III/42 Physics of Covered Solid Surfaces 

A
: Adsorbed Layers on Surfaces 
Part 1
: Adsorption on Surfaces and Surface Diffusion of Adsorbates 
1	
Introduction to physical and chemical properties of adlayer/substrate systems (H.P. BONZEL).......................................................................... 1

1.1	
General background .................................................................... 1

1.2	
Surface thermodynamics ................................................................ 3


1.3	
Kinetics of adsorption/desorption and adsorption isotherms .............................. 9

1.3.1	
Thermal rates of adsorption/desorption .................................................. 9

1.3.2	
Isotherms.............................................................................. 15

1.3.3	
Non-thermal desorption ................................................................ 16


1.4	
Physical and chemical properties of adsorbed species ................................... 17

1.4.1	
Sticking coefficient .................................................................... 17

1.4.2	
Heat of adsorption ..................................................................... 18

1.4.3	
Orientation of adsorbed molecules ..................................................... 19

1.4.4	
Surface diffusion coefficients .......................................................... 22

1.4.5	
Long-range order ...................................................................... 25

1.4.6	
Vibrational frequencies ................................................................ 27

1.4.7	
Structure and adsorption site ........................................................... 30


1.4.8	
Molecular orbital energies, dispersion and 2d band structure ............................ 32

1.4.9	
Core level binding energies ............................................................ 34

1.4.10	
Two-dimensional phase diagrams and order-disorder transitions......................... 38

1.4.11	
Chemical state ......................................................................... 39

1.4.12	
Influence of surface structural defects .................................................. 40


1.4.13	
Influence of chemical surface additives ("promotors") .................................. 42

1.5	
Adsorbate-induced changes of substrate properties ...................................... 44

1.5.1	
Changes of structure: surface relaxation and surface reconstruction ...................... 44


1.5.2	
Changes of electron work function ..................................................... 46

1.5.3	
Electron binding energy changes, core and valence levels ............................... 48

1.5.4	
Changes of surface free energy and surface stress ....................................... 50


1.5.5	
Changes of surface phonon dispersion .................................................. 53

1.5.6	
Changes of surface optical properties ................................................... 54


References for 1 ....................................................................... 59

2	
Characterization of adsorbate overlayers: measuring techniques 
(CH. WLL) ......................................................see subvolume III/42A2 
3	
Data: Adsorbate properties ............................................................. 67

3.1	
Adsorption of noble gases.............................................................. 67


3.1.1	
Noble gases on metals and semiconductors (P. ZEPPENFELD) ............................ 67

3.1.1.1	
Introduction ........................................................................... 67

3.1.1.1.1	
General remarks ....................................................................... 67


3.1.1.1.2	
The interaction of noble gases at surfaces............................................... 67

3.1.1.1.3	
Sticking and accomodation............................................................. 68

3.1.1.1.4	
Adsorption energies ................................................................... 69


3.1.1.1.5	
Desorption energies and desorption kinetics ............................................ 70

3.1.1.1.6	
Structure and phase diagram ........................................................... 70

3.1.1.1.7 
Adsorption site ........................................................................71

3.1.1.1.8 
Electronic structure ....................................................................72

3.1.1.1.9 
Diffusion kinetics......................................................................73

3.1.1.1.10 
Lattice dynamics.......................................................................73

3.1.1.2 
Data...................................................................................75


3.1.1.2.1 
Sticking coefficients of the noble gases .................................................76

3.1.1.2.2 
Binding energies, thermodynamic quantities and phase diagrams ........................77

3.1.1.2.3 
Monolayer structures and phase diagrams...............................................82


3.1.1.2.4	
Electronic structure ....................................................................87

3.1.1.2.5	
Surface diffusion coefficients ..........................................................94


3.1.1.2.6	
Vibration frequencies and phonon dispersion ...........................................95

Figures for 3.1.1 .......................................................................96

References for 3.1.1 ................................................................. 111



3.1.2	
Noble gases on graphite, lamellar halides, MgO and NaCl (M. BIENFAIT) .............. 117


3.1.2.1	
Thermodynamics .................................................................... 117

3.1.2.1.1	
Rare gases adsorbed on graphite (0001) ............................................. 117

3.1.2.1.1.1	
Xenon on graphite ................................................................... 117

3.1.2.1.1.2	
Krypton on graphite ................................................................. 117

3.1.2.1.1.3	
Argon on graphite ................................................................... 118

3.1.2.1.1.4	
Neon on graphite .................................................................... 118

3.1.2.1.1.5	
Rare gas mixtures on graphite ........................................................ 118

3.1.2.1.1.6	
Helium on graphite .................................................................. 118

3.1.2.1.2	
Rare gases on BN.................................................................... 118


3.1.2.1.3	
Rare gases on lamellar halide surfaces ................................................ 118

3.1.2.1.4	
Rare gases on MgO(100) and NaCl(100) ............................................ 119


3.1.2.2	
Structure ............................................................................ 119

3.1.2.2.1	
Xenon on graphite ................................................................... 119

3.1.2.2.2	
Krypton on graphite ................................................................. 119

3.1.2.2.3	
Argon on graphite ................................................................... 119

3.1.2.2.4	
Neon on graphite .................................................................... 120

3.1.2.2.5	
Rare gas mixtures on graphite ........................................................ 120

3.1.2.2.6	
Rare gas on lamellar halides.......................................................... 120


3.1.2.2.7	
Rare gases on MgO(100) and NaCl(100) ............................................ 120

3.1.2.3	
Influence of structural defects ........................................................ 120

3.1.2.3.1	
Thermodynamics and phase transitions ............................................... 120

3.1.2.3.2	
Structure ............................................................................ 120

3.1.2.4	
Vibrations ........................................................................... 121

3.1.2.5	
Kinetics of adsorption and desorption ................................................ 121

Figures for 3.1.2 ..................................................................... 122

References for 3.1.2 ................................................................. 128



3.2	
Adsorption of alkali metals........................................................... 131


3.2.1	
Alkali metals on metals (R.D. DIEHL, R. McGRATH) .................................. 131

3.2.1.1	
Introduction ......................................................................... 131

3.2.1.2	
Adsorbed alkali metals: Data ......................................................... 132

3.2.1.2.1	
Adsorption bonds.................................................................... 132

3.2.1.2.2	
Work function changes .............................................................. 133

3.2.1.2.3	
Electronic structure of adatoms....................................................... 138

3.2.1.2.4	
Heats of adsorption/desorption ....................................................... 140

3.2.1.2.5	
Adatom vibrational frequencies ...................................................... 141


3.2.1.2.6	
Adsorption sites and bond lengths (commensurate structures) ........................ 143

3.2.1.2.7	
Incommensurate overlayer rotations .................................................. 147

3.2.1.2.8	
Monolayer saturation lattice parameters .............................................. 149

3.2.1.2.9	
Condensation transition parameters................................................... 150

3.2.1.2.10	
Two-dimensional phase diagrams .................................................... 152

3.2.1.2.11	
Adsorbate substrate intermixing ...................................................... 154

Figures for 3.2.1 ..................................................................... 157

References for 3.2.1 ................................................................. 169




3.2.2	
Alkali metals on semiconductors (E.G. MICHEL, R. MIRANDA) ........................ 179

3.2.2.1	
Introduction ......................................................................... 179

3.2.2.1.1	
Historical layout and general background ............................................. 179

3.2.2.1.2	
Alkali metal/semiconductor interfaces ................................................ 180


3.2.2.1.3	
Experimental techniques ............................................................. 180

3.2.2.2	
Adsorption on covalent semiconductors: physical and chemical properties ............. 180

3.2.2.2.1	
Adsorption site, structure and long range order ....................................... 181

3.2.2.2.2	
Adsorption energy and saturation coverage ........................................... 185

3.2.2.2.3	
Metallization and electronic structure................................................. 186

3.2.2.2.4	
Overlayer plasmons and electron excitations .......................................... 189

3.2.2.2.5	
Core level binding energies and components.......................................... 189

3.2.2.2.6	
Chemical state and nature of the bond ................................................ 191

3.2.2.3	
Adsorption on III-V semiconductors: physical and chemical properties ................ 193

3.2.2.3.1	
Long range order, structure and adsorption site ....................................... 193

3.2.2.3.2	
Metallization and electronic structure................................................. 193

Figures for 3.2.2 ..................................................................... 195

References for 3.2.2 ................................................................. 210




3.3	
Adsorption of metals................................................................. 217

3.3.1	
Metals on metals (H. BRUNE) ........................................................ 217

3.3.1.1	
Introduction ......................................................................... 217

3.3.1.2	
Adsorption energies ................................................................. 218

3.3.1.3	
Atom condensation .................................................................. 225

3.3.1.3.1	
Transient mobility ................................................................... 225

3.3.1.3.2	
Neighbor-driven mobility ............................................................ 226

3.3.1.4	
Adsorbate  adsorbate interactions ................................................... 227

3.3.1.4.1	
Dimer bond energies................................................................. 228

3.3.1.4.2	
Long range interactions .............................................................. 230

3.3.1.5	
Overlayer structure .................................................................. 231

Acknowledgements .................................................................. 243

Figures for 3.3.1 ..................................................................... 244

References for 3.3.1 ................................................................. 251




3.3.2	
Metals on semiconductors (V.G. LIFSHITS, K.OURA, A.A. SARANIN, A.V. ZOTOV) ............................... 259

List of Abbreviations ................................................................ 259

3.3.2.1	
Introduction ......................................................................... 260

3.3.2.1.1	
Outline .............................................................................. 260


3.3.2.1.2	
Metal adsorption and surface phase formation ........................................ 261

3.3.2.1.3	
Notations for surface structures and adsorption sites .................................. 263


3.3.2.1.4	
Preparation .......................................................................... 265

3.3.2.1.5	
Techniques of surface characterization ............................................... 267

3.3.2.2	
List of structures..................................................................... 268

3.3.2.3	
Metallic adsorbates on silicon ........................................................ 284

3.3.2.3.1	
Ag (Silver) on Si .................................................................... 284

3.3.2.3.2	
Al (Aluminum) on Si ................................................................ 292

3.3.2.3.3	
As (Arsenic) on Si ................................................................... 299

3.3.2.3.4	
Au (Gold) on Si ..................................................................... 303

3.3.2.3.5	
Ba (Barium) on Si ................................................................... 310

3.3.2.3.6	
Bi (Bismuth) on Si................................................................... 311

3.3.2.3.7	
Ca (Calcium) on Si .................................................................. 316

3.3.2.3.8 
Ce (Cerium) on Si ................................................................... 317

3.3.2.3.9 
Co (Cobalt) on Si .................................................................... 317

3.3.2.3.10 
Cu (Copper) on Si ................................................................... 320

3.3.2.3.11 
Eu (Europium) on Si ................................................................. 324

3.3.2.3.12 
Ga (Gallium) on Si .................................................................. 324

3.3.2.3.13 
Gd (Gadolinium) on Si............................................................... 331

3.3.2.3.14 
Hg (Mercury) on Si .................................................................. 331

3.3.2.3.15 
In (Indium) on Si .................................................................... 332

3.3.2.3.16 
Mg (Magnesium) on Si .............................................................. 340

3.3.2.3.17 
Ni (Nickel) on Si .................................................................... 342

3.3.2.3.18 
Pb (Lead) on Si...................................................................... 347

3.3.2.3.19 
Pd (Palladium) on Si................................................................. 353

3.3.2.3.20 
Pt (Platinum) on Si .................................................................. 354

3.3.2.3.21 
Sb (Antimony) on Si ................................................................. 355

3.3.2.3.22 
Sm (Samarium) on Si ................................................................ 362

3.3.2.3.23 
Sn (Tin) on Si ....................................................................... 362

3.3.2.3.24 
Sr (Strontium) on Si ................................................................. 368

3.3.2.3.25 
Te (Tellurium) on Si ................................................................. 369

3.3.2.3.26 
Tl (Thallium) on Si .................................................................. 370

3.3.2.3.27 
Yb (Ytterbium) on Si ................................................................ 372

3.3.2.4 
Metallic adsorbates on germanium ................................................... 372

3.3.2.4.1 
Ag (Silver) on Ge.................................................................... 372

3.3.2.4.2 
Al (Aluminum) on Ge................................................................ 374

3.3.2.4.3 
As (Arsenic) on Ge .................................................................. 374

3.3.2.4.4 
Au (Gold) on Ge..................................................................... 375

3.3.2.4.5 
Bi (Bismuth) on Ge .................................................................. 376

3.3.2.4.6 
Cu (Copper) on Ge .................................................................. 377

3.3.2.4.7 
Ga (Gallium) on Ge.................................................................. 378

3.3.2.4.8	
In (Indium) on Ge ................................................................... 381

3.3.2.4.9	
Pb (Lead) on Ge ..................................................................... 384

3.3.2.4.10	
Sb (Antimony) on Ge ................................................................ 389

3.3.2.4.11	
Sn (Tin) on Ge ...................................................................... 392


References for 3.3.2 ................................................................. 396

3.4	
Non-metallic atomic adsorbates on metals and semiconductors ....see subvolume III/42A3 
3.4.1	
Chemisorbed hydrogen on metals and semiconductors 
(K. CHRISTMANN) ................................................see subvolume III/42A3

3.4.2	
C, N, O on metals and semiconductors 
(H. OVER) .......................................................see subvolume III/42A3

3.4.3	
Halogens on metals and semiconductors (E.I. ALTMAN) .............................. 421


3.4.3.1	
Introduction ......................................................................... 421

3.4.3.2	
General features of halogen adsorption ............................................... 422

3.4.3.3	
Halogen adsorption on metal surfaces ................................................ 423

3.4.3.3.1	
FCC transition metals ................................................................ 423

3.4.3.3.1.1	
FCC (100) surfaces .................................................................. 423

3.4.3.3.1.2	
FCC (111) surfaces .................................................................. 426

3.4.3.3.1.3	
FCC (110) surfaces .................................................................. 429

3.4.3.4	
BCC transition metals................................................................ 431

3.4.3.4.1	
BCC (100) surfaces.................................................................. 432

3.4.3.4.2	
BCC (110) surfaces.................................................................. 434

3.4.3.4.3	
BCC (111) surfaces.................................................................. 437

3.4.3.5	
HCP transition metals................................................................ 438

3.4.3.6	
Semiconductor surfaces .............................................................. 439

3.4.3.6.1	
Diamond cubic semiconductors ...................................................... 439


3.4.3.6.1.1 Diamond cubic (100) surfaces........................................................ 439

3.4.3.6.1.2 Diamond cubic (111) surfaces........................................................ 440

3.4.3.6.2	Zinc blende III-V semiconductor surfaces ............................................ 441

3.4.3.6.2.1	Zinc blende (110) surfaces ........................................................... 441

3.4.3.6.2.2	Zinc blende (100) surfaces ........................................................... 441

3.4.3.6.2.3	Zinc blende (111) surfaces ........................................................... 442
Figures for 3.4.3 ..................................................................... 443
References for 3.4.3 ................................................................. 450

3.4.4	P, S, As, Sb on metals and semiconductors

(M. ENACHESCU, M. SALMERON) .................................see subvolume III/42A3

3.5	Surface segregation of atomic species (non-metal on metal)
(H.-J. GRABKE, CH. UEBING, H. VIEFHAUS) .......................see subvolume III/42A3

3.6	Molecules on graphite, BN, MgO (except noble gases)

(H. WIECHERT, J. SUZANNE) ......................................see subvolume III/42A3

3.7	Molecular diatomic adsorbates on metals and semiconductors ......see subvolume III/42A3

3.7.1	CO and N2 on metals

(A. FHLISCH, A. NILSSON, H.P. BONZEL) .........................see subvolume III/42A3

3.7.2	NO, CN, O2 on metals

(W.A. BROWN) ..................................................see subvolume III/42A3

3.7.3	Diatomic molecules on alloys

(B. E. NIEUWENHUYS) ............................................see subvolume III/42A3

3.7.4	Diatomic molecules on semiconductors

(K. HORN)........................................................see subvolume III/42A3

3.8	Molecular polyatomic adsorbates on metals and semiconductors....see subvolume III/42A3

3.8.1	H2O and OH on metals

(G. PIRUG) ......................................................see subvolume III/42A3

3.8.2	H2O and OH on semiconductors

(W. JAEGERMANN, T. MAYER) ...................................see subvolume III/42A3

3.8.3	NH3 and PF3 on metals and semiconductors

(E. HASSELBRINK) ...............................................see subvolume III/42A3

3.8.4	CO2, NO2, SO2, OCS, N2O, O3

(B.E. KOEL) 	.....................................................see subvolume III/42A3

3.8.5	Substituted hydrocarbons on metals

(W.T. TYSOE, D.R. MULLINS) ....................................see subvolume III/42A3

3.8.6	Linear hydrocarbons and CH4 on metals and semiconductors

(G. SOMORJAI, G. RUPPRECHTER) .................................see subvolume III/42A3

3.8.7	Cyclic hydrocarbons on metals and semiconductors

(G. HELD, H.P. STEINRCK) ......................................see subvolume III/42A3

3.8.8	Oxygenated hydrocarbons on metals and semiconductors

(J. VOHS) ........................................................ see subvolume III/42A3

3.8.9	Halogen-substituted hydrocarbons on metals and semiconductors

(J. FIEBERG, J.W. WHITE) ........................................see subvolume III/42A3

3.8.10	Polyatomic chain-like hydrocarbons on metals and semiconductors

(M. GRUNZE) ....................................................see subvolume III/42A3

3.8.11	Large aromatic adsorbates on metals and semiconductors

(M. SOKOLOWSKI, E. UMBACH) ...................................see subvolume III/42A3

3.9	Adsorption on oxides

(H. KUHLENBECK, H.J. FREUND) ..................................see subvolume III/42A3

3.10	Adsorption on alkali halides

(J. HEIDBERG) ...................................................see subvolume III/42A3

3.11	Surface diffusion on metals, semiconductors, and insulators

(E.G. SEEBAUER, M.Y.L. JUNG)...................................................... 455

3.11.1	Introduction ......................................................................... 455

3.11.1.1 
General remarks ..................................................................... 455

3.11.1.2 
Intrinsic and mass transfer diffusion .................................................. 456

3.11.2 
Methodology ........................................................................ 458

3.11.2.1 
Experimental techniques ............................................................. 458

3.11.2.1.1 
Single-atom imaging ................................................................. 458

3.11.2.1.2 
Field emission ....................................................................... 459

3.11.2.1.3 
Electron diffraction .................................................................. 459

3.11.2.1.4 
Chemical state relaxation ............................................................ 460

3.11.2.1.5 
Spin axis relaxation .................................................................. 460

3.11.2.1.6 
Profile evolution..................................................................... 461

3.11.2.1.7 
Capillarity-driven effects............................................................. 463

3.11.2.1.8 
Island growth........................................................................ 463

3.11.2.1.9 
Miscellaneous ....................................................................... 464


3.11.2.2 
Classification of experimental techniques ............................................. 464

3.11.2.3 
Computational techniques............................................................ 466

3.11.2.3.1 
Molecular dynamics ................................................................. 466

3.11.2.3.2 
Monte Carlo method ................................................................. 467

3.11.2.3.3 
Ab initio methods .................................................................... 467

3.11.2.3.4 
Classical interatomic potentials....................................................... 467

3.11.2.3.5 
Semi-empirical potentials ............................................................ 469

3.11.2.3.6 
Quantum mechanical potentials ...................................................... 470

3.11.3 
Tables of data ....................................................................... 470

3.11.3.1 
Commentary to tables................................................................ 470

3.11.3.2 
Surface diffusion tables .............................................................. 472

3.11.3.2.1 
Thermal diffusion in vacuum......................................................... 472

3.11.3.2.1.1 
Intrinsic diffusion.................................................................... 472

3.11.3.2.1.2 
Mass transfer diffusion............................................................... 486

3.11.3.2.1.3 
Impurity-influenced diffusion ........................................................ 489

3.11.3.2.2 
Non-thermal diffusion ............................................................... 490

3.11.3.2.3 
Diffusion under liquids .............................................................. 491

3.11.3.2.4 
Computational data .................................................................. 492

3.11.4 
Discussion and correlations .......................................................... 495

3.11.4.1 
Thermal diffusion in vacuum......................................................... 495

3.11.4.1.1 
Intrinsic diffusion on metals.......................................................... 495


3.11.4.1.2 
Intrinsic diffusion on semiconductors................................................. 496

3.11.4.1.3 
Intrinsic diffusion on insulators....................................................... 497

3.11.4.1.4 
Mass transfer diffusion on metals..................................................... 497


3.11.4.1.5 
Mass transfer diffusion on semiconductors............................................ 498

3.11.4.1.6 
Mass transfer diffusion on insulators ................................................. 498

3.11.4.1.7 
Comparison of mass transfer diffusion on various substrates........................... 499

3.11.4.1.8 
Adsorbate concentration dependence ................................................. 499


3.11.4.1.9 
Impurity-influenced diffusion ........................................................ 500

3.11.4.2 
Non-thermal diffusion ............................................................... 500

3.11.4.2.1	
Tunneling diffusion .................................................................. 500


3.11.4.2.2	
Ion- and photon-influenced diffusion ................................................. 500

3.11.4.3	
Diffusion under aqueous liquids ...................................................... 501

3.11.4.4	
Computational results................................................................ 501

Acknowledgements .................................................................. 501

Figures for 3.11 ..................................................................... 502




Special references: review articles for 3.11 ........................................... 517

References for 3.11 .................................................................. 519

3.12	
Dynamics of activated adsorption 

(A.C. LUNTZ) ....................................................see subvolume III/42A3

4 Data: adsorbate-induced changes of substrate properties ...........see subvolume III/42A2

4.1 Surface structure on metals and semiconductors 
(M.A. VAN HOVE, P.R. WATSON, K. HERMANN) ..................see subvolume III/42A2


4.2 Electron work function of metals and semiconductors 
(K. JAKOBI) ......................................................see subvolume III/42A2


4.3 Electron binding energy of metals and semiconductors 
(R. DENECKE, N. MARTENSSON, A. NILSSON) .....................see subvolume III/42A3


4.4 Surface free energy and surface stress 
(D. SANDER, H. BACH) ...........................................see subvolume III/42A2


4.5 Surface phonon dispersion 
(M. ROCCA) ......................................................see subvolume III/42A2


4.6 Surface optical properties 
(N. ESSER, W. RICHTER) ..........................................see subvolume III/42A3


