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Contents
1. Introduction........................................................................................................................................................................... 432
2. Fundamental aspects of metal¨Coxide interaction ......................................................................................................................... 434
2.1. Physics and chemistry of heterophase interface contacts .................................................................................................... 434
2.1.1. Physics at metal¨Csemiconductor interfaces .......................................................................................................... 434
2.1.2. Chemistry at metal¨Csemiconductor interfaces....................................................................................................... 435
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2.2. Electronic interaction of metals with oxides ¡ª charge redistribution ................................................................................... 436
2.2.1. Local charge redistribution ............................................................................................................................... 436
2.2.2. Space charge transfer ....................................................................................................................................... 437
2.3. Chemical interaction of metals with oxides ¡ª mass transport............................................................................................. 438
2.3.1. Chemical interactions at metal/oxide interfaces .................................................................................................... 438
2.3.2. Thermodynamic considerations .......................................................................................................................... 440
2.3.3. Kinetic consideration ....................................................................................................................................... 441
2.4. Interplay between electronic and chemical interactions ...................................................................................................... 442
2.4.1. Cabrera¨CMott theory in solid¨Cgas interface reactions ............................................................................................ 442
2.4.2. Cabrera¨CMott theory in solid¨Csolid interface reactions .......................................................................................... 443
2.4.3. Generalized Cabrera¨CMott theory in interface reactions ........................................................................................ 445
3. Experimental methods ............................................................................................................................................................ 445
3.1. Preparation of model systems ........................................................................................................................................ 446
3.1.1. Oxide surfaces ................................................................................................................................................ 446
3.1.2. Metal overlayers on oxide surfaces ..................................................................................................................... 447
3.1.3. Inverse model systems...................................................................................................................................... 449
3.2. Characterization techniques........................................................................................................................................... 449
3.2.1. Electron-based spectroscopy .............................................................................................................................. 449
3.2.2. Scanning probe techniques ............................................................................................................................... 450
3.2.3. Transmission electron microscopy ...................................................................................................................... 451
3.2.4. Other techniques ............................................................................................................................................. 452
4. Interaction of metals with mixed conducting oxides .................................................................................................................... 453
4.1. Metals on TiO2 ............................................................................................................................................................ 453
4.1.1. TiO2 surfaces .................................................................................................................................................. 453
4.1.2. TiO2 bulk defect chemistry ............................................................................................................................... 455
4.1.3. Metal¨CTiO2 interactions ................................................................................................................................... 457
4.2. Metals on SrTiO3 ......................................................................................................................................................... 463
4.2.1. SrTiO3 surfaces............................................................................................................................................... 463
4.2.2. SrTiO3 bulk defect chemistry............................................................................................................................ 465
4.2.3. Metal¨CSrTiO3 interactions................................................................................................................................ 467
5. Interaction of metals with insulating oxides............................................................................................................................... 471
5.1. Metals on Al2O3 .......................................................................................................................................................... 472
5.1.1. -Al2O3 surfaces ............................................................................................................................................ 472
5.1.2. Metal interactions with bulk Al2O3 .................................................................................................................... 475
5.1.3. Metal interactions with alumina films.................................................................................................................. 476
5.2. Metals on MgO............................................................................................................................................................ 477
5.2.1. Metal interactions with bulk MgO ...................................................................................................................... 477
5.2.2. Metal interactions with MgO films ..................................................................................................................... 480
5.3. Metals on SiO2 ............................................................................................................................................................ 480
5.3.1. Metal interactions with bulk SiO2....................................................................................................................... 480
5.3.2. Metal interactions with silica films ..................................................................................................................... 482
6. Summary .............................................................................................................................................................................. 484
Acknowledgements ................................................................................................................................................................ 485
References ............................................................................................................................................................................ 485
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