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Contents

1 1. CERAMIC FILMS AND COATINGS-AN OVERVlEW ....... John 6. Wachtman and Richard A. Haber 1 1.0 Introduction .............................. 2.0 Areas of Application of Ceramic Films and . Coatings ................................ 3 3.0 Processing of Ceramic Films and Coatings ...... 4.0 Characterization of Ceramic Films and Coatings . . 6 10 5.0 Trends in Ceramic Films and Coatings ......... 11 5.1 Diamond Coatings ...................... 5.2 High Tc Superconducting Ceramic Thin Films . . 11 5.3 The Sol-Gel Method for Making Ceramic Thin ..12 Films ............................. 13 5.4 Ceramic Thin Films on Cutting Tools ......... 5.5 Ceramic Thin Films in Semiconductor 13 Integrated Circuits ...................... 5.6 Ceramic Thin Films on Architectural and 14 Automotive Glass ...................... 15 6.0 Concept of the Present Book ................ 16 Appendix . List of Abbreviations and Acronyms .... References..................................1 8 2. CVD COATED CUTTING TOOLS ..................... Thomas E. Hale 1.0 Introduction . . . . . . . . . . . . . . . . . . . . . . . . 2.0 TIC Coatings . . . . . . . . . . . . . . . . . . . . . . . 2.1 CVD Process Conditions for TIC Coatings TIC Deposition Rate . . . . . . . . . . . . . xi

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22 23 24 25

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Contents TIC Coating-Substrate Interface ......... 26 3.0 TONCoatings ............................ 27 3.1 CVD Process Conditions for TIN Coatings ..... 27 4.0 A&O, Coatings ........................... 28 4.1 CVD Process for AI,O, Coatings ............ 29 5.0 Multi-Layer Coatings ...................... 30 5.1 TIN-TIC Type Multi-Layers ............... 31 5.2 A&O, Layer Multi-Coatings ............... 32 5.3 CVD Processes for Multi-Layer Coatings ..... 33 6.0 Coating Thickness Optimization .............. 33 6.1 Cutting Tool Wear Modes ................. 33 6.2 Influence of Thickness upon Flank Wear Resistance ........................... 34 6.3 Thickness Influence on Crater Wear Resistance and Strength ................. 36 6.4 Thickness of Multi-Layer Coatings .......... 36 7.0 Other Coatings ........................... 36 7.1 Hafnium and Zirconium Based Coatings ...... 38 Influence of Coating Composition on Machining Performance of Zr/HfCN Coatings ......................... 38 Commercial Uses of Zr/Hf Based Coatings . . 38 7.2 TiB, Coatings ......................... 39 CVD Process for TiB, Coatings .......... 39 7.3 Tungsten Carbide Coatings ............... 40 CVD Process Conditions for Tungsten Carbide Coatings ................... 40 References .................................. 41

3. WEAR RESISTANT THIN FILMS BY ION IMPLANTATION Carl J. McHargue 1.0 Introduction ............................. 2.0 Wear Processes in Ceramics ................ 2.1 Friction .............................. 2.2 Adhesive Wear ........................ 2.3 Abrasive Wear ........................ 2.4 Surface Fracture ....................... 3.0 Fundamental Processes in Ion-Solid Interactions ............................. 3.1 Range of Incident Ions ................... 3.2 Defect Production and Retention ........... 4.0 Ion Implantation of Ceramics ................ 4.1 Microstructuraland Property Changes in Ion Implantation .......................

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61 62 65 70 71

4.2 Compound Synthesis by Ion Implantation 5.0 Ion Beam Mixing ......................... .............. 6.0 Ion Beam Assisted Deposition 7.0 Summary ............................... References ..................................

4. CORROSION RESISTANT THICK FILMS BY ENAMELLING ................................... Frank A. Kuchinski 1.0 Introduction to Porcelain Enamels ............ 1.1 History of Porcelain Enamelling ............ 1.2 Reasons for Porcelain Enamelling ........... 1.3 General Applications for Porcelain Enamels .... 2.0 Porcelain Enamelling Principles and Theories ... 2.1 Porcelain Enamel Smelting and Ftitting ....... 2.2 Metals Selection and Preparation for Porcelain Enamelling .................... 2.3 Porcelain Enamel Milling ................. 2.4 Porcelain Enamel Application Methods ....... 2.5 Porcelain Enamel Bond Theories ........... 2.6 Covercoat Opacity Mechanisms ............ 2.7 Drying, Firing and Defects in Porcelain Enamels ............................ 2.8 Other Comments on Materials and Processing .......................... 3.0 Applications and Improvement Methods for Protective Porcelain Enamel Coatings ........ 3.1 Applications and Competitive Coatings ...... 3.2 Porcelain Enamel Properties Testing ........ 3.3 Enhancement of Porcelain Enamel Protective Properties ................... 4.0 Summary .............................. References .................................

77 77

78 79 81 80 82 83

87 90

92 97 100 105 105 105 111 115 118 119

131 5. PLASMA SPRAYED CERAMIC COATINGS ............ Herbert Herman, Christopher C. Berndt, and Hougong Wang 131 1.0 Introduction ............................ 132 ........................ 2.0 Plasma Spraying 135 .................... Feedstock Powders 2.1 136 ................... 2.2 The Ceramic Coating 2.3 Special Features of Plasma-Sprayed 138 Coatings ............................ 139 3.0 Alumina-Based Ceramics .................. 143 4.0 Thermal Barrier Coatings ..................

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Contents 4.1 Applications ......................... Aero-Engines ...................... Diesel Engine Applications ............. Power Generation Plant Applications ..... 4.2 Materials Properties .................... Routine Quality Control Tests ........... Mechanical Properties ................ Cyclic Thermal Testing ............... Thermal Expansion Tests ............. Acoustic Emission Tests .............. Overview of TBC’s .................. .... 5.0 Plasma Sprayed High Tc Superconductors 5.1 Spray Parameter Optimization ............ 5.2 Post-Spray Annealing and Improving Superconducting Properties .............. 5.3 Texturing: Improving the Transport Critical Current Density ....................... 5.4 Coating/Substrate lnterdiff usion ........... ...................... 6.0 Test Methodologies 6.1 Characteristics of Coatings ............... 6.2 Properties of Coatings .................. References .................................

6. OPTICAL THIN FILMS ............................ David G. Coult 1.0 Introduction ............................ 2.0 Optical Thin Film Design .................. 2.1 Antireflection Coatings .................. 2.2 Multilayer Stacks ...................... 3.0 Thin Film Materials ....................... 4.0 Deposition Process ...................... 5.0 Film Properties .......................... 5.1 Effects of Deposition Conditions ........... 5.2 Effects of Film Microstructure ............. 6.0 Attempts at Improved Properties ............ 6.1 Sputtering Techniques .................. DC Sputtering ...................... RF Sputtering ...................... Ion Beam Sputtering ................. 8.2 Evaporation Techniques ................. Activated Reactive Evaporation (ARE) Ion Plating ........................ Ion-Assisted Deposition (IAD) .......... 7.0 Conclusion .............................

143 144 145 149 149 149 150 153 157 158 158 160 161 163 168 173 175 175 177 180 189

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189 190 191 193 195 197 201 201 202 208 208 210 211 212 213 213 213 215 217

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References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 224 7. SOL-GEL DERIVED CERAMIC COATINGS ............ Brian D. Fabes, Brian J.J. Zelinski and Donald R. Uhlmann 224 1.0 Introduction ............................ 225 2.0 Sol-Gel Processing ...................... 225 ..................... 2.1 Coating Chemistry 225 Oxides ........................... 228 ....................... Non-Oxides 229 2.2 Drying and Firing ...................... 231 ............ 3.0 Coatings via Sol-Gel Processing 231 3.1 Special Solution Requirements ............ 232 .................... 3.2 Coating Techniques ..... 238 3.3 Unique Advantages of Sol-Gel Coatings 237 4.0 Applications ............................ 237 4.1 ElectricalApplications .................. 242 4.2 Optical Applications .................... 242 Antireflection Coatings ................ 244 .................. Planar Waveguides 245 Surface Patterning .................. Colored Coatings and Reflective Coatings . . 250 250 Electra-Optic Materials ............... 254 Dyes in Gels ...................... 255 ElectrochromicFilms ................. Organic/Inorganic Composites as 258 Non-Linear Optical Materials ......... 260 5.0 Outstanding Problems .................... 260 5.1 Film Cracking ........................ 263 5.2 Removal of Residual Species ............. ....... 264 5.3 Precursor Characterization and Aging 5.4 Impact of Deposition Conditions on Film 264 Properties ........................... ..... 267 5.5 Low Temperature Densification of Films 5.6 Comparison of Thin Film vs. Bulk Ceramics ... 268 268 5.7 The Nature of Sol-Gel Research .......... 269 ........................ 6.0 Future Directions 271 References ................................. 6. ELECTRONIC THICK FILM TECHNOLOGY . . . . . . . . Daniel J. Shanefield 1.0 Introduction . . . . . . . . . . . . . . . . . . . . . . . . 1.l Comparisons to Competing Technologies 2.0 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Substrates . . . . . . . . . . . . . . . . . . . . . .

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Contents 2.2 Conductors .......................... Resistors .............................. 4.0 Dielectrics ............................. 5.0 Capacitors ............................. 6.0 Future Directions ........................ References.. ............................... 3.0

290 295 296 297 297 300

9. ELECTRONIC FILMS FROM METALLO-ORGANIC 303 PRECURSORS ................................. Robert W. Vest 303 1.O Introduction ............................ 303 1.1 Overview of MOD Technology ............ 305 1.2 Historical Review ...................... 306 1.3 Advantages and Limitations .............. 307 2.0 Metallo-Organic Systems .................. 307 2.1 Selection of Compounds ................ 311 2.2 Synthesis of Compounds ................ 311 Neutralization ...................... Double Decomposition from Ammonium 311 soap .......................... Double Decomposition from Amine Soap . . 312 Metathesis Reaction from Metal Acetate ... 313 Metathesis Reaction from Metal Alkoxide . . 314 314 Metal Amine Carboxylates ............. 315 2.3 Solvent Considerations ................. 315 Requirements ...................... 316 Solvency ......................... 320 Selection Procedure ................. 321 3.0 Processing ............................. 321 3.1 Film Deposition ....................... 325 3.2 Pyrolysis ........................... 330 3.3 Annealing ........................... 334 3.4 Patterning ........................... 336 4.0 Examples of MOD Films ................... 336 4.1 Conductor Films ...................... 336 Metals ........................... 337 Oxides ........................... 338 4.2 Resistor Films ........................ 339 4.3 Dielectric Films ....................... 339 Linear Dielectrics ................... 339 Ferroelectrics ...................... 341 5.0 Summary .............................. 343 References .................................

Contents 10. CHEMICAL CHARACTERIZATION TECHNIQUES FOR THIN FILMS ................................... Robert Caracciolo 1.0 Introduction ............................ 2.0 X-Ray Photoelectron Spectroscopy (XPS) ..... 2.1 Experimental Considerations ............. 2.2 Radiation Sources ..................... 2.3 Electron Energy Analyzers ............... 2.4 The XPS Spectrum .................... 2.5 Insulators ........................... 2.8 Sampling Depth in XPS ................. 2.7 The ‘Chemical Shift in XPS .............. 3.0 Auger Electron Spectroscopy (AES) .......... 3.1 General Theory ....................... 3.2 Sampling Depth in AES ................. 3.3 The Chemical Shift in AES ............... 4.0 Backscattering Spectrometry (RBS and ISS) .... 4.1 Kinematics of the Elastic Collision .......... 4.2 Energy Loss ......................... 4.3 Depth Profiles by FIBS .................. 4.4 Ion Scattering Spectroscopy .............. 5.0 Secondary Ion Mass Spectroscopy (SIMS) ..... 6.0 Summary .............................. References.. ............................... 11. HIGH T, SUPERCONDUCTING THIN FILMS ............ X. D. Wu, A. ham, T. Venkatesan 1.0 Introduction ............................ 2.0 Vacuum Deposition ...................... 2.1 Thermal and Electron Beam Evaporation ..... 2.2 Sputtering ........................... 2.3 Ion Beam Deposition ................... 2.4 Pulsed Laser Deposition ................ 2.5 Molecular Beam Epitaxy ................ 2.6 Chemical Vapor Deposition (CVD) and Organometallic CVD ................... 3.0 Non-Vacuum Deposition .................. 3.1 Liquid-Phase Epitaxy .................. 3.2 Plasma Spray ........................ 3.3 Solution Method ...................... 4.0 Comparison of the Thin Film Techniques ...... 5.0 Other High T, Superconductors ............. 6.0 Substrate .............................. 6.1 Lattice Constant ......................

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348 348 350 350 353 354 355 355 357 362 363 364 367 367 369 369 370 371 374 374 379 380 382 382 387 387 390 391 392 393 394 395 395 396 396 396 399 399 399

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Contents 6.2 Thermal Expansion Coefficient ............ 6,3 Reactivity ........................... 6.4 DielectricConstant .................... 7.0 Applications ............................ Wires and Tapes ................... ElectromagneticShielding ............. Passive Microwave Components ........ Discrete Devices .................... Interconnection ..................... 8.0 Conclusion ............................. References .................................

12. CHEMICAL VAPOR DEPOSITED DIAMOND ............ Albert Feldman, Edward N. Farabaugh, and Lawrence H. Robins 1.0 Introduction ............................ 2.0 Historical Background .................... 3.0 Methods of Deposition .................... 4;O Growth and Quality of CVD Diamond ......... 5.0 Thermal Properties of CVD Diamond ......... 8.0 Optical Properties ........................ 7.0 Mechanical Properties .................... 8.0 Polishing CVD Diamond ................... 9.0 Conclusion ............................. References.. ............................... INDEX

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