Ch 7 The Crystalline Solid State

I. Formulas and Structures

A. Simple Structures
1) Unit Cell = simplest repeating unit of the regular crystalline array

2) Bravais Lattices = 14 possible basic crystal structure unit cell types

Space Lattice -- atoms arranged in a pattern that repeats itself in three dimensions.
Unit cell -- smallest grouping which can be translated in three dimensions to
recreate the space lattice.
Cubic
a=b=c
 =  =  = 90º

tetragonal Cubic Close Packing (ccp)

a=b≠c = Face-Centered Cubic =
 =  =  = 90º (fcc)

hexagonal
a=b≠c
=  = 90º Hexagonal Close Packing
 = 120º (hcp)

trigonal
a=b=c
120º >  =  =  ≠ 90º

orthorhombic
a≠b≠c
 =  =  = 90º

monoclinic
a≠b≠c
 =  = 90º
 ≠ 90º
triclinic
a≠b≠c
 ≠  ≠  ≠ 90º
 Bravais Lattices

Cubic Unit Cells and Their Origins

hexagonal close packing crystal structure

 a) Atoms on corners and edges are shared between unit cells
i. Rectangular corners shared by 8 unit cells (8 x 1/8 = 1 total atom in cell)
ii. Other corners shared unequally, but still contribute 1 atom to unit cell
iii. Edges shared by 4 cells, contribute (4 x ¼ = 1 atom to unit cell)
iv. Faces shared by 2 cells, contribute ½ atom to each

b) Angles and Dimensions can vary: triclinic has all different lengths and angles

c) Lattice Points = positions of atoms needed to generate the whole crystal

i. Body Centered Cubic: (0,0,0) = origin and (½ , ½, ½) = center
ii. All other atoms can be generated from these 2 by moving them exactly
one cell length

3) Cubic Structures
a) Primitive Cubic is the simplest type
i. To fully describe: length of side, 90o angles, (0,0,0) lattice point
ii. 8 x 1/8 = 1 atom in the unit cell
iii. each atom surrounded by 6 others (Coordination Number = CN = 6)
iv. Not efficiently packed; only 52.4% of volume is occupied (74.1% max)
v. Vacant space at center with CN = 8 0.73r sphere would fit here
 4) Body-Centered Cubic (bcc)
a) One more atom is added to the center of the cube
4r b) Size of unit cell must increase over simple cubic
l c) Diagonal across center = 4r (r = radius of one atom)
d) Corner atoms not in contact with each other due to cell size expansion
2l e) Side = 2.31r (Calculate this in Ex. 7-1)
f) Unit cell contains 1(1) + 8(1/8) = 2 atoms
g) Lattice Points: (0,0,0) and ( ½ , ½ , ½ )

5) Close-Packed Structures
a) Spheres will arrange to take up the least space, not cubic or bcc
b) Two structures have almost identical packing efficiency (74.1%)
i. Hexagonal Close Packing = (hcp)
ii. Cubic Close Packing = (ccp) = Face-Centered Cubic = (fcc)
iii. Both have CN = 12 for each atom: 6 in its layer, 3 above, and 3 below
iv. HCP has 3rd layer in identical position as first ABA; second layer above
holes; CCP has 3rd layer displaced so above holes in first layer ABC
v. Both have 2 tetrahedral (Td) holes per atom (CN = 4) formed by 3
atoms in one layer and one atom above/below
vi. Both have 1 octahedral (Oh) hole per atom (CN = 6) formed by 3 atoms
in one layer and 3 atoms above/below
c) HCP unit cell is smaller than the hexagonal prism
i) Take four touching atoms in 1st layer and extend lines up to 3rd layer
ii) 8(1/8) + 1 = 2 atoms in unit cell
iii) Dimensions = 2r, 2r, and 2.83r
iv) Angles = 120o, 90o, and 90o
v) Lattice Points = (0,0,0,) and ( 1/3, 2/3, 1/2)
 Close-packed Structures
I. Metallic materials have isotropic bonding
II. In 2-D close-packed spheres generate a hexagonal array
III. In 3-D, the close-packed layers can be stacked in all sorts of sequences
IV. Most common are
A. ABABAB..
B. ABCABCABC…

Hexagonal close-packed
Cubic close-packed
AB A
BABABA….
 A at (0,0)
B at (2/3, 1/3)
C at (1/3, 2/3)
a2 A c
A
C
a1 B
A
What are the unit cell dimensions?
let atomic radius be R |a1| = |a2| = 2R
A 2R
3R  face diagonal = 23R = AA
2
AB = 1/3 (face diagonal)  R
½c{
R 3
A 2R A
4 2
R  x2  4R2
3
8 8 8 2 A B C A
x  R2
2
x R  c 2 R R
3 3 3 3
Hexagonal Close-packed Structure
8
|a1| = |a2| = 2R c 2 R
3
1 = 2 = 90°;  = 120°
c 8

ideal: a 3

coordination number? 12
atoms per unit cell? 2
lattice points per unit cell? 1
atoms per lattice point? 2
a unit cell with only one lattice point is a primitive cell
HCP
lattice type of HCP is called “primitive hexagonal”
reminder: the hexagon is not an acceptable unit cell shape
 Close-packed Structures
I. Metallic materials have isotropic bonding
II. In 2-D close-packed spheres generate a hexagonal array
III. In 3-D, the close-packed layers can be stacked in all sorts of sequences
IV. Most common are
A. ABABAB..
B. ABCABCABC…

Hexagonal close-packed
Cubic close-packed
ABCABCABC….
What are the unit cell dimensions?

face diagonal is
close-packed
direction

2a  4 R

a  2 2R

|a1| = |a2| = |a3|

1 = 2 = 3 = 90°
 Cubic Close-packed Structure

|a1| = |a2| = |a3|  2 2R

1 = 2 = 3
only one cell parameter to
be specified

coordination number? 12
atoms per unit cell? 4
lattice points per unit cell? 4
atoms per lattice point? 1 CCP

a unit cell with more than one lattice point is a non-primitive cell
lattice type of CCP is called “face-centered cubic”
CCP structure is often simply called the FCC structure (misleading)
 Cubic “Loose-packed” Structure

Body-centered cubic (BCC)

coordination number? 8
atoms per unit cell? 2
a
lattice points per unit cell? 2

atoms per lattice point? 1

another example of a non-primitive cell

body diagonal is closest-
packed direction lattice type of ‘CLP’ is “body-centered cubic”
4
3a  4 R  a  R
3 no common name that distinguishes lattice
|a1| = |a2| = |a3| type from structure type

1 = 2 = 3 = 90°
d) CCP unit cell
i) One corner from layer 1, opposite corner from layer 4
ii) 6 atoms each from layers 2 and 3 in the unit cell
iii) Unit cell is fcc
iv) 8(1/8) + 6(1/2) = 4 atoms in the unit cell
v) Lattice Points = (0,0,0), ( ½ , 0 , ½), ( ½ , ½, 0), (0 , ½ , ½)
e) Holes
i) 2 Td and 1 Oh hole per atom in both (hcp) and (ccp)
ii) If ionic compound, small cations can fill these holes
iii) Td hole = 0.225r Oh hole = 0.414r
iv) NaCl has Cl- in (ccp) with Na+ (ccp) but also in the Oh holes
v) Na+ = 0.695r, so it forces the Cl- to be farther apart, but still CN = 6
Metallic Crystals
Most metals crystallize in (bcc), (ccp), or (hcp) structures
Changing pressure or temperature can interchange these forms for a
metal
Must consider bonding, not just geometric packing only
Soft and malleable metals usually have (ccp) structure (copper)
Harder and more brittle metals usually have the (hcp) structure (zinc)
Most metals can be bent due to non-directional bonding
Weak bonding to all neighbors, not strong bonding to any single one
Atoms can slide past each other and then realign into crystal form
Dislocations = imperfections in lattice; make it easier to bend
Impurities = other elements; allow slippage of layers
Work Hardening = hammer until impurities are together
Heat: can soften by dispersing impurities or harden if control cooling
 7) Diamond
a) Each atom is tetrahedrally bonded to 4 other carbon atoms
b) Directional single bonds, unlike metals, cause hardness

B. Binary Compound Structures

1) Simplest structures just have 2nd element in holes of the first element’s lattice
a) Small cations can fit in Td/Oh holes of large anions
b) Large cations may only be able to fit in Oh holes
c) Even larger cations may cause changes in structure if they don’t fit in holes
2) Relative Number of Cations/Anions
a) M2X won’t allow close-packing of anion lattice with cations in Oh holes
because there are more cations than holes
b) Alternatives: cations in Td holes, vacancies, not close-packed
2) Sodium Chloride Structure: NaCl
a) Na+ in (fcc) and Cl- in (fcc)
b) Offset by ½ unit cell length
c) Na+ are centered in edges of Cl- lattice (or vice versa)
d) Most alkali halides have this same structure
e) Large size difference of ions facilitate this structure
f) Each Cl- has CN = 6 Na+ Each Na+ has CN = 6 Cl-

3) Cesium Chloride Structure: CsCl

a) Cs in simple cubic structure with Cl- in center (or vice versa)
b) Cl- = 0.83Cs+ size (0.73r in center is ideal)
c) Rare structure, need big cation (Cs, Tl only cations known with this
structure)
4) Zinc Blende Structure: ZnS
a) Same as diamond structure with alternating Zn and S atoms
b) Alternate: Zn and S each in (fcc) lattices combined so each ion is in a Td
hole of the other lattice
c) Stoichiometry: only ½ of the Td holes are occupied and ½ are vacant
5)Wurtzite Structure: ZnS
Rarer than Zinc Blende structure for ZnS; formed at
higher Temperatures
Zn and S each in (hcp) lattices combined so each ion is
in a Td hole of the other lattice
Again, ½ of the Td holes are vacant
6) Fluorite Structure: CaF2
a) Ca2+ in (ccp) lattice with 8 F- surrounding each and occupying all Td holes
b) Alternate: F- in simple cubic lattice with Ca 2+ in alternate body centers
c) Nearly perfect radius fits for this structure
d) Antifluorite Structure
i. Reverse stoichiometry compounds like Na2O
ii. Every Td hole in the anion lattice is occupied by a cation
The Fluorite (CaF2) and Antifluorite structures
A face-centered cubic arrangement of Ca2+ ions
with F- ions in all of the tetrahedral holes
7) Nickel Arsenide Structure: NiAs
a) As atoms in close packed layers exactly above each other
b) Ni atoms in all the Oh holes
c) Both Ni and As have CN = 6
d) Alternate: Ni atoms occupy all Oh holes of (hcp) As lattice
e) Usual for MX compounds where X = Sn, As, Bi, S, Se, Te

8) Rutile Structure: TiO2

a) Distorted TiO6 octahedral forming columns by sharing edges
b) Ti CN = 6; O CN = 3
c) Adjacent columns connected by sharing corners of octahedra
d) Unit cell has Ti at corners and in the body center, 4 O in the faces, and 2 O in
the plane of the body center Ti
e) MgF2, ZnF2 are other examples
D) The Radius Ratio
1) We can crudely predict CN by using the ratio r+/r-
2) This assumes atoms are just packing as hard spheres (not really all that occurs)
3) Examples:
a) NaCl r+/r- = 113/167 (CN = 4) = 0.667
r+/r- = 116/167 (CN = 6) = 0.695 Fits
best with CN = 6

b) ZnS r+/r- = 74/170 (CN = 4) = 0.435 Fits

best with CN = 4
r+/r- = 88/170 (CN = 6) = 0.518 CN = 4
in actual structure

4) Exercise 7-2 CaF2 has fluoride ions in a simple cubic array and calcium ions in
alternate body centers, with r+/r- = 0.97. What are the coordination numbers of the
two ions predicted by r+/r- ? What are the coordination numbers observed?
Predict coordination numbers of Ca2+ in CaCl2 and CaBr2.
II. Thermodynamics of Ionic Crystal Formation
A) The Born-Haber Cycle = series of elementary steps leading to an overall reaction
1) Used to determine electron affinity when all other reactions experimentally known
2) Today, we can measure EA’s easily, so Cycle is used to find Lattice Enthalpies
3) Sample Cycle
Li(s) ----> Li(g) Hsub = 161 kJ/mol
½ F2(g) ----> F(g) Hdis = 79 kJ/mol
Li(g) ----> Li+(g) + e- Hion = 531 kJ/mol
F(g) + e- ----> F-(g) Hioin = -328 kJ/mol
Li+(g) + F-(g) ----> LiF(s) Hxtal = -1239 kJ/mol
Li(s) + ½ F2(g) -- LiF(s) Hform = -769 kJ/mol

Sublimation
Dissociation
Ionization, electron affinity, lattice energy,
Formation energy
 Hform = -769 kJ/mol
Li(s) + ½ F2(g) ---------------- LiF(s)
Hdis = 79 kJ/mol
Hsub = 161 kJ/mol

Li(g) F(g)
Hion = 531 kJ/mol Helectron affinity = -328 kJ/mol

Li+(g) + e- F-(g)
Hlattice energy = -1239 kJ/mol
B) The Madelung Constant
1) Calculating Lattice Enthalpy appears straightforward: calculate
attractions

Zi Z j  e2  e = 1.602 x 10-23 C
U   4o = 1.11 x 10-10 C2N-1m-2
ro  4 o  [ ] = 2.307 x 10-28 J m
2) Problem: Long-range interactions change the Lattice Enthalpy
a) NaCl Na+ has 6 Cl- nearest neighbors at ro = ½ a (accounted for in equation)
b) Na+ also has 12 Na+ neighbors at r = 0.707 a (not accounted for)
c) Na+ also has many other Na+ and Cl- neighbors at longer distances

3) M = Madelung Constant takes into account all attractions

4) Born-Mayer Equation incorporates Madelung Constant as well as accounting for

repulsions (much more complicated than attractions)
NMZ  Z   e 2   
U  1  
ro  4 o  ro 
a)  = constant = 30 pm works well
b) Increase in charge causes corresponding increase in Lattice Enthalpy
2+/2+ charges would give 4 x Lattice Enthalpy
C) Solubility, Size, and HSAB
1) We can use a Born-Haber Cycle to calculate dissolution energies
AgCl(s) ----> Ag+(g) + Cl-(g) HLattEnth = 917 kJ/mol
Ag+(g) + H2O -- Ag+(aq) Hsolvation = -475 kJ/mol
Cl-(g) + H2O ----> Cl-(aq) Hsolvation = -369 kJ/mol
AgCl(s) + H2O ----> Ag+(aq) + Cl-(aq) Hdissolution = 73 kJ/mol

2) Factors effecting solubility

a) Size
i. Small ions have strong attractions; larger ions have small attractions
ii. Large ions may have more water molecules surrounding them
iii. Large/Large and Small/Small salts are less soluble than Large/Small
iv. LiF = CsI < LiI = CsF 1. Lattice Energy 2. HSAB
Cation Hydr. E. Anion Hydr. E Latt. Enth Net Enth.
Li+ -519 F- -506 -1025 0
Li+ -519 I- -293 -745 -67
Cs+ -276 F- -506 -724 -58
Cs+ -276 I- -293 -590 +21

Reaction: LiI(s) + CsF(s) ----> CsI(s) + LiF(s) H = 917 kJ/mol

III. Molecular Obitals and Band Structure
A) Band Formation
1) Overlap of 2 AO’s gives 2 MO’s
2) Overlap of n AO’s gives n MO’s
3) Solids have very large values of n, sometimes multiples of N
4) Band = many closely spaced MO’s of nearly continuous energy
a) Valence Band = highest occupied band (HOMO)
b) Conduction Band = next highest empty band (LUMO)

holes

Insulator Conductor w/ no Voltage Conductor with applied Voltage

5) Insulator = large energy gap between Valence and Conduction bands
a) Electrons can’t move through material
b) Electron motion is what allows conduction of electricity and heat
6) Conductor = partly filled Valence and Conduction bands (Most Metals)
a) Little energy required for electron movement
b) Hole = electron vacancy that can also “move” in partially occupied bands
7) Density of State = concentration of E levels in a Band = N(E)

8) Temperature Effect on Conductors (Metals)

a) Vibrations increase as temperature increases
b) Vibrations interfere with electron movement, slow conductance (increase
resistance)

9) Semiconductors= full Valence Band, Empty Conductance Band, close together

a) Energy gap < 2 eV
b) Si, Ge are common pure substances that are semiconductors
c) At low temperature they are insulators (not as good as true insulators)
d) At higher temperature they are conducturs (not as good as true conductors)
e) Opposite temperature effects as metals (true conductors)
10) Doped Semiconductors
a) We can closely control on/off properties of semiconductors: this has led to
the entire field of solid state electronics (computers)
b) Intrinsic Semiconductor = pure form is semiconductor (Si, Ge)
c) Doped Semiconductor = small amount of impurity effects semiconduction
i. n-type semiconductor = dopant has more e- than host (P in Si)
ii. p-type semiconductor = dopant has less e- that host (Al in Si)
iii. Careful doping results in tailored materials
d) Fermi Level = EF = Energy at which e- equally likely to be in either band
i. Intrinsic: EF about in middle of gap
ii. n-type: EF raised above new band
iii. p-type: EF lowered below new band

n-type semiconductor p-type semiconductor

B. Devices Using Semiconductors
1) p-n Junction
a) Diode = device where current flows only in one direction
b) At equilibrium a few e- have moved from n-type to p-type (n is +, p is -)
EF is at same level in n-type and p-type at equilibrium
c) Apply negative pot. to n-type and positive pot. to p-type
a) Forward Bias
b) Extra electrons allow e- in n-type to flow to p-type holes
c) Holes move to junction from p-type side
d) Current flows readily
d) Reverse Bias: holes and electrons move away from juction = no current
flows

Forward Bias Reverse Bias

2) Photovoltaic Cells
a) A p-n Junction with the energy gap = h of a light source
b) Light causes e- to jump to p-type even under reverse bias conditions
c) Light detector; Calculator battery

3) LED = Light Emitting Diode

a) A p-n Junction with forward bias
b) Electrons move from n to p and release energy in the form of light
c) Lower temp increases efficiency by decreasing vibrations

4) Laser = Light Amplification by Stimulated Emission of Radiation

a) LED with large band gap in p-type to prevent e- from escaping middle band
b) If Length = (n/2), reflection by edges stimulate more in-phase photons
LED 是利用電能直接轉化為光能的原理，在半導體內正負極 2 個端子施
加電壓，當電流通過，使電子與電洞相結合時，剩餘能量便以光的形式
釋放，依其使用的材料的不同，其能階高低使光子能量產生不同波長的
光，人眼所能接受到各種顏色的光，其波長介於 400-780nm ，在此區間
之外則為不可見光，包括紅外光及紫外光 (UV) 。

多數 LED 被稱為Ⅲ -Ⅴ 族化合物半導體，是由Ⅴ族元素 ( 氮、磷、砷等 ) 與

Ⅲ族元素 ( 鋁、鎵、銦等 ) 結合而成，與 IC 半導體所使用之矽 (Si) 等Ⅳ族
元素區別。傳統液相磊晶法 (Liquid Phase Epitaxy, LPE) 與氣相磊晶法
(Vapor Phase Epitaxy, VPE) ，以磷化鎵 (GaP) 或砷化鎵 (GaAs) 為基板，用於
生產中低亮度 LED 及紅外光 IrDa 晶粒，其亮度在 1 燭光 (1000mcd) 以下。
有機金屬氣相磊晶法 (Metal Organic Vapor Epitaxy, MOCVD) 用於生產高亮度
LED ，其亮度約在 6000-8000mcd 。以 AlGaInP 四種元素為發光層材料在砷
化鎵基板上磊晶者，發出紅、橙、黃光之琥珀色系，通稱為四元 LED ；以
GaN 為材料所生產的藍、綠光 LED ，則稱為氮化物 LED ，一般以藍寶石
(Sapphire) 為基板，美國大廠 CREE 則發展出以碳化矽 (SiC) 為基板的製程。
Plasma 電漿原理

氣體分子因光、放射線、電子等具有能量的粒子衝撞而激發、離子化
( 電子衝撞所致氣體激發及離子化的現象稱為放電 ) ，因放電而激發及
離子化的氣體 (ionized gas) 中，有中性分子、原子、各種離子、電子，
此為「電漿狀態」。像這樣「氣體被離子化後所產生的物質狀態」與
傳統的物質三態（即固、液、氣態）明顯不同，被科學家稱為物質的
第四態，科學家估計宇宙中百分之九十九的物質是以電漿狀態存在。

產生方式
藉由外加的電場能量來促使氣體內的電子獲得能量並加速撞擊不帶
電中性粒子，由於不帶電中性粒子受加速電子的撞擊後會產生離子
與另一帶能量的加速電子，這些被釋出的電子，在經由電場加速與
其他中性粒子碰撞。如此反覆不斷，進而使氣體產生崩潰效應 (gas
breakdown) ，形成電漿狀態。
電漿性質
1. 整體來說，電漿的內部是呈電中性的狀態，也就是帶負電粒子的密度與帶
正電粒子的密度是相同的。
2. 因為電漿中正、負離子的個數幾乎是一比一，因此電漿呈現電中性。
3. 電漿是由一群帶電粒子所組成，所以當有一部分受到外力作用時，遠處部
份的電漿，乃至整群的電漿粒子都會受到影響，這叫做「電漿的群體效應」。

4. 具有良好的導電性和導熱性。

日常生活中的電漿
1. 日常生活中最常見的日光燈，就是電漿的應用！當我們開燈時，點燈器
會產生極高的電壓，並產生電漿粒子，這些電漿粒子會轟擊燈管中的水銀
蒸氣、螢光物質，而使其發光。五顏六色的霓虹燈也是相同原理。
2. 富士通（ Fujitsu ）於 1993 年發表的電漿顯示器（ Plasma Display Panne
l ），其基本顯像原理：由前、後二塊玻璃基板夾成，玻璃上附有透明電極、
誘電層、保護層、紅綠藍三色螢光體等結構。這二塊玻璃基板中間的間隙
只有 0.1mm ，而在這 0.1mm 空間中填充了一種氣體。當施加電壓於電極上
時，電極會放電而產生 UV 光。而 UV 光打擊到玻璃基板上的紅、綠、藍
螢光物質時，這些螢光物質就會產生紅、綠、藍三原色，這些紅綠藍三原
色最後就合成各種彩色影像。
IV. Superconductivity
A) The Phenomenon
1) The conductivity of some metals changes abruptly
around 10 K (Critical Temperature = TC)
2) Superconductor = no resistance to e- flow
a) Kammerling and Onnes 1911 discover
for Hg cooled by liquid He
a) Major use today is superconducting magnets for NMR

B) Low Temperature Alloys

1) Type I Superconductors are often Nb-Ti alloys
a) Abrupt change between superconducting and normal conduction
b) Meissner Effect = no magnetic flux can enter superconductor below TC
“Floating Magnets” demonstration
c) Strong magnetic fields destroy superconduction above HC
d) Nb3Ge has highest TC = 23.3 K for this type of superconductor

2) Type II Superconductors work below TC1 and are complex between TC1 and TC2
a) Some magnetic flux can enter them in complex region (Floating Magnets)
b) Possible to use for Levitated Trains
C) Theory = Cooper Pairs
1) 1950’s Bardeen, Cooper, and Schrieffer propose BCS Theory
2) Electrons travel through superconductors in pairs (Cooper Pairs)
3) Opposite spin electrons are slightly attracted at low temperatures
4) As one e- moves past +nucleus in metal, the next +nucleus attracts it
5) This increases the charge density, so the second e- of the pair is attracted to
6) Cooper pairs move through metal like a wave
7) Lattice helps push/pull e- through; no resistance because energetically favorable
8) When T > TC the thermal motion of the +nuclei disrupt the “wave”

D) High Temperature Superconductors

1) (La2-xSrX)CuO4 found to have TC = 30 K in 1986
2) YBa2Cu3O7 found to have TC = 92 K in 1987
a) Type II superconductors
b) Cool with N2(l) [cheap, bp = 77K] instead of He(l) [expensive, bp = 3K]
c) Ceramic = brittle; can’t easily make into wire, etc…
3) Structure: copper oxide planes and chains
4) Theory: BCS Theory applies, but not completely understood
V. Bonding in Ionic Crystals
A) Simplest Idea = hard spheres with only electrostatic interactions
B) Deviations form Simple Idea
1) Ionic size is difficult to measure
a) Pauling Li+ = 60 pm (from calculations)
b) Shannon Li+ = 90 pm (from crystal structures)
c) Sharing of electrons back from anion effects the size of the cation
2) Covalent Interactions very important as well: ZnS is strongly covalent
3) Complex theory involving MO’s = Crystal Field Theory (Chapter 10)

VI. Imperfections in Solids

A) Crystal Growth
1) Slowly grown crystals are more perfect
2) Quickly grown crystals are usually made up of many small crystals which have
run into each other = grain boundaries
3) Even “perfect crystals” have impurities and vacancies
B) Vacancies and Self-Interstitials
1) Vacancy = missing atom, ion, or molecule in the crystal = simplest imperfection
a) More formed at higher T, but only 1/10,000 even near the melting point
b) Effect is small; localized in one unit cell and/or layer of the crystal
 2) Self-Interstitials = atoms/ions/molecules in the wrong place
a) Effect is felt for several layers of the crystal
b) Usually much rarer than vacancies

C) Substitutions = one element/ion in place of the expected element/ion

1) Common occurrence leading to a “Solid Solution”
2) Ni/Cu similar in size and electronegativity; both have (fcc) structure
a) Mixtures stable in any proportion = alloy
b) Random arrangement of atoms since they are so similar
3) Small atoms in holes between larger ones
a) Occupying a hole usually has small effect on the rest of the structure
b) May have large effect on properties of the material (C in Fe makes steel)
c) If impurity is large than hole: lattice strain or new solid phase

D) Dislocations
1) Atoms in one layer don’t match up with the next
2) Distances and angles effected for several layers in each direction
3) Screw Dislocation = one layer shifted a fraction of unit cell
a) Rapid growth location (more attraction into solution) = helical result
b) Mechanically weak; Electronically inefficient
Substitutional alloys have a structure in which sites of the solvent
metal are occupied by solute metal atoms. An example is brass, an
alloy of zinc and copper

These alloys may form if:

1. The atomic radii of the two metals are within 15% if each other.
2. The unit cells of the pure metals are the same.
3. The electropositive nature of the metals is similar (to prevent a
redox reaction)
Interstitial alloys are solid solutions in which the solute atoms
occupy holes (interstices) within the solvent metal structure.
An example is steel, an alloy of iron and carbon

These alloys often have a non-metallic solute that will fit in the
small holes of the metal lattice. Carbon and boron are often
used as solutes. They can be dissolved in a simple whole
number ratio (Fe3C) to form a true compound, or randomly
distributed to form solid solutions
VII. The Silicates
A) Abundance
1) O, Si = 80% of Earth’s Crust
2) Many compounds and minerals formed, some industrially important

B) Silica = SiO2
1) Three crystalline forms: Quartz (low T form), Tidymite, and Cristobalite
2) Molten SiO2 often forms glasses instead of crystalline forms
a) Glass = disordered solid structure
b) Actually a solution that continues to “flow” but very slowly
3) SiO4 tetrahedra in all crystal forms with Si—O—Si angle = 143.6o
4) Quartz
a) Most common form
b) Helical chains of SiO4 tetrahedra make it chiral
i. Each full turn of the helix has 3 Si and 3 O atoms
ii. Six helices combine to give a hexagonal structure
5) Other Silicates also have SiO4 units in chains, sheets, rings, arrays, etc…

6) Al3+ can substitute for Si4+ = Aluminosilicates

a) Other cations needed to balance charge
b) Al3+, Mg2+, Fe2+, Ti3+ common cations; occupy holes

7) Kaolinite = Al2(OH)2Si4O10
1) Talc = 3 Mg substitute for 2 Al Mg3 (OH)2Si4O10
2) OH- bridge between Al or Mg and Si
8) Mica
a) Layers of K+ ions between silicate and aluminate layers
b) Al in about 25% of the Si positions
c) Can be cleaved into incredibly smooth, flat sheets
9) Asbestos = fibrous mineral
a) Chrysotile = Mg3(OH)4Si2O5
b) Mg and Silicate layers differ in size leading to curling fibrous structure

10) Zeolites = mixed aluminosilicates with:

a) (Si,Al)nO2n frameworks and cations added to balance the charge
b) Used as water softeners before polymer resins developed (Cation exchange)
c) Cavities large enough for molecules to enter; may make stable complex
i. Water removal from organic solvent = Molecular Sieves
ii. Cat litter and oil absorbant
iii. Catalysts and catalyst support for petroleum cracking