1 Introduction ................................................. 1
1.1 Diamond in History and Research ......................... 1
1.2 Types of Diamond Samples ................................ 5
1.2.1 Natural Diamond .................................. 5
1.2.2 High Pressure Synthetic Diamond (HPHT) ........... 6
1.2.3 Low Pressure Synthetic Diamond (CVD) ............. 6
1.2.4 Modified Diamond ................................. 7
1.2.5 Diamond-Related Materials ........................ 7
1.3 Optical Techniques ...................................... 8
1.3.1 Absorption ....................................... 8
1.3.2 Photoluminescence Excitation ..................... 8
1.3.3 Luminescence ..................................... 8
1.3.4 Raman Scattering ................................. 9
1.3.5 Photoconductivity ................................ 9
1.4 Organization of the Tables in Chaps. 2-7 ................ 9
2 Spectral Lines in Natural Diamond ........................... 13
2.1 Absorption lines (NA) .................................. 14
2.2 Excitation of Photoluminescence Lines (NE) ............. 33
2.3 Luminescence Lines (NL) ................................ 38
2.4 Broad Bands (NB) ....................................... 61
3 Spectral Lines in High Pressure Synthetic (HPHT) Diamond .... 65
3.1 Absorption Lines (HA) .................................. 66
3.2 Excitation of Photoluminescence Lines (HE) ............. 77
3.3 Luminescence Lines (HL) ................................ 78
3.4 Broad Bands (HB) ....................................... 89
4 Spectral Lines in Low Pressure Synthetic (CVD) Diamond ...... 93
4.1 Absorption Lines (LA) .................................. 94
4.2 Excitation of Photo Luminescence Lines (LE) ........... 102
4.3 Luminescence Lines (LL) ............................... 105
4.4 Broad Bands (LB) ...................................... 123
5 Spectral Lines in Modified Diamond (Irradiation, Heat,
etc.) ...................................................... 127
5.1 Absorption Lines (MA) ................................. 128
5.2 Excitation of Photo Luminescence Lines (ME) ........... 166
5.3 Luminescence Lines (ML) ............................... 178
5.4 Broad Bands (MB) ...................................... 227
6 Spectral Lines in Diamond-Related Materials: DLC,
Lonsdaleite, etc ........................................... 233
6.1 Absorption Lines (RA) ................................. 234
6.2 Luminescence Lines (RL) ............................... 242
6.3 Broad Bands (RB) ...................................... 244
7 Spectral Line Shifts from Substituted and Natural
Isotopes ................................................... 247
7.1 Isotopic Shifts from 2H (Deuterium) (i2, i4, i6, i8) .. 248
7.2 Isotopic Shifts from 13C(i13,i26) ..................... 252
7.3 Isotopic Shifts from 15N (i15, i30) ................... 263
7.4 Isotopic Shifts from Si2 (28Si+29Si or 30Si) (i57,
i58) .................................................. 266
7.5 Isotopic Shifts from Ni1(i60, i61, i62, i64), or
Ni2(i118,i120,i122) ................................... 267
8 Intrinsic Defects and Their Associates in Diamond .......... 269
8.1 Lattice Vacancies and Associates ...................... 269
8.1.1 The Isolated Single Vacancy .................... 269
8.1.2 The Isolated Divacancy ......................... 272
8.1.3 Associates of Single or Double Vacancies
with Nitrogen .................................. 272
8.1.4 Associates of the Single Vacancy with Ni1,
Ni2 and N3 ..................................... 280
8.1.5 Centers of Nil in the Double Vacancy and
Association with Nitrogen Ligands (S2-*S9) ..... 281
8.1.6 Centers of Si2, Ni2, or Co2 in the Triple
Vacancy ........................................ 283
8.1.7 Associates of the Vacancies with H, (H + N),
He, Li, B, N, Al, Si, Ti, Cr, Co, Ni, Zn, As,
Zr, Ag, Xe, Ta, W, and Tl ...................... 285
8.2 The (100) Split Self-Interstitial and Associates ...... 289
8.2.1 The Isolated ( 100) Split Self-Interstitial .... 289
8.2.2 The Multiple (100) Split Self-Interstitial ..... 291
8.2.3 Associates of the (C2)i Split Interstitial
with N1, N2, with B1, B2, B3, or with Ni ...... 292
8.2.4 The (100) Split Nitrogen-Carbon Interstitial
(N1C1)i and Associates with B1-, B1°, B1+ ...... 295
8.3 Discussion of Spectral Data from Intrinsic Defects .... 298
8.3.1 Thermal Stability of the Intrinsic Defects ..... 298
8.3.2 Donor-Acceptor Pair Transitions at Intrinsic
Defects ........................................ 298
8.3.3 Quasilocal Vibrational Mode Sidebands at
Intrinsic Defects .............................. 299
8.3.4 Local Vibrational Mode Sidebands at Intrinsic
Defects ........................................ 300
8.3.5 Infrared Vibrational Absorption Lines .......... 300
8.3.6 Vibrational Isotope Shifts from 13C and 15N
Substitution ................................... 301
8.3.7 Isotope Shifts of the Zero Phonon Lines by
13C and 15N Substitution ....................... 301
9 Impurity Defects in Diamond ................................ 303
9.1 Nitrogen in Diamond ................................... 303
9.1.1 Isolated Nitrogen Centers ...................... 304
9.1.2 Associates of Nitrogen with Single or Double
Vacancies ...................................... 309
9.1.3 Associates of the Split Self-interstitial
(C2)j with One or Two Nitrogens ................ 311
9.1.4 The (1 0 0) Split Nitrogen-Carbon Interstitial
(N1C1)j in Three Charge States, Associates
with Boron, and the (N2)1° center .............. 311
9.1.5 Donor-Acceptor Pairs of Nitrogen (N1 and N2)
with a Single Boron and of Nitrogen (N2)
with an Unknown Acceptor ....................... 311
9.1.6 Discussion ..................................... 313
9.2 Boron in Diamond ...................................... 316
9.2.1 Isolated Substitutional Boron .................. 317
9.2.2 Standard DAP of Boron with Nitrogen (DAP1, 9,
18, 19, 20, 67, 70), Phosphorous (DAP2), or
Oxygen (DAP17) ................................. 317
9.2.3 Associate of Boron with a Lattice Vacancy ...... 319
9.2.4 Associates of B1, B2, or B3 with the (1 0 0)
(C2)j Split Self-interstitial .................. 320
9.2.5 Associates of B1 with the (1 0 0) Split
(N1C1)i Interstitial in Three Charge States .... 320
9.2.6 Boron-Bound Exciton Lines ...................... 320
9.2.7 Discussion ..................................... 321
9.3 Hydrogen in Diamond ................................... 322
9.3.1 Hydrogen Lines in Natural Diamond .............. 322
9.3.2 Hydrogen Bend Lines in Polycrystalline CVD
Diamond ........................................ 324
9.3.3 Hydrogen Stretch Lines in Polycrystalline
CVD Diamond .................................... 325
9.3.4 Abundances of C-H Configurations ............... 325
9.3.5 Frequencies of C-C Vibrations from H-Bonded
Carbon ......................................... 330
9.3.6 Additional Hydrogen Lines in Homoepitaxial
CVD Diamond .................................... 333
9.4 Silicon in Diamond .................................... 334
9.4.1 Five Silicon Centers in Diamond ................ 334
9.4.2 Resolved ZPL Isotope Shifts from Natural
Silicon ........................................ 334
9.4.3 Effects of Annealing ........................... 337
9.4.4 Time-Resolved Spectroscopy ..................... 337
9.4.5 Local Vibrational Modes ........................ 337
9.4.6 Quasi-Local Vibrational Modes .................. 337
9.4.7 DAP Transition at Nickel Centers ............... 337
9.4.8 Considerations for Structure Assignments ....... 338
9.5 Nickel in Diamond ..................................... 338
9.5.1 Twenty Nickel Centers in Diamond ............... 338
9.5.2 Resolved Isotope Shifts from Natural Nickel .... 343
9.5.3 Nickel Implantation and Resulting Centers ...... 344
9.5.4 Electron Paramagnetic Resonance and Zeeman
Effect of Nickel Centers ....................... 345
9.5.5 Influence of Nitrogen Concentration ............ 345
9.5.6 Effects of Annealing of Nickel Centers ......... 345
9.5.7 Local Vibrational Modes ........................ 349
9.5.8 Quasi-Local Vibrational Modes .................. 350
9.5.9 DAP Transition at Nickel Centers ............... 350
9.5.10 The S2 to *S9 Family (DAP57-61,11, 16, 4)
with the (V2Ni\) Nucleus and 0-3 Nitrogen
Ligands ........................................ 352
9.5.11 Discussion of 20 Individual Nickel Centers .... 352
9.6 Cobalt in Diamond ..................................... 357
9.6.1 The *Co 1.47 Center at 1.472eV from *V1Co1+ .... 357
9.6.2 The *Co 2.59 Center at 2.590 eV from *V1Co2- ... 357
9.6.3 The *Co 2.89 Center at 2.889 eV from * V1
Co2° ........................................... 357
9.6.4 The *Co 1.85 Center at 1.852 eV from *V1Co1+ ... 359
9.6.5 The *Co-S5 Center in the Range 2.135-
2.82OeV from *(V2Co1)Nx+y+z° ................... 359
9.6.6 The *Co 1.99 Center at 1.989eV from *
(V3Co2)+ ....................................... 359
9.6.7 Discussion of Spectral Data from Cobalt
Centers in Diamond ............................. 360
9.7 Other Impurities in Diamond ........................... 361
9.7.1 Main Group Impurities: H, Li, B, Al, In, Tl,
Si, N, P, As, Sb, O, He, Ne, and Xe in
Diamond ........................................ 361
9.7.2 Transition Metal Impurities: Ag, Zn, Ti, Zr,
Ta, Cr, W, Fe, Co, and Ni in Diamond ........... 361
9.7.3 Effects of Annealing ........................... 366
9.7.4 Local Vibrational Modes ........................ 366
9.7.5 Quasi-Local Vibrational Modes .................. 366
9.7.6 DAP Transitions ................................ 366
9.7.7 Bound Excitons from Li, В and P ................ 366
9.7.8 Considerations for Structure Assignments ....... 367
10 Donor-Aceeptor Pair Transitions in Diamond ................. 369
10.1 Resolved Lines in Absorption and Luminescence ......... 369
10.2 Broad Bands from Unresolved Lines ..................... 397
10.3 Depth of Donors (N, О, P) from Analysis of DAPs
with В Acceptor ....................................... 399
10.4 Dependence of the Dielectric Factor D on the Number
of Electrons .......................................... 399
10.5 Dependence of the Dielectric Factor D on the Charge
State ................................................. 405
11 Vibrational Frequencies of Defect Centers in Diamond ....... 407
11.1 Local Vibrational Modes ............................... 407
11.2 Quasilocal Vibrational Modes .......................... 412
11.3 Lattice Phonons in Free and Bound Exciton Sidebands ... 412
12 Modification of Diamond by Irradiation and Heat ............ 413
12.1 High Energy Irradiation by X-rays, Electrons, or
Neutrons .............................................. 413
12.2 Ion Implantation ...................................... 413
12.3 Heat Treatment ........................................ 414
13 Isotopic Line Shifts in Diamond ............................ 415
13.1 Isotopic Line Shifts at Zero Phonon Lines ............. 415
13.2 Isotopic Frequency Shifts at Local Vibrational
Modes ................................................. 416
13.3 Isotopic Frequency Shifts at Quasilocal Vibrational
Modes ................................................. 416
14 Spectroscopic Discrimination Between Natural and
Nonnatural Diamond ......................................... 419
14.1 Existing Methods ...................................... 419
14.2 Alternate Methods ..................................... 420
15 Conclusions and Outlook .................................... 423
15.1 Conclusions ........................................... 423
15.2 Outlook ............................................... 424
A Appendix ................................................... 427
A.l Historical, Existing, and New Names of Centers in
Diamond ............................................... 427
A.1.1 Historical Names ............................... 427
A.1.2 Existing Names ................................. 427
A.1.3 New Names ...................................... 427
A.2 Calculated Coulomb Factors for Donor-Acceptor Pairs ... 445
A.3 Calculated Frequencies and Linewidths for Quasilocal
Vibrational Modes ..................................... 451
References .................................................... 455
Index ......................................................... 465
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