강의자료 저작권 관련 유의사항 안내

“본 강의자료는 연세대학교 학생들을 위해

수업목적으로 제작ㆍ게시된 것이므로 수업목적 외
용도로 사용할 수 없으며, 다른 사람들과 공유할 수
없습니다. 위반에 따른 법적 책임은 행위자 본인에게
있습니다.”

나. 금지되는 행위
(1) 위와 같이 내려 받은 강의자료를 수강생 본인 외 제3자에게 배포(출력물의 경우), 전송(파일
업로드)하는 행위
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하는 복제방지조치를 무력화하는 행위. 예컨대 강의자료가 게시된 와이섹 등에 접근할 수 있는
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저작물이 포함되어 있을 수 있고, 그것이 외국에서 접근가능한 상태가 되기 때문입니다. 따라서,
강의자료를 타인과 공유하거나 전송 및 공개하는 행위를 하여서는 안 됩니다.
Materials Inorganic Chemistry

Chapter 7. The Crystalline Solid

State
 Formulas and Structures
- A macroscopic crystal can reasonably be described as a single molecule
with MOs extending throughout.
- Crystals vs. amorphous materials
- Unit cell: crystalline solids have atoms,
ions, molecules packed in regular
geometric arrays with the structural unit
called unit cell.

7 Crystal Systems
14 Bravais Lattices
 Formulas and Structures
Unit cell: the smallest section which, by translation along its edges,
generates the entire structure.
- There are four types of locations or lattice positions
: corners (1/8), edge centers (1/4), face centers (1/2),
internal (1) position
Lattice points: The positions of atoms
expressed as fractions of the unit cell
dimensions
Coordination number: The number of surrounding atoms

Cubic Lattice Types

1. Simple cubic: 1atom per unit cell (0,0,0)
2. Body-centered cubic lattice (bcc): 2 atoms per unit cell (0,0,0), (0.5,0.5,0.5)
3. Face-centered cubic lattice (fcc): 4 atoms per unit cell (cubic closest
packing) (0,0,0), (0.5,0.5,0), (0.5,0,0.5), (0,0.5,0.5)
- Larger ions form a sublattice of basic structures and smaller ions then
occupy octahedral (CN = 6) and/or tetrahedral (CN = 4) holes.
 Close-Packed Structures
- Hexagonal close packing (hcp) ABAB
- Cubic close packing (ccp) ABCABC = face centered cubic
- In both structures, there are two tetrahedral holes and one octahedral hole
per atom. In both structures, the spheres
occupy 74.0% of the total volume.
- The minimal unit cell of hcp is smaller
than the hexagonal prism.
 Close-Packed Structures
- Cubic close packing (ccp) ABCABC = face centered cubic
- The tetrahedral holes are occupied by ions with radius 0.225r.
- The octahedral holes occupied by ions with radius 0.414r.
- In ionic crystals, larger ions form close packing structure and smaller ions
occupy octahedral holes and tetrahedral holes.
- In metallic crystal, most metals crystallize
in bcc, ccp, and hcp structures.
- Metals have high conductivity of electricity
and heat.
- Some metals are soft and easily deformed
by pressure, whereas the others are hard and
brittle.
- Most metal can be shaped by hammering
or bending. The atoms can slide over each
other and realign into new structures with
nearly the same energy.
: dislocation
 Structures of Binary Compounds
Occupation of holes in close packing structure
1. The relative sizes of the atoms or ions (radius ratio r+/r-)
2. The relative numbers of cations and anions
- Diamond has a similar structure to
zinc blende structure.

- NaCl structure:
Cl-(ccp), Na+(Oh)

- CsCl structure:
Cl-(simple cubic),
Cs+(CN=8)
 Structures of Binary Compounds
- Zinc blende ZnS structure:
S2-(ccp), Zn2+(Td)
- Wurzite ZnS structure:
S2-(hcp), Zn2+(Td)
- Fluorite CaF2 structure:
Ca2+(ccp), F-(Td)
- Antifluorite structure:
alkali metal oxides/sulfides, O2-(ccp), Li+(Td)
 Structures of Binary Compounds
- NiAs structure:
Ni(Oh), As(Trigonal prism)
- Rutile TiO2 structure:
Distorted TiO6 octahedra that form
columns by sharing edges.
- More complex compounds:
: It is possible to form many compounds
by substitution of one ion for another
in part of the locations in a lattice.
- The substitution of ions with different
charges and sizes leave vacancies.
- When the anions are complex and
nonspherical, the crystal structure are
distorted.
- A large number of salts adopt the calcite structure.
 Radius Ratio
Relative Size of Ions: Radius Ratios
: Radius ratio = R.R. = r+/r-
- For electrostatic attractions to be maximized, each cation must be in
contact with four anions in the plane.
- If the radius ratio is sufficiently large,
then the cation can be in contact
with all anions and also separate
them from one another.

- For any radius ratio less than 0.414,

the stability of the rocksalt lattice is
diminished.
- Most ionic salt maintain some degree of covalent character. This
covalent bonding involves p orbital overlap, and therefore is most
effective for M-X-M angle of 90o. (preference for NaCl structure)
 Radius Ratio
- There are also compounds in which the cations are larger than the anions.
In these cases, r-/r+ determines the CN of the anions in the holes of a
cation lattice.
- If the ions are nearly equal in size, a cubic arrangement of anions with the
cations in the body center results, as in CsCl structure with CN=8.
Thermodynamics of Ionic Crystal Formation
- Born-Haber Cycle is the process of considering the series of component
reactions that can be imagined as the individual steps in compound
formation.

- Historically such calculations were used to determine electron affinity.

- The complete cycle can be used to determine more accurate lattice

enthalpies.
Lattice Energy and the Madelung Constant
- The lattice energy can be calculated by the summation of the
electrostatic energy between each ion pair.

- The sum of all these geometric factors carried out until the interactions
become infinitesimal is called the Madelung constant (M).

- Repulsion between close neighbors is a more complex function,

frequently involving an inverse six- to twelfth-power dependence on
distance.
- The Born-Mayer equation: attraction + repulsion
- The lattice enthalpy
Dn is the change in the number of gas-phase particles on formation of
the crystal DnRT is small. DHxtal ~ DU
Lattice Energy and the Madelung Constant
Madelung constant (M) depends only on the structure type not on
the type of component atoms or ions.

M
 Solubility, Ion Size, and HSAB
- It is possible to estimate the solvation effects of many ions by comparing
similar measurements on a number of difference compounds.

- Many factors are involved in the thermodynamics of solubility, including

ionic size and charge, the hardness and softness of the ions, the crystal
structure of the solid, and the electronic structure of each ion.
- Compounds formed of two large ions or of two small ions are less soluble
than compounds containing one large ion and one small ion.

- The reaction LiI(s) + CsF(s) -> CsI(s) + LiF(s) is exothermic because of

the large enthalpy of LiF.
Molecular Orbitals and Band Structure
- When n atoms are used, the same approach results in n MOs.
- The lowest energy MO would have no nodes, and the highest energy
MO would have n-1 nodes.
- Because the number of atoms is large, the number of orbitals and
energy levels with closely spaced energies is also large, resulting in a
band of orbitals of similar energy.
- Valence band (VB): the highest energy band containing electrons
- Conduction band (CB): the next higher empty band
- Bandgap: a large energy difference between VB and CB
Molecular Orbitals and Band Structure
- Insulator: a large bandgap energy
- Metal: no bandgap with partially filled orbitals, good conductor of
electricity and heat
- Hole: electron vacancy
- The concentration of energy levels within bands is described as the
density of states N(E)
- An insulator with a filled VB and a metal with partially filled VB.
- When an electric potential is applied, some of the electrons can move to
slightly higher energies, leaving vacancies in the lower part of the band.
- The electrons at the top of the
filled portion can move in one
direction, and the holes can
move in the other.
Molecular Orbitals and Band Structure
- Metal: The conductance decreases with increasing temperature because
of increasing vibrational motion of the atoms
- Semiconductor: They differ from insulators by having the bands very
close in energy (>2 eV). Conductance increases with increasing
temperature.
- At higher temperatures, a few electrons can jump
into the higher CB.
- These electrons are then free to move through
the crystal. The vacancies, or holes, left in the
lower energy band can also appear to move
as electrons move into them.
Molecular Orbitals and Band Structure
- Intrinsic semiconductors: pure materials have semiconductive property.
- Doped semiconductors: other elements that are not semiconducting in the
pure state can be modified by adding a small amount of dopant with
energy levels close to those of the host.
- n-type semiconductor: if the added material has more electrons in the
valence shell than the host material.
- p-type semiconductor: if the added
material has fewer electrons in the
valence shell than the host material.
- In an intrinsic semiconductor, the Fermi
level, the energy at which an electron is
equally likely to be in each of the two levels,
is near the middle of the bandgap.
 Diodes, the Photovoltaic Effect, and
Light-Emitting Diodes
Diodes: p-n junction with p-type and n-type semiconductors
- A few of the electrons in the CB of the n-type material can migrate to the
VB of the p-type material, leaving the n-type positively charged and the
p-type negatively charged.
- An equilibrium is quickly established and the separation of charges then
prevents transfer of any more electrons. As this point, the Fermi levels are
at the same energy. The bandgap remains the same in both layers, with
the energy levels of the n-type layer lowered by the buildup of positive
charge.
 Diodes, the Photovoltaic Effect, and
Light-Emitting Diodes
- Forward bias: if a negative potential is applied to the n-type side of the
junction and a positive potential is applied to the p-type side. The excess
electrons raise the level of the n-type CB and then have enough energy to
move into the p-type side. Current can flow readily.
- If the potential is reversed, the holes and electrons both move away from
the junctions, and very little current flows.
- A diode allows current to flow Readily in one direction.
- A junction of this sort can be used as a light-sensitive switch. With a
reverse bias, visible light irradiation on the junction lifts electrons from
the VB to CB.
 Diodes, the Photovoltaic Effect, and
Light-Emitting Diodes
- Photovoltaic cell: If no external voltage is applied and the gap has
appropriate energy, light falling on the junction can increase the transfer
of electrons from the p-type material into the CB of the n-type one.
If external connections are made to the two layers, current can flow.
- Light emitting diode (LED): A forward-biased junction can reverse this
process and emit light as a light-emitting diode. The current is carried by
holes on the p-type side and by electrons on the n-type side.
 Quantum Dots
Quantum dots: nanoparticles showing quantum confinement
effect that have diameters smaller than ~10 nm.
Quantum confinement effect: quantized energy states in small
nanoparticles
- The energy level spacings of quantum dots are related to their size.
- The bandgap energy increases as the particle size gets smaller.
- Exciton: the combination of
excited electron and hole
- Use of quantum dots: photovoltaics,
biosensors, drug delivery, LED
 Superconductivity
Superconductors: conductors with zero resistance
- Below critical temperature Tc, zero resistance and complete expelling of
external magnetic field occur. (Meissner effect)
- Type I superconductor: compete expelling, no formation of vortex
- Type II superconductor: formation of vortex between Tc1 & Tc2

- BCS theory: the formation of electron pair (Cooper pair) assisted by the small
vibrations of the atoms in the lattice.
- High temperature superconductors: oxygen-deficient ceramic copper oxides
 Bonding in Ionic Crystals
- There are both ionic and covalent bondings in solid lattice.
- In practice, all crystals have imperfections. If a substance crystallizes
rapidly, it is likely to have many more imperfections.
- Grain boundary: the boundaries between small crystallites.
- Slow crystal growth reduces the numbers of grain boundaries.
- Type of Crystal Defects
1. Schottky defect: Absence of ions, vacancy
2. Frenkel defect: Presence of ions in interstitial sites, self-interstitials
- Solid solution: homogeneous substitution of one atom for another
- Dislocations: Edge dislocations result when atoms in one layer do not
match up precisely with those of the next. As a result, the distances
between the dislocated atoms and atoms in adjacent rows are larger than
usual and the angle is distorted.
- A screw dislocation is one that has part of one layer shifted a fraction of a
cell dimension and causes a rapidly growing site during crystal growth via
the provision of helical path.
 Silicates
- The crystal structures of most silicates are composed of corner-shared
SiO4 tetrahedra.
- The linkage of SiO4 tetrahedra forms chain, double chains, rings, sheets,
and 3D arrays.
- Al3+ can substitute for Si4+. Al3+, Mg2+, Fe2+, and Ti4+ ions can occupy
octahedral holes in the aluminosilicate structures.
 Silicates
- Hydrated montmorillonite has water between the silicate-aluminate-
silicate layers.
- Zeolite contains porous structure with cation.
They were used in water softeners to remove
excess Ca2+ and Mg2+ before the development
of polystyrene ion-exchange resins.
- The extreme range of pore size (260-1120 pm)
makes it possible to control entry to and escape
from the pores based on the size and branching
geometry of the added material.