Inhoudsopgave
Hoorcollege 1 ............................................................................................................................... 3
Properties of solids: .........................................................................................................................3
Bonding in solids .............................................................................................................................3
Molecular Solids: Van der Waals interactions ................................................................................4
Ionic solids..................................................................................................................................4
Covalent solids ...........................................................................................................................5
Metallic solids .............................................................................................................................5
Overview types of solids...............................................................................................................5
Ketelaar van Arkel triangle ............................................................................................................6
Structures of solids ......................................................................................................................6
Possible cristal systems ...............................................................................................................7
Close packed structures ..............................................................................................................8
Packing fraction fcc .....................................................................................................................9
Holes (voids) in close-packed structures .......................................................................................9
Octahedral holes ....................................................................................................................... 10
Tetrahedral hole ......................................................................................................................... 10
Hoorcollege 2 ..............................................................................................................................12
Atomic radius ................................................................................................................................ 12
Polymorphism metals .................................................................................................................... 13
Hardness of metals ........................................................................................................................ 13
Addition of atoms ...................................................................................................................... 13
Mixing metals (= alloys) .................................................................................................................. 14
Holes (voids) in close-packed structures ..................................................................................... 14
Ionic solids .................................................................................................................................... 14
Ideal ratios (r/R) for coordination ..................................................................................................... 15
Calculation of the ideal ratio (r/R) ............................................................................................... 15
Ionic radius ................................................................................................................................... 16
Trends: ...................................................................................................................................... 16
Perovskite structure ....................................................................................................................... 16
Hoorcollege 3 ..............................................................................................................................18
Lattice enthalpy ............................................................................................................................. 18
Born-Haber cycle ........................................................................................................................... 18
Theoretical calculation lattice enthalpy ........................................................................................... 19
Comparison experimental and theoretical lattice enthalpies ............................................................ 20
Estimating the lattice enthalpies ..................................................................................................... 20
Kapustinskii equation ..................................................................................................................... 21
Stability ......................................................................................................................................... 21
Dissociation temperatures carbonates ....................................................................................... 21
Solubility of salts ....................................................................................................................... 22
Defect chemistry ........................................................................................................................... 23
Intrinsic point defects ................................................................................................................ 23
, Kröger-Vink notation for defects .................................................................................................. 23
Special point defect ................................................................................................................... 24
Anti-site defects ........................................................................................................................ 25
Defect equilibria for intrinsic defects .......................................................................................... 25
Defect concentrations at thermal equilibrium ............................................................................. 25
Ionic conductivity of crystal ............................................................................................................ 26
Intrinsic vs. extrinsic point defects .............................................................................................. 27
Hoorcollege 4 ..............................................................................................................................28
Formation of bands (MO theory) ..................................................................................................... 28
Model conductivity metals: Drude model ........................................................................................ 29
The effect of defects and temperature on conductivity. ..................................................................... 29
Movement in electric field: drift velocity vd ....................................................................................... 29
Ohm’s law connected to the drude model ....................................................................................... 30
Semiconductors (covalent, ionic or molecular) ................................................................................ 31
Bands and bandgaps in solids ........................................................................................................ 31
Band structure for type IV semiconductors (C, Si, Ge, etc) ................................................................ 32
Type III-V (or II-VI) semiconductors .................................................................................................. 33
Conductivity intrinsic semiconductors → number of free charges n .................................................. 33
Hoorcollege 5 ..............................................................................................................................35
II–VI semiconductors (example: CdSe) ............................................................................................ 35
Energy band structure as a function of k-vector................................................................................ 35
Direct and indirect bandgap semiconductors .................................................................................. 36
Recall: Intrinsic semiconductors .................................................................................................... 37
Extrinsic semiconductors ............................................................................................................... 37
Conduction in semiconductors .................................................................................................. 38
Electrical conductivity and mobility................................................................................................. 38
Concentration of free electrons (n) or free holes (p) .......................................................................... 39
Intrinsic semiconductors ........................................................................................................... 39
Extrinsic (doped) semiconductors .............................................................................................. 39
Band diagrams for n-type and p-type semiconductors ..................................................................... 40
Extrinsic and intrinsic regions ......................................................................................................... 40
Essential for applications: diode (pn junction) .................................................................................. 41
IV curves : current I versus voltage V ................................................................................................ 42
Applications of semiconductors ..................................................................................................... 42
Solar cells ................................................................................................................................. 42
Computerchips ......................................................................................................................... 44
Photoredox Chemistry ............................................................................................................... 44
LEDS ......................................................................................................................................... 45
Quantum confinement → between molecule and bulk ................................................................ 45
,Samenvatting vaste stof chemie
Hoorcollege 1
Properties of solids:
- Electric properties
o Insulators → Semiconductors → Conductors (metals)
- Magnetic properties
o Ferro- and ferrimagnets, anti-ferromagnets, diamagnetism
- Optical properties
o Absorption (color), photolumescence, light scattering
- Surface properties
o Nanostructures: Reactivity, color (plasmon)
Bonding in solids
The type of bonding refers to the type of solid
- Molecular solids
- Ionic solids
- Covalent solids
- Metallic solids
Variations between these bonds:
- Bond strength (eV per bond or KJ/mol)
o eV → The energy needed to increase electron energy with one volt (~ 96
kJ/mol)
- Directionality
o If bonds are non-directional the structures formed are typically closed
packing tot maximize interaction
o Directional → Covalent & Molecular
non-directional → Ionic & metallic
, Molecular Solids: Van der Waals interactions
Van der Waals interactions are relatively
weak
- 50 kJ/mol → With permanent dipole
moment
- 2-20 kJ/mol → Without permanent
dipole moment
Van der Waals interactions become stronger for heavier atoms with a more extended
and polarizable electron cloud.
- e.g. increase from F2 to Cl 2 (gases) to Br2 (liquid) to I2 (solid).
Properties of molecular solids:
- Close Packed Structures (non-directional bonding)
- Low melting points and boiling points (weak interactions)
- Poor conductors of heat and electrons (no delocalized electronic states, no free
electrons
- Example: Water (or ice), iodine and xenon
Ionic solids
→ Electrostatic (Coulomb) interactions between positively and negatively charged ions
Coulomb interactions are relatievely strong → 500-2000 kJ/mol.
Distance dependence is weak → long range interactions
- not only nearest neighbors (NN) but also next nearest
neigbours (NNN) and NNNN, NNNNN etc
Properties Ionic Solids:
- Close Packed Structures (non-directional bonding)
- High melting points and boiling points (strong interactions)
- Poor conductors of heat and electrons (fully filled orbitals, no delocalized
electronic states, no free electrons)
- Example: NaCl , MgO. FeO
Hoorcollege 1 ............................................................................................................................... 3
Properties of solids: .........................................................................................................................3
Bonding in solids .............................................................................................................................3
Molecular Solids: Van der Waals interactions ................................................................................4
Ionic solids..................................................................................................................................4
Covalent solids ...........................................................................................................................5
Metallic solids .............................................................................................................................5
Overview types of solids...............................................................................................................5
Ketelaar van Arkel triangle ............................................................................................................6
Structures of solids ......................................................................................................................6
Possible cristal systems ...............................................................................................................7
Close packed structures ..............................................................................................................8
Packing fraction fcc .....................................................................................................................9
Holes (voids) in close-packed structures .......................................................................................9
Octahedral holes ....................................................................................................................... 10
Tetrahedral hole ......................................................................................................................... 10
Hoorcollege 2 ..............................................................................................................................12
Atomic radius ................................................................................................................................ 12
Polymorphism metals .................................................................................................................... 13
Hardness of metals ........................................................................................................................ 13
Addition of atoms ...................................................................................................................... 13
Mixing metals (= alloys) .................................................................................................................. 14
Holes (voids) in close-packed structures ..................................................................................... 14
Ionic solids .................................................................................................................................... 14
Ideal ratios (r/R) for coordination ..................................................................................................... 15
Calculation of the ideal ratio (r/R) ............................................................................................... 15
Ionic radius ................................................................................................................................... 16
Trends: ...................................................................................................................................... 16
Perovskite structure ....................................................................................................................... 16
Hoorcollege 3 ..............................................................................................................................18
Lattice enthalpy ............................................................................................................................. 18
Born-Haber cycle ........................................................................................................................... 18
Theoretical calculation lattice enthalpy ........................................................................................... 19
Comparison experimental and theoretical lattice enthalpies ............................................................ 20
Estimating the lattice enthalpies ..................................................................................................... 20
Kapustinskii equation ..................................................................................................................... 21
Stability ......................................................................................................................................... 21
Dissociation temperatures carbonates ....................................................................................... 21
Solubility of salts ....................................................................................................................... 22
Defect chemistry ........................................................................................................................... 23
Intrinsic point defects ................................................................................................................ 23
, Kröger-Vink notation for defects .................................................................................................. 23
Special point defect ................................................................................................................... 24
Anti-site defects ........................................................................................................................ 25
Defect equilibria for intrinsic defects .......................................................................................... 25
Defect concentrations at thermal equilibrium ............................................................................. 25
Ionic conductivity of crystal ............................................................................................................ 26
Intrinsic vs. extrinsic point defects .............................................................................................. 27
Hoorcollege 4 ..............................................................................................................................28
Formation of bands (MO theory) ..................................................................................................... 28
Model conductivity metals: Drude model ........................................................................................ 29
The effect of defects and temperature on conductivity. ..................................................................... 29
Movement in electric field: drift velocity vd ....................................................................................... 29
Ohm’s law connected to the drude model ....................................................................................... 30
Semiconductors (covalent, ionic or molecular) ................................................................................ 31
Bands and bandgaps in solids ........................................................................................................ 31
Band structure for type IV semiconductors (C, Si, Ge, etc) ................................................................ 32
Type III-V (or II-VI) semiconductors .................................................................................................. 33
Conductivity intrinsic semiconductors → number of free charges n .................................................. 33
Hoorcollege 5 ..............................................................................................................................35
II–VI semiconductors (example: CdSe) ............................................................................................ 35
Energy band structure as a function of k-vector................................................................................ 35
Direct and indirect bandgap semiconductors .................................................................................. 36
Recall: Intrinsic semiconductors .................................................................................................... 37
Extrinsic semiconductors ............................................................................................................... 37
Conduction in semiconductors .................................................................................................. 38
Electrical conductivity and mobility................................................................................................. 38
Concentration of free electrons (n) or free holes (p) .......................................................................... 39
Intrinsic semiconductors ........................................................................................................... 39
Extrinsic (doped) semiconductors .............................................................................................. 39
Band diagrams for n-type and p-type semiconductors ..................................................................... 40
Extrinsic and intrinsic regions ......................................................................................................... 40
Essential for applications: diode (pn junction) .................................................................................. 41
IV curves : current I versus voltage V ................................................................................................ 42
Applications of semiconductors ..................................................................................................... 42
Solar cells ................................................................................................................................. 42
Computerchips ......................................................................................................................... 44
Photoredox Chemistry ............................................................................................................... 44
LEDS ......................................................................................................................................... 45
Quantum confinement → between molecule and bulk ................................................................ 45
,Samenvatting vaste stof chemie
Hoorcollege 1
Properties of solids:
- Electric properties
o Insulators → Semiconductors → Conductors (metals)
- Magnetic properties
o Ferro- and ferrimagnets, anti-ferromagnets, diamagnetism
- Optical properties
o Absorption (color), photolumescence, light scattering
- Surface properties
o Nanostructures: Reactivity, color (plasmon)
Bonding in solids
The type of bonding refers to the type of solid
- Molecular solids
- Ionic solids
- Covalent solids
- Metallic solids
Variations between these bonds:
- Bond strength (eV per bond or KJ/mol)
o eV → The energy needed to increase electron energy with one volt (~ 96
kJ/mol)
- Directionality
o If bonds are non-directional the structures formed are typically closed
packing tot maximize interaction
o Directional → Covalent & Molecular
non-directional → Ionic & metallic
, Molecular Solids: Van der Waals interactions
Van der Waals interactions are relatively
weak
- 50 kJ/mol → With permanent dipole
moment
- 2-20 kJ/mol → Without permanent
dipole moment
Van der Waals interactions become stronger for heavier atoms with a more extended
and polarizable electron cloud.
- e.g. increase from F2 to Cl 2 (gases) to Br2 (liquid) to I2 (solid).
Properties of molecular solids:
- Close Packed Structures (non-directional bonding)
- Low melting points and boiling points (weak interactions)
- Poor conductors of heat and electrons (no delocalized electronic states, no free
electrons
- Example: Water (or ice), iodine and xenon
Ionic solids
→ Electrostatic (Coulomb) interactions between positively and negatively charged ions
Coulomb interactions are relatievely strong → 500-2000 kJ/mol.
Distance dependence is weak → long range interactions
- not only nearest neighbors (NN) but also next nearest
neigbours (NNN) and NNNN, NNNNN etc
Properties Ionic Solids:
- Close Packed Structures (non-directional bonding)
- High melting points and boiling points (strong interactions)
- Poor conductors of heat and electrons (fully filled orbitals, no delocalized
electronic states, no free electrons)
- Example: NaCl , MgO. FeO
