Chapter 1. Magnetron Sputtered Hard and Yet Tough
Nanocomposite Coatings with Case Studies:
Nanocrystalline TiN Embedded in Amorphous SiNx ....... 1
Sam Zhang, Deen Sun and Xuan Lam Bui
1. Introduction ................................................. 1
2. Deposition ................................................... 3
2.1. Design of Microstructure ................................ 3
2.2. Synthesis of Thin Films ................................. 7
3. Characterization ............................................ 11
3.1. Composition ............................................ 11
3.2. Topography ............................................. 13
3.3. Microstructure ......................................... 15
3.4. Mechanical Properties .................................. 17
3.5. Oxidation Resistance ................................... 24
4. Case Studies: Silicon Nitride Nanocomposite Coating ......... 24
4.1. Nanocrystalline TiN Embedded in Amorphous SiNx
or nc-TiN/a-SiNx ....................................... 24
4.2. Ni-Toughened nc-TiN/a-SiNx ............................. 67
References ................................................. 104
Chapter 2. Magnetron Sputtered Hard and Yet Tough
Nanocomposite Coatings with Case Studies:
Nanocrystalline TiC Embedded in Amorphous Carbon ... 111
Sam Zhang, Xuan Lam Bui and Deen Sun
1. Al-doped Amorphous Carbon: a-C(Al) ......................... 1ll
1.1. Composition and Microstructure ........................ 112
1.2. Mechanical Properties ................................. 117
2. Nanocrystalline TiC Embedded in Amorphous Carbon:
nc-TiC/a-C ................................................. 120
2.1. Composition ........................................... 120
2.2. Topography ............................................ 122
2.3. Microstructure ........................................ 124
2.4. Mechanical Properties ................................. 130
2.5. Summary ............................................... 134
3. Al-Toughened nc-TiC/a-C .................................... 134
3.1. Composition ........................................... 135
3.2. Microstructure ........................................ 135
3.3. Mechanical Properties ................................. 138
3.4. Thermal Stability and Oxidation Resistance ............ 150
3.5. Application in Piston Ring ............................ 156
3.6. Summary ............................................... 161
References ................................................. 164
Chapter 3. Properties of Chemical Vapor Deposited
Nanocrystalline Diamond and Nanodiamond/
Amorphous Carbon Composite Films ................... 167
S.С. Tjong
1. Introduction ............................................... 167
2. Chemical Vapor Deposition .................................. 170
3. NCD Film Formation from Hydrogen-Deficient Plasma .......... 176
4. NCD Films Formation from Hydrogen-Rich Plasma .............. 183
5. Nanocomposite Film ......................................... 186
6. Mechanical Behavior of NCD Films ........................... 189
7. Field Emission Characteristics ............................. 193
8. Conclusions ................................................ 201
References ................................................. 202
Chapter 4. Synthesis, Characterization and Applications of
Nanocrystalline Diamond Films ...................... 207
Zhenqing Xu and Ashok Kumar
1. Synthesis of Diamond ....................................... 207
1.1. History of Diamond .................................... 207
1.2. Structure of Diamond .................................. 208
1.3. Properties of Diamond ................................. 209
1.4. Chemical Vapor Deposition (CVD) ....................... 210
1.5. Growth Mechanisms of Microcrystalhne Diamond (MCD)
Films ................................................. 215
1.6. Growth Mechanisms of Nanocrystalline Diamond (NCD)
Films ................................................. 217
2. Characterization of Nanocrystalline Diamond Films .......... 220
2.1. Scanning Electron Microscopy (SEM) .................... 220
2.2. Transmission Electron Microscopy (ТЕМ) ................ 224
2.3. Raman Spectroscopy .................................... 227
2.4. Near Edge X-Ray Absorption Fine Structure (NEXAFS) .... 231
2.5. X-Ray Diffraction (XRD) ............................... 234
2.6. Characterization of Mechanical Properties of NCD ...... 234
2.7. Electron Energy Loss Spectroscopy (EELS) .............. 238
2.8. Characterization of Electrical Properties of Doped
NCD Films ............................................. 239
3. Applications of NCD ........................................ 244
3.1. MEMS/NEMS Applications of NCD Films ................... 244
3.2. Electrochemistry Applications of NCD Films ............ 251
3.3. Biomedical Applications of NCD Films .................. 260
3.4. Field Emission Devices ................................ 266
3.5. Other Applications of NCD Films ....................... 271
4. Conclusions ................................................ 273
References ................................................. 274
Chapter 5. Properties of Hard Nanocomposite Thin Films ........ 281
J. Musil
1. Introduction ............................................... 281
2. Present State of Knowledge ................................. 281
3. Enhanced Hardness .......................................... 282
3.1. Origin of Enhanced Hardness ........................... 282
3.2. Formation of Nanocomposite Films ...................... 283
3.3. Microstructure of Films Produced in Transition
Regions ............................................... 283
3.4. Microstructure of Nanocomposites with Enhanced
Hardness .............................................. 289
3.5. New Advanced Materials Composed of Nanocolumns ........ 290
4. Mechanical Properties of Nanocomposite Coatings ............ 291
5. High Temperature Behavior of Hard Nanocomposites ........... 293
5.1. Thermal Stability of Film Properties .................. 293
5.2. Si3N4/MeNx; Composites with High (≥50 vol.%)
of a-Si3N4 Phase ...................................... 294
5.3. Thermal Stability of Amorphous Me-Si-N
Nanocomposites ........................................ 299
5.4. Crystallization of Amorphous Zr-Si-N Films During
Post-Deposition Thermal Annealing ..................... 299
5.5. Oxidation of Amorphous Me-Si-N Films in Flowing Air ... 306
5.6. Summary of Main Issues ................................ 308
6. Toughness of Thin Nanocomposite Coatings ................... 310
6.1. Toughening Mechanisms ................................. 310
6.2. Fracture Toughness of Bulk Materials and Thin Films ... 311
6.3. Films and Methods Used for Characterization of Thin
Film Toughness ........................................ 313
6.4. Formation of Cracks ................................... 313
6.5. Assessment of Toughness of Thin Films ................. 317
6.6. Summary of Main Issues ................................ 321
7. Future Trends ............................................ 322
References ................................................. 323
Chapter 6. Nanostructured, Multifunctional Tribological
Coatings ........................................... 329
John J. Moore, In- Wook Park, Jianliang Lin,
Brajendra Mishra and Kwang Ho Kim
1. Introduction ............................................... 329
2. Classification of Nanostructured, Multifunctional
Tribological Coatings ...................................... 330
2.1. Nanoscale Multilayer Coatings ......................... 330
2.2. Nanocomposite Coatings ................................ 332
2.3. Functionally Graded Coatings .......................... 332
3. Background of Nanostructured Superhard Coatings ............ 337
3.1. Nanoscale Multilayer Coatings ......................... 339
3.2. Single Layer Nanocomposite Coatings ................... 341
4. New Directions for Nanostructured Supertough Coatings ...... 342
4.1. Functionally Graded Multilayer Coatings ............... 343
4.2. Functionally Graded Nanocomposite Coatings ............ 345
5. Other Possible Properties of Nanostructured Coatings ....... 346
6. New Processes for Industrial Applications of
Multifunctional Tribological Coatings ...................... 347
6.1. Hybrid Coating System of Cathodic Arc Ion
Evaporation (CAE) and Magnetron Sputtering (MS) ....... 347
6.2. Pulsed Closed-Field Magnetron Sputtering (P-CFUBMS) ... 348
6.3. High-Power Pulsed DC Magnetron Sputtering (HPPMS) ..... 353
7. Preparation-Microstructure-Properties of Nanostructured
Coatings ................................................... 354
7.1. Hybrid Coating System of Ti-Al-Si-N Coatings .......... 354
7.2. Unbalanced Magnetron Sputtering of Ti-Si-B-C-N
Coatings .............................................. 357
7.3. Pulsed Closed-Field Magnetron Sputtering of Cr-Al-N
Coatings .............................................. 363
8. Concluding Remarks ......................................... 375
References ................................................. 376
Chapter 7. Nanocomposite Thin Films for Solar Energy
Conversion ......................................... 381
Yongbai Yin
1. Introduction ............................................... 381
2. Solar Thermal Energy Conversion Nanocomposite Thin Films ... 381
2.1. Solar Thermal Energy Conversion Thin Films ............ 381
2.2. Theories of Nanocomposite and Nanoparticles in
Solar Thermal Energy Conversion ....................... 384
2.3. Complications in Nanocomposite Thin Film Materials
in Solar Thermal Selective Surfaces: The Effects of
Particle Size, Shape, and Orientation ................. 390
3. Nanocomposite Thin Films in Solar Electrical Energy
Conversion ................................................. 395
3.1. Photovoltaic Solar Electricity Generation ............. 395
3.2. Nanocomposite Materials in Thin Film Solar Cells ...... 398
3.3. Dye-Sensitized Solar Cells ............................ 407
3.4. Hot-Carrier Junction Nanocomposite Solar Cells ........ 410
4. Summary .................................................... 414
References ................................................. 414
Chapter 8. Application of Silicon Nanocrystal in Non-
Volatile Memory Devices ............................ 419
T.P. Chen
1. Introduction ............................................... 419
2. Conventional Floating Gate Non-Volatile Memory
Devices .................................................... 420
3. Non-Volatile Memory Devices Based on Si Nanocrystal ........ 424
3.1. Device Structure ...................................... 424
3.2. Operation Mechanisms .................................. 425
4. Synthesis and Characterization of Si Nanocrystal ........... 429
4.1. Synthesis of Si Nanocrystal ........................... 429
4.2. Properties of Si Nanocrystal .......................... 433
5. Memory Behaviors and Performance of Si Nanocrystal
Memory Devices ............................................. 443
5.1. Memory Characteristics ................................ 443
5.2. Effects of Tunnel Oxide Thickness and Programming
Mechanism ............................................. 449
6. Single-Electron Memory Effect .............................. 462
7. Summary .................................................... 466
References ................................................. 467
Chapter 9. Nanocrystalline Silicon Films for Thin Film
Transistor and Optoelectronic Applications ......... 473
Youngjin Choi, Yong Qing Fu and Andrew
J. Flewitt
1. Introduction ............................................... 473
2. Deposition Techniques and Growth Models .................... 474
2.1. Deposition Techniques ................................. 474
2.2. Growth Models ......................................... 479
3. Characterization and Properties of nc-Si Films ............. 482
3.1. Electrical Properties ................................. 482
3.2. Physical Properties ................................... 484
3.3. Stress Issues in Nanocrystalline Si Films ............. 491
4. Device Applications ........................................ 495
4.1. Thin Film Transistors (TFTs) .......................... 495
4.2. Solar Cells ........................................... 499
4.3. Light Emitting Diodes ................................. 504
5. Conclusions ................................................ 506
References ................................................. 506
Chapter 10.Amorphous and Nanocomposite Diamond-Like Carbon
Coatings for Biomedical Applications ............... 513
T.I.T. Okpalugo, N. All, A.A. Ogwu, Y. Kousar
and W. Ahmed
1. Introduction ............................................... 513
2. Amorphous and Nanocomposite Diamond-Like Carbon Coatings ... 515
2.1. Electronic Structure .................................. 515
2.2. Plasma-Based Deposition Methods ....................... 517
2.3. Characterization ...................................... 522
2.4. Doping DLC ............................................ 528
2.5. Thermal Annealing ..................................... 530
2.6. Biological Properties and Biocompatibility ............ 532
2.7. Biomedical Applications ............................... 536
3. Surface Energy of Diamond-Like Carbons ..................... 538
4. Electrical Conductivity and Conduction Mechanisms .......... 542
5. Work Function / Contact Potential Difference ............... 545
6. Protein Adsorption on Biomaterials ......................... 549
6.1. Non-Adhesive Proteins ................................. 549
6.2. Adhesive Proteins ..................................... 549
6.3. Non-Adhesive / Adhesive Protein Ratios ................ 549
7. Endothelial Cell Interactions with Diamond-Like Surfaces ... 550
7.1. Silicon-Doped Diamond-Like Carbon Nanocomposite
Films ................................................. 552
7.2. Chromium-Doped Diamond-Like Carbon Nanocomposite
Films ................................................. 556
8. Summary .................................................... 561
References ................................................. 561
Chapter 11.Nanocoatings for Orthopaedic and Dental
Application ........................................ 573
Weiqi Yan
1. Introduction ............................................... 573
1.1. Clinical Background ................................... 573
1.2. Biomimetic Nanoscale Biomaterials ..................... 574
2. Properties of Bone Implants ................................ 575
2.1. Concept of Biocompatibility ........................... 575
2.2. Classification of Biomaterial Implants ................ 576
2.3. Osteogenesis Around Bone Implants ..................... 577
2.4. Materials for Orthopaedic and Dental Use .............. 578
3. Bone Structure and Formation ............................... 581
3.1. Bone and Cells ........................................ 582
3.2. Bone Formation ........................................ 584
3.3. Bone Properties ....................................... 585
3.4. Bone Remodeling ....................................... 587
4. Bone Healing Around Implants ............................... 588
5. Implant Surface Modifications and Coatings ................. 592
5.1. Bioactive Material Coatings ........................... 592
5.2. Hydroxyapatite-Coated Implants ........................ 593
5.3. Biomimetic Coatings on Titanium-Based Implants ........ 595
5.4. Hybrid Coatings with Nanomaterials .................... 598
6. Conclusion and Future Work ................................. 599
References .................................................... 601
Index ......................................................... 607
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