.3.5 Parameterization of the Free-ion Interactions......Page 35
1.3.6 Energy Levels of 4f[sup(N)] Configurations and Binding Energies Relative to Host Band......Page 40
1.4 Crystal-field Interaction......Page 43
1.4.1 Crystal-field Hamiltonian and Matrix Element Evaluation......Page 45
1.4.2 Symmetry Rules......Page 49
1.4.3 Empirical Evaluation of Crystal-field Parameters......Page 54
1.4.4 Theoretical Evaluation of Crystal-field Parameters......Page 56
1.4.5 Corrections to the Crystal-field Hamiltonian......Page 63
1.5 Analysis of Crystal-field Spectra......Page 67
1.5.1 Experimental Data......Page 68
1.5.2 Computational Modeling......Page 71
1.6.1 Energy Gaps Between the 4f[sup(N)] and Excited Configurations......Page 74
1.6.2 Hamiltonian for 4f[sup(N−1)] 5d Configurations......Page 76
1.6.3 Determination of Hamiltonian Parameters......Page 77
1.7 Magnetic and Hyperfine Interactions......Page 81
1.7.1 Zeeman Effect......Page 82
1.7.2 Magnetic Hyperfine Interaction......Page 84
1.7.3 Nuclear Electric Quadrupole Interaction......Page 86
1.7.4 Ion-ligand Hyperfine Interaction......Page 89
1.7.5 Pr[sup(3+)]......Page 90
1.7.6 Eu[sup(3+)]......Page 93
1.7.7 Tb[sup(3+)]......Page 102
1.7.8 Other Ions......Page 105
References......Page 106
2.1 Introduction......Page 112
2.2.1 Electric and Magnetic Dipole Operators......Page 113
2.2.2 Polarization Selection Rules......Page 115
2.2.3 Vibronic Transitions......Page 117
2.3 One Photon Transitions Within the 4f[sup(N)] Configuration......Page 119
2.3.1 General Theory......Page 120
2.3.2 Transitions Between Crystal-field Levels......Page 121
2.3.3 Transitions Between J Multiplets......Page 125
2.3.5 Vibronic Transitions......Page 126
2.3.6 Circular Dichroism......Page 127
2.3.7 Parameter Fits......Page 128
2.3.8 Comparison with First-principles Calculations......Page 134
2.3.9 Extensions to the Models......Page 138
2.4.1 4f[sup(N)] ↔ 4f[sup(N−1)] 5d Transitions......Page 139
2.4.2 Charge Transfer......Page 140
2.5.1 f[sup(N)] ↔ f[sup(N)] Transitions......Page 141
References......Page 143
3.1 Introduction......Page 147
3.2 Basic Concepts: Hamiltonian of the Ion-phonon Interaction, Adiabatic and Nonadiabatic Terms......Page 148
3.3 Coupling Constants......Page 156
3.4 Density Matrix Formalism in the Quantum Theory of Relaxation......Page 162
3.5 Thermal Shifts of Zero-phonon Line Positions......Page 168
3.6.1 One- and Two-phonon Transition Rates......Page 170
3.6.2 Phonon Contributions to Linewidths......Page 172
3.6.3 Multiphonon Relaxation......Page 175
3.7 Vibrational Structure of the Optical Spectra......Page 183
3.8 Simulations of the Ion-phonon Interaction Effects......Page 187
3.8.1 Impurity Rare Earth Single Ion Centers in the LiYF[sub(4)] Crystal......Page 188
3.8.2 Relaxation Broadening of Optical Transitions in Pr[sup(3+)] Dimer Centers in CsCdBr[sub(3)]......Page 199
3.9 Conclusions......Page 202
References......Page 203
4.1 Introduction......Page 208
4.2.1 Zero-phonon Linewidths of 4f→4f and 4f→5d Transitions......Page 211
4.2.2 Line Broadening from Defects and Disorder......Page 212
4.2.3 Site-selective Spectroscopy......Page 214
4.2.4 Ultranarrow Inhomogeneous Linewidths......Page 218
4.3.1 Hyperfine Structure and Isotope Shifts......Page 219
4.3.2 Vibronic Sidebands......Page 220
4.4 Homogeneous Broadening......Page 221
4.4.1 Ion-phonon Interactions......Page 222
4.4.2 Ion-ion Interactions......Page 225
4.4.3 Ion-nuclear Spin-spin Interactions......Page 230
4.5 Measurement of Line Broadening and Examples......Page 231
4.5.1 Fluorescence Line-narrowing......Page 232
4.5.2 Spectral Hole Burning......Page 235
4.5.3 Coherent Transient Spectroscopy......Page 244
4.6 Disordered, Low-dimensional and Nanostructure Crystalline Materials......Page 255
4.6.1 Disordered Materials......Page 256
4.6.2 Low Dimensional Systems......Page 263
4.6.3 Nanocrystalline Materials......Page 268
References......Page 274
5 Up-conversion in RE-doped Solids......Page 283
5.1 Introduction and Historical Background......Page 284
5.2.1 Recall of Basics of Energy Transfer with Activator in Its Ground State......Page 285
5.2.2 Up-conversion Processes by Sequential Energy Transfers; Comparison with ESA and Typical Examples......Page 293
5.3 Up-conversion in Single-ion and Pair-level Level Description; Theoretical and Experimental Discrimination......Page 296
5.3.1 Application of Cooperative Luminescence; Theory and Examples......Page 301
5.3.2 Some Experimental Results for APTE Effect and Their Implications in Various Field......Page 303
5.4 Cross-relaxation and the Photon Avalanche Effect......Page 313
5.4.1 The Avalanche Process as a Positive Feedback System......Page 315
5.4.2 Conditions for Observing an Avalanche Threshold......Page 317
5.4.3 Er[sup(3+)]:LiYF[sub(4)] as an Avalanche Model Experiment......Page 319
5.4.4 Photon Avalanche in Er[sup(3+)]-doped Fluoride Glasses in Fibre and Bulk Shape......Page 323
5.4.5 Avalanche in Co-doped Systems......Page 326
5.4.6 Up-conversion Laser with Multiphonon-assisted Pumping Scheme and Photon Avalanche......Page 327
5.5.1 Up-conversion UV Tunable Lasers......Page 328
5.5.3 Up-conversion Material Intrinsic Bistability......Page 329
5.6 Conclusions......Page 331
References......Page 332
6.1 Introduction......Page 337
6.2 Spectroscopic and Laser Parameters......Page 338
6.2.1 Basic Laser Parameters......Page 339
6.2.2 Determination of Absorption Cross Sections......Page 345
6.2.3 Determination of Emission Cross Sections......Page 346
6.2.4 Determination of Radiative Lifetimes and Branching Ratios......Page 353
6.3.1 Compact and Tunable UV Lasers Based on Ce[sup(3+)] Doped Crystals: Prospects with Other Ions......Page 357
6.3.2 Lasers Based on Nd[sup(3+)] and Yb[sup(3+)] Doped Nonlinear Crystals......Page 362
6.4.1 High-power and Ultrafast Lasers Based on Yb[sup(3+)] Doped Materials......Page 366
6.4.2 Rare-earth Doped Crystals for Telecommunications and Eyesafe Laser Applications......Page 372
6.4.3 Low-frequency Phonon Materials for Mid-infrared Lasers......Page 381
6.5 Conclusions......Page 386
6.A Laser Threshold Condition......Page 387
6.C Energy Transfer Rates......Page 388
6.E List of Acronyms......Page 389
References......Page 390
7.1 Introduction......Page 396
7.1.1 Equivalence of Holeburning and Photon Echoes in Storage and Signal Processing Applications......Page 398
7.1.3 Dephasing and Spectral Diffusion......Page 399
7.2 Eu[sup(3+)] Materials......Page 401
7.2.1 Properties of Y[sub(2)]SiO[sub(5)]......Page 402
7.2.2 Eu[sup(3+)]:Y[sub(2)]SiO[sub(5)]......Page 403
7.2.4 Eu[sup(3+)]:Y[sub(2)]O[sub(3)]......Page 408
7.2.5 Eu[sup(3+)]:YAlO[sub(3)]......Page 410
7.3.1 Pr[sup(3+)]:Y[sub(2)]SiO[sub(5)]......Page 411
7.3.2 Pr[sup(3+)]:YAlO[sub(3)]......Page 414
7.3.3 Pr[sup(3+)]:Y[sub(3)]Al[sub(5)]O[sub(12)]......Page 415
7.4 Tm[sup(3+)] Materials......Page 416
7.4.1 Tm[sup(3+)]:Y[sub(3)]Al[sub(5)]O[sub(12)]......Page 418
7.4.2 Tm[sup(3+)]:Lu[sub(3)]Al[sub(5)]O[sub(12)]......Page 421
7.4.3 Tm[sup(3+)]:Y[sub(1.5)]Lu[sub(1.5)]Al[sub(5)]O[sub(12)]......Page 422
7.4.4 Tm[sup(3+)]:Y[sub(3)]Ga[sub(5)]O[sub(12)]......Page 423
7.4.6 Tm[sup(3+)]:Y[sub(2)]SiO[sub(5)]......Page 424
7.4.7 Tm[sup(3+)]:Y[sub(2)]Si[sub(2)]O[sub(7)]......Page 425
7.4.9 Tm[sup(3+)]:YAlO[sub(3)]......Page 426
7.4.10 Tm[sup(3+)] Materials Summary......Page 427
7.5 Er[sup(3+)] Materials......Page 428
7.5.1 Properties of Er[sup(3+)]:Y[sub(2)]SiO[sub(5)]......Page 429
7.5.3 Properties of Er[sup(3+)]:LiNbO[sub(3)]......Page 433
7.5.4 Properties of Er[sup(3+)]:YAlO[sub(3)]......Page 434
7.5.5 Properties of Er[sup(3+)]:Y[sub(3)]Al[sub(5)]O[sub(12)]......Page 436
7.5.7 Er[sup(3+)] Materials Summary......Page 437
7.6 Other Materials......Page 438
7.6.1 Eu[sup(2+)] Materials......Page 439
7.6.2 Deuterated Fluorides......Page 440
7.6.4 Nd[sup(3+)] Systems......Page 441
References......Page 443
8.1 Introduction......Page 447
8.2.1 Opto-geometrical Parameters......Page 449
8.2.2 Spectroscopic Parameters......Page 450
8.2.3 Amplification into a Waveguide......Page 455
8.2.4 Material Requirements for Fabrication of Waveguide......Page 458
8.2.5 Other Specific Properties: Photosensitivity and Photorefractivity......Page 459
8.3 Waveguide Amplifiers and Lasers......Page 460
8.3.1 Erbium-doped Fiber Amplifier......Page 461
8.3.2 Praseodymium-doped Fiber Amplifier......Page 466
8.3.3 Thulium-doped Fiber Amplifier......Page 467
8.3.4 Fiber Lasers......Page 469
8.3.5 Optical Integrated Amplifiers and Lasers......Page 470
8.4 Optical Microcavities and Nanoconfinement......Page 471
8.4.1 Optical Confinement......Page 472
8.4.2 Experimental Evidences......Page 473
8.4.3 Various Devices......Page 474
References......Page 475
9.1 Introduction......Page 479
9.2.1 Establishing the Importance of the Triplet State......Page 481
9.2.2 Mechanisms of Energy Transfer......Page 484
9.3.1 Vibrational Deactivation Processes......Page 486
9.3.2 Electronic Deactivation Processes......Page 489
9.4.1 Qualitative Rules......Page 493
9.4.2 Quantitative Estimates......Page 494
9.5 Luminescent Lanthanide Complexes with Organic Ligands......Page 498
9.6.1 Fluoroimmunoassays......Page 503
9.6.2 Responsive Systems......Page 506
9.A Chemical Formulae of Compounds Cited in the Text......Page 508
9.B Glossary and Chemical Formulae......Page 513
References......Page 514
10.1 X-ray Phosphors......Page 517
10.2 X-ray Phosphors Used for Intensifying Screens......Page 519
10.2.1 Calcium Tungstate......Page 520
10.2.2 Rare Earth Tantalate Based Phosphors......Page 521
10.2.3 Europium Activated Barium Fluoro-chloride Phosphors......Page 526
10.2.4 Tb- and Tm-activated Lanthanum Oxbromides......Page 528
10.2.5 Tb[sup(3+)]-activated Gadolinium Oxysulfide......Page 530
10.3 X-ray Storage Phosphors and Their Applications......Page 531
10.3.1 Physical Mechanism of Photostimulated Luminescence......Page 532
10.4 X-ray Phosphors for Computed Tomography......Page 535
10.4.1 Scintillators for X-ray Computed Tomography......Page 538
10.5 Scintillators for Electromagnetic Calorimetric Detection......Page 541
10.5.1 Cerium Fluoride......Page 542
10.5.2 Ce[sup(3+)]-activated Gd[sub(2)]SiO[sub(5)] and Lu[sub(2)]SiO[sub(5)]......Page 543
References......Page 544
A.1 Effective Hamiltonians and Effective Operators......Page 547
A.2 Perturbation Expansions......Page 548
A.3 Symmetries and Selection Rules......Page 551
A.4 Implications......Page 552
References......Page 553
B.2 Clebsh-Gordan Coefficients and 3-j Symbols......Page 554
B.3 Tensor Operators and the Wigner-Eckart Theorem......Page 555
B.4 More Complex Situations......Page 556
References......Page 557
E......Page 558
J......Page 559
S......Page 560
Z......Page 561
Materials Index......Page 562