Set 1

CHEM 713
1
Suggested reading material
CHEM 410/713/7130-01 - Prof. Holger Kleinke
Chemistry of Inorganic Solid State Materials
- A. R. West, Solid State Chemistry and its Applications, J ohn Wiley.
- R. Hoffmann, Solids and Surfaces, VCH.
- J . K. Burdett, Chemical Bonding in Solids, Oxford University Press.
- C. Kittel, Introduction to Solid State Physics, J ohn Wiley.
- M. O'Keeffe, B. G. Hyde, Crystal structures: Patterns and Symmetry.
gg g
1
- H. F. Franzen, Physical Chemistry of Solids.
- plus review articles, TBA
Course web page: https://uwaterloo.ca/learn
Periodic Table
2
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From molecules to the SOLID: is the solid state special?
Frequently used classifications for solids
a) elements: new modifications (e.g. fullerenes), structure comparisons,
growth of high purity crystals ...
b) crystalline materials: synthesis and crystal growth, defects, structure
chemical bonding physical properties ...
c) noncrystalline/amorphous materials: special physical and chemical
properties ...
d) (quasi)molecular solids (e.g. phosphides): structural relations ...
e) covalent solids (e.g. diamond, boron nitride): extreme hardness, very
3
) ( g ) y
high melting points ...
f) ionic solids (e.g. NaCl): structural chemistry, ionic conductivity ...
g) metals, semiconductors, isolators: close packings of spheres, alloys,
mechanical and electrical properties, chemical bonding ...
Crystalline Solids and Crystallography
Mechanical Properties
Electrical Properties
Metals/Alloys, e.g. Titanium for aircraft
Cement/Concrete Ca
3
SiO
5
'Ceramics', e.g. clays, BN, SiC
Lubricants, e.g. Graphite, MoS
2
Abrasives, e.g. Diamond, Corundum
Magnetic Properties
Optical Properties
Metallic Conductors, e.g. Cu, Ag ...
Semiconductors, e.g. Si, GaAs
Superconductors, e.g. Nb
3
Sn, YBa
2
Cu
3
O
7
Electrolytes, e.g. LiI in pacemakers
Piezoelectrics, e.g. o-Quartz in watches
CrO
2
, Fe
3
O
4
for recording technology
Pigments, e.g. TiO
2
in paints
4
Catalysts
g g
2
p
Phosphors, e.g. Eu
3+
in Y
2
O
3
is red on TV
Lasers, e.g. Cr
3+
in Al
2
O
3
is ruby
Zeolite ZSM-5 (an aluminosilicate)
- Petroleum refining
- methanol to octane
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Solid State Chemistry - Permutations
Example
Superconducting Tc (K)
Elements - A 80-106 (known) Nb (9)
Binary - AB (80 x 79)/2 =3160 (known) Nb
3
Ge (23)
Mg
3
B
2
(39)
Ternary - ABC (80 x 79 x 78)/6 (5% known) La
2
CuO
4
(40)
Quaternary - ABCD 1.5 M (surface scratched) YBa
2
Cu
3
O
7
(93)
ABCDE Gazillions (trace) HgBa
2
Ca
2
Cu
3
O
8
(134)
5
DONT mix up atoms (the motif) with
CRYSTAL STRUCTURE
UNIT CELL
The periodic arrangement of atoms in the crystal.
The smallest component of the crystal, which when replicated in (one,
two or) three dimensions reproduces the whole crystal.
The solid state: some basic definitions
DONT mix up atoms (the motif) with
lattice points
Lattice points are infinitesimal points
in space
Atoms are physical objects
Lattice Points do not necessarily lie
6
Lattice Points do not necessarily lie
at the centre of atoms
Primitive (P) unit cells contain only one lattice point
Non-primitive (NP) contains more than one lattice point
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The unit cell
The smallest repeat unit of a crystal structure, in 3D,
which shows the full symmetry of the structure
The unit cell is a box
(parallelepipedon) with:
3 sides - a, b, c
3 angles - o, |,
7
Atomic position: (x, y, z)
(fractional coordinates)
Atoms in different positions in a unit cell are shared by differing
numbers of unit cells
Counting Atoms in 2D unit cells Counting Atoms in 2D unit cells
Atoms at the corner of the 2D unit cell contribute only 1/4 to unit cell count
Atoms at the edge of the 2D unit cell contribute only 1/2 to unit cell count
Atoms within the 2D unit cell contribute 1 (i.e. uniquely) to that unit cell
Counting Atoms in 3D Cells
8
Vertex atom shared by 8 cells 1/8 atom per cell
Edge atom shared by 4 cells 1/4 atom per cell
Face atom shared by 2 cells 1/2 atom per cell
Body unique to 1 cell 1 atom per cell
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1-dimensional lattice symmetries are found in many ornaments
2-dimensional lattice symmetries were famously exploited by the artist
M.C. Escher in many patterns
9
http://www.mcescher.com/Gallery/gallery-symmetry.htm
2D-Lattices, e.g., graphene
10
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3D-Lattices, e.g., graphite
Clinographic
view
Plan
view
11
Note staggering of consecutive layers
(contrast with Boron Nitride)
LATTICE
An infinite array of points in space, in which each point
has identical surroundings to all others.
12
P = Primitive
I = Body-centred
F = Face-centered
C = Side-centered
plus 7 crystal classes
14 Bravais Lattices
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Bravais Lattice Equivalencies
There are fourteen Bravais lattices. It easy to
see that a cubic system cannot be side
centered (because it would no longer be cubic).
But how about these possibilities....?
Show that an I-centered monoclinic
b
a
c
lattice should be transformed into a
C-centered one.
c
13
Show that an F-centered tetragonal
lattice must be transformed into a
smaller I-centered.
How about monoclinic B - or tetragonal C?
Close Packing of Spheres
1926 Goldschmidt proposed atoms could be considered as packing in
solids as hard spheres
This reduces the problem of examining the packing of like atoms to that of
examining the most efficient packing of any spherical object,
- e.g. have you noticed howoranges are most effectively packed in displays e.g. have you noticed how oranges are most effectively packed in displays
at your local shop?
14
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A single layer of spheres is closest-packed with
a HEXAGONAL coordination of each sphere
A second layer of spheres is placed in the indentations left by the first layer
space is trapped between the layers that is
not filled by the spheres
TWO different types of HOLES
(INTERSTITIAL sites) are left
15
OCTAHEDRAL (O) holes with 6 nearest
sphere neighbours
TETRAHEDRAL (T) holes with 4 nearest
sphere neighbours
T
O
P
P
When a third layer of spheres is placed in the
indentations of the second layer there are TWO
choices:
1. The third layer lies in indentations directly in line
(eclipsed) with the 1st layer,
Layer ordering may be described as ABA
16
2. The third layer lies in the alternative
indentations leaving it staggered with respect to
both previous layers,
Layer ordering may be described as ABC
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17
ccp/fcc hcp
Mg, Be, Sc, Ti
Hexagonal Close Packing
hcp
18
Cubic Close Packing
Cu, Ca, Sr, Ag, Au,
ccp/fcc
http://kleinke.uwaterloo.ca/simplestruc.html
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Hexagonal Close Packing a = b, c = 1.63a,
o =| =90, =120
A
B
A
B
A
C
Cubic Close Packing
Coordination number CN. 12
Anti-Cuboctahedral
2 atoms per unit cell
(1/3, 2/3, 1/4) (2/3, 1/3, 3/4)
a = b = c, o =| = =90
B
C
A
Note the shift in origin!
ABABAB (HCP)
B
A
19
Coordination number CN. 12
Cuboctahedral
4 atoms per unit cell
(0, 0, 0) (0, , )
(, 0, ) (, , 0)
A
B
C
A
ABCABC (CCP/FCC)
The most efficient way to fill space with spheres
Is there another way of packing spheres that is more space-efficient?
In 1611 Kepler asserted that there was no way of packing equivalent spheres
at a greater density than that of a face-centred cubic arrangement. This is now
known as the Kepler Conjecture.
This assertion has long remained without rigorous proof In 1998 Hales This assertion has long remained without rigorous proof. In 1998 Hales
announced a computer-based solution. This proof is contained in over 250
manuscript pages and relies on over 3 gigabytes of computer files and so it will
be some time before it has been checked rigorously by the scientific
community to ensure that the Kepler Conjecture is indeed proven! (Simon
Singh, Daily Telegraph, Aug. 13th 1998)
G l S filli R V /V ith
20
General Space filling R
fill
=V
atoms
/V
cell
, with
V
atoms
=Sum of atom volumes per cell, thus
V
atoms
=Z 4/3 t r
3
with Z =number of atoms per cell;
V
cell
=volume of the unit cell.
CCP: V
cell
=a
3
, Z =4
(4r)
2
= 2a
2
R
fill
= 0.74
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Alternatives
a = b = c, o =| = =90
2 atoms in the unit cell:
(0 0 0) (1/2 1/2 1/2) (0, 0, 0) (1/2, 1/2, 1/2)
W, Li, V, Cr
Packing efficiency R
fill
=V
atoms
/V
cell
V
atoms
=Z 4/3 t r
3
=8/3 t r
3
; V
cell
=a
3
d =4r
21
Hence: not that close-packing!
d
2
=a
2
+a
2
+a
2
=3 a
2
=>d =\3 a =4r Pythagorean theorem
<=>a =4/\3 r =2.31 r
=> V
cell
=(4/\3 r)
3
=(4/\3)
3
r
3
R
fill
=V
atoms
/V
cell
=8/3 t / (4/\3)
3
=\3 t/8
R
fill
= 0.68
Primitive Cubic [o-Po]
Coordination Number 6
52% Packing Efficiency
V
atoms
/V
cell
=0.52, since
Comparison of Packing Efficiencies
atoms cell
V
cell
=a
3
and
V
atoms
=Z 4/3 t r
3
with a =2r and Z =1
Body Centered Cubic [W]
Close-Packed (ccp or hcp)
ccp
22
(increased pressure favors higher packing efficiency)
Body-Centered Cubic [W]
bcc
hcp
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Periodic Table of Metal Structures
Classification seems unpredictable, but patterns emerge from an understanding of band
structures (stability of a particular structure as a function of electron count).
23
Other examples
Polymorphism:
Some metals exist in different structure types at ambient temperature &
pressure
Many metals adopt different structures at different temperature/pressure
Not all metals are close-packed
Why different structures?
=>Residual effects from some directional effects of atomic orbitals
Difficult to predict structures
24
Trend: BCC clearly adopted for low number of valence electrons
Best explanations are based on Band Theory of Metals (later)
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Polymorphism:
Some metals exist in different structure types at ambient temperature & pressure
pressure
> 92 kbar
pressure
T < 13.2C
92 kbar
Gray tin
- semiconductor
- diamond structure
- CN 4
White tin
- metal
- tetragonal structure
- CN 6
d(S S ) 3 02 3 18
High pressure tin I
- metal
- tetragonal structure
CN 8
25
- d(Sn-Sn): 2.81
- density: 5.7 gcm
-3
- d(Sn-Sn): 3.02 - 3.18
- density 7.2 gcm
-3
- CN 8
d(Sn-Sn): 3.11 - 3.70
density 8.4 gcm
-3
High pressure tin II
- Metal
- bcc
- CN (8+6)
p > 500 kbar
- d(Sn-Sn) 2.85 - 3.29
- density 10.9 gcm
-3
More complex close-packing sequences than simple HCP & CCP are
possible:
HCP & CCP are merely the simplest close-packed stacking sequences,
others are possible!
All spheres in an HCP or CCP structure have identical environments
Repeats of the form ABCBABCBABCB.... are the next simplest
There are two types of sphere environment
surrounding layers are both of the same type (i.e. anti-cuboctahedral
coordination) like HCP, so labelled h
surrounding layers are different (i.e. cuboctahedral coordination) like CCP,
so labelled c
26
Layer environment repeat is thus hchc...., so labeled hc
Alternative: unit cell is alternatively labeled 4 H,
because it has 4 layers in the c-direction and is hexagonal
The hc (4 H) structure is adopted by early lanthanides
Samarium (Sm) has a 9-layer chh repeat sequence
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Non-Ideality of Structures
Cobalt metal that has been cooled from T >500C has a close-packed
structure with a random stacking sequence
"Normal" hcp cobalt is actually 90% AB... & 10% ABC...
- i.e. non-ideal HCP
Many metals deviate from perfect HCP by "axial compression"
e.g. for Beryllium (Be) c/a =1.57 (c.f. ideal c/a =1.63)
C di ti i [6 +6]
27
Coordination is now [6 +6]
with slightly shorter distances to neighbors in adjacent layers
Layers and Interstitial Cavities in Close packed Structures
28
There are one O
h
and two T
d
holes per site in CCP - hence K
3
C
60
.
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Location of interstitial holes in close-packed structures
The HOLES in close-packed arrangements may be filled with atoms of a
different kind.
It is therefore important to know:
where holes are placed in space relative to the positions of the spheres where holes are placed in space relative to the positions of the spheres,
where holes are placed relative to each other.
fcc packing
fcc packing with O
h
holes (+)
29
30
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31
Different cavity sizes: the octahedral hole
r: radius of packing atom;
r
h
: radius of hole
ccp/fcc
M: metal atom (hole);
X: anion (packing atom)
a = r
X
+ 2 r
M
+ r
X
a = r
M
+ r
X
(I)
d
2
= a
2
+ a
2
=> d = \2 a
d = 4 r
X
= \2 a
a = 2/\2 r
X
= r
X
\2 (II)
32
(I) = (II):
r
M
+ r
X
= r
X
\2
r
M
= (\2 1) r
X
r
M
/r
X
= \2 1 = 0.414
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Different cavity sizes: the tetrahedral hole
d
2
= a
2
+ a
2
=> d = \2 a
d = 4 r
X
= \2 a <=> a = r
X
\2
=> r
X
= a \2
g = r
X
+ 2 r
M
+ r
X
g/2 = r
M
+ r
X
(g/2)
2
= (a/4)
2
+ (b/2)
2
33
(g/2)
2
= (a/4)
2
+ (b/2)
2
(r
M
+ r
X
)
2
= ( r
X
\2)
2
+ r
X
2
(r
M
+ r
X
)
2
= r
X
2
+ r
X
2
= 3/2 r
X
2
r
M
+ r
X
= \(3/2) r
X
= \6 r
X
r
M
= ( \6 1) r
X
r
M
/r
X
= \6 1 = 0.225
Ionic (and other) structures may be derived from the occupation of
interstitial sites in close packed arrangements.
34 http://kleinke.uwaterloo.ca/simplestruc.html
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ccp
Li
3
Bi type
filling of all O
h
and T
d
voids
35
K C
3 60
C
60
Close Packing of Spheres:
descriptions based on linking polyhedra; e.g. triangle, tetrahedron,
square pyramid, trigonal bipyramid, octahedron, trigonal prism,
pentagonal bipyramid, square antiprism, cube, and capped variants
thereof.
36
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Overview: coordination numbers and polyhedra
37
cf. VSEPR rules (CHEM212): http://www.shef.ac.uk/chemistry/vsepr/
Examples? Point groups? Missing polyhedra?
Perfect packing occurs
when anions touch and
cations fit perfectly in the
pocket. Then, anions
touch anions and cations
to ch anions touch anions.
If cations are too large
(larger r
M
/r
X
), anions
cannot touch (not ideal).
If anions are too large
(smaller r
M
/r
X
), cations
ttl i k t ( )
38
rattle in pocket (worse).
Conclusion:
The listed r
M
/r
X
ratios are
the minima, not maxima.
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Limiting Radius Ratios
What's the Numerical Value of a Specific Ionic Radius?
Ionic radii in most scales do not generally meet at experimental
electron density minima,
because of polarization of the anion by the cation
39
The various scales are designed to be selfconsistent in reproducing
r
o
=r
M
+r
X
[ or: r
o
=r
+
+r
]
{Use the same scale for cation and anion!}
Ionic radii change with coordination number r
8
>r
6
>r
4
{Use the appropriate one!}
What's the Numerical Value
of a Specific Ionic Radius?
40
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Limiting Radius Ratios: do they work?
For Li
+
and Na
+
salts, ratios
calculated from both r
6
and r
4
are
indicated
Radius ratios suggest adoption of
C Cl t t th i CsCl structure more than is
observed in reality
NaCl structure is observed more
than is predicted
Radius ratios are only correct ca.
50% of the time, not very good for a
family of archetypal ionic solids -
randomchoice might be just as
41
random choice might be just as
successful as radius ratio rules and
saying that all adopt the NaCl
structure more so!
Is the Goldschmidt cation-anion
Contact Criterion all there is to it?
No!
too simplifying!
Lattice energy must be considered!
Limiting Radius Ratios: why dont they work better?
U A/r
Energy rises as r
+
/r
-
falls until the structure
can no longer support cation-anion
contact.
At the geometric limiting radius ratio the
-U
L
A/r
0
At the geometric limiting radius ratio, the
energy remains constant as r
+
/r
-
falls,
because r
o
=r
+
+r
-
but instead is limited by
"anion-anion contact".
NaCl-CsCl transition at r
+
/r
-
=0.71
ZnS-NaCl transition at r
+
/r
-
=0.32
Taking r
8
>r
6
into account indicates that
the CsCl structure is never favorable
42
(dotted line)
CsCl structure is only adopted where 8:8
coordination maximizes Dispersion
Forces
NaCl structure is highly favored by
covalency (best utilization of Cl
-
p
3
orbitals)
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When the radius ratio rules work, do they do so for the right reasons?
Radius ratios might appear to work well for predicting structures of
oxides, e.g. TiO
2
(consider r(Ti
4+
)/r(O
2-
) )
75 pm / 126 pm (Shannon & Prewitt) =0.60
61 pm / 140 pm (Pauling) =0.44
Limiting Radius Ratios
6:3 Coordination, as is observed in practice for TiO
2
But...
Ti
4+
is very polarizing - covalencyin bonding?!
r(O
2-
) was determined in systems like MgO, CaO etc...
Perhaps we really should use covalent radii?
r
cov
(O)/r
cov
(Ti) =73 pm / 95 pm =0.77
8:4 Coordination, i.e. fluorite structure - NOT what's observed!
43
,
Alternative reasoning?
Ti in TiO
2
is 6-coordinate because this maximizes covalent bonding, not
because the radius ratio rules are necessarily correct!
Beware! Use radius ratios as a simple predictional tool, not as a
means of rationalizing structures.
Ternaries
Binaries AB
Structure Maps Is there any general influence of ionic radii on structure?
44
Separation of structure types is achieved on structure diagrams,
... but the boundaries are complex
Conclusion: Size matters, but not necessarily in any simple way!
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Mooser-Pearson Plots
Combine bond directionality,
size and electronegativity
x-axis is A_, (bond ionicity)
y axis is the average PQN y-axis is the average PQN
larger orbitals (larger PQN)
lead to less directionality
45
-Sharp borderlines, a critical ionicity which determines structure
-Boundaries are curved - not so helpful!
- Indicates the increased ionicity of Wurtzite over Zinc Blende
(higher Madelung Constant of Wurtzite)
Unit cell
Sodium Chloride
Cl with Na in all O
h
holes
Lattice: fcc
Motif: Cl at (0,0,0);
Na at (1/2,0,0)
4 NaCl in unit cell (Z =4)
Coordination: 6:6 (octahedral)
46
[NaCl
6
] and [ClNa
6
] octahedra
Linking of [NaCl
6
] octahedra
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Structure variants of NaCl
NaSbS
2
:
Na
+
and Sb
3+
randomly on the Na
+
sites; S
2-
on Cl
-
.
Long termannealing: Na and Sb order Long term annealing: Na and Sb order.
d(Na-S): 2.85, 2.88, 2x 2.92, 2.97, 3.00 ;
d(Sb-S): 2.44, 2.73, 2.74, 2x 2.92, 3.38 .
=> Monoclinic distortion.
FeS
2
:
Fe
2+
on Na
+
;
a
b
c
47
CaC
2
:
Ca
2+
on Na
+
;
C
2
2-
on Cl
-
.
S
2
2-
on Cl
-
.
Pyrite: fools gold
Nickel Arsenide
HCP As atoms with Ni atoms in all
octahedral holes
a =b =3.57 , c =5.10
Positions:
2 Ni at (0, 0, 0) & (0, 0, 1/2)
2 As at (1/3, 2/3, 1/4) & (2/3, 1/3, 3/4)
0
( , , ) ( , , )
2 NiAs in unit cell, thus Z =2
0, 0,
0,
0,
48
Face and edge-sharing
[NiAs
6
] octahedra
[NiAs
6
] octahedra
[AsNi
6
] trigonal prism
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Cadmium Iodide
HCP I atoms with Cd atoms in all
octahedral holes of every other layer.
0
0
0 0
0
CdI
2
49
Edge-sharing
[CdI
6
] octahedra
0, 0,
0,
0,
NiAs
ZINC BLENDE or Sphalerite
CCP S
2-
with Zn
2+
in half of the T
d
holes
Lattice: FCC
4 ZnS in unit cell (Z =4)
Motif: S at (0, 0, 0);
WURTZITE
HCP S
2-
with Zn
2+
in half of the T holes
Motif: S at (0, 0, 0);
Zn at (1/4, 1/4, 1/4)
Coordination: 4:4 (tetrahedral)
50
in half of the T
d
holes
Lattice: Hexagonal - P
a =b, c =\(8/3)a
Motif: 2 S at (0,0,0) & (2/3, 1/3, 1/2);
2 Zn at (2/3, 1/3, 1/8) & (0, 0, 5/8)
2 ZnS in unit cell (Z =2)
Coordination: 4:4 (tetrahedral)
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Polymorphs of
Zinc Sulfide
WURTZITE ZINC BLENDE
51
4 nearest neighbors
12 next-nearest neighbors
Cub-octahedral
Anti-Cub-octahedral
plus different next-next-nearest neighbor coordination
ccp Ca
2+
with F
-
in all tetrahedral holes
Lattice: fcc
Motif: Ca
2+
at (0, 0, 0);
2 F
-
at (1/4, 1/4, 1/4) & (3/4, 3/4, 3/4)
4 CaF
2
in unit cell (Z =4)
Fluorite (CaF
2
)
,
,
,
,
2
( )
Coordination: Ca
2+
8 (cubic) : F
-
4 (tetrahedral)
anti-Fluorite: Na
2
O
52
Linking of [FCa
4
] tetrahedra
K
2
[PtCl
6
]
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Rutile (TiO
2
)
HCP anions (distorted), Ti atoms in of the O
h
sites
Unit Cell: Primitive Tetragonal (a =b =4.59 , c =2.96 )
Positions: 2 Ti at (0, 0, 0) & (1/2, 1/2, 1/2)
4 O at (0.3, 0.3, 0), (0.7, 0.7, 0), (0.2, 0.8, 1/2), (0.8, 0.2, 1/2)
Ti: 6 (octahedral coordination); O: 3 (trigonal planar coordination)
53
Rhenium Trioxide
Lattice: Primitive Cubic
1ReO
3
per unit cell
Motif: Re at (0, 0, 0);
3 O at (1/2, 0, 0), (0, 1/2, 0), (0, 0, 1/2)
Re: 6 (octahedral coordination)
O: 2 (linear coordination) ( )
ReO
6
octahedra share only vertices (=corners)
54

CHEM 713
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CdI
2
: HCP anions (I), Cd atoms in all O
h
sites of every other layer
CdCl
2
: CCP anions (Cl), Cd atoms in all O
h
sites of every other layer
Layered AB
2
structure types
CdCl
2
CdI
2
55
NiAs
Transition metals with chalcogen and pnictogenatoms
e.g. Ti(S,Se,Te); Cr(S,Se,Te,Sb); Ni(S,Se,Te,As,Sb,Sn)
Examples of Structure Adoption
g ( ) ( ) ( )
CdI
2
Iodides of moderately polarizing cations; bromides and chlorides
of strongly polarizing cations; e.g. PbI
2
, FeBr
2
, VCl
2
Hydroxides of many divalent cations; e.g. (Mg,Ni)(OH)
2
Di-chalcogenides of many quadrivalent cations; TiS
2
, ZrSe
2
, CoTe
2
CdCl
2
(ccpequivalent of CdI
2
)
56
Chlorides of moderately polarizing cations; e.g. MgCl
2
, MnCl
2
Di-sulfides of quadrivalent cations; e.g. TaS
2
, NbS
2
(CdI
2
form as well)
Cs
2
O has the anti-cadmium chloride structure
CHEM 713
29
For these structure types:
NaCl rock salt
CaF
2
fluorite
ZnS zinc blende
NiAs nickel arsenide
ZnS wurtzite
Binary Solids AB
x
ZnS wurtzite
Na
2
O sodium oxide
TiO
2
rutile
CdCl
2
, CdI
2
, MoS
2
(cadmium dichloride, cadmium diiodide,
molybdenum dissulfide)
Li
3
Bi lithium bismuthide
ReO
3
rhenium oxide
C
57
Can you:
0. Give examples?
1. Describe the structure as filling of interstitial holes in close-packing?
2. Draw the unit cell in a plan (layer) or perspective view?
3. Recognize the structure from a plan or perspective view of a unit cell?
4. Identify coordination numbers & geometries & point groups of atoms?
5. Calculate density, distances, and formula units?
1 CCP =ABCABCABC (coord #=12)
2. HCP =ABABABABAB (coord #=12)
One O
h
hole per lattice point, and two T
d
holes (hence K
3
C
60
)
3. BCC (coord #=8 or 8+6) [not close packed]
4. Derivative (AB
x
) Structures
Close packed spheres - a Summary of Geometrical Features
(
x
)
AB NaCl - interpenetrating CCP, O
h
sites
NiAs - HCP As atoms, with Ni atoms in O
h
sites
ZnS (Zinc blende) - interpenetrating CCP, T
d
sites
ZnS (Wurtzite) - interpenetrating HCP, T
d
sites
AB
2
CaF
2
- Fluorite - cations CCP, anions fill all T
d
sites
Na
2
O - Antifluorite - anions CCP, cations fill all T
d
sites
58
CdCl
2
- CCP anions, cations O
h
sites (alternate layers) filled
CdI
2
- HCP anions, cations O
h
sites (alternate layers) filled
TiO
2
- Rutile - "HCP" anions, cations fill O
h
sites (ordered frame)
AB
3
ReO
3
- Cubic, with cations at all corners, anions along all edges
[not close packed]
Li
3
Bi and K
3
C
60
- CCP anions with all T
d
and O
h
holes filled
CHEM 713
30
Layered AB
2
structure types
MoS
2
: S anions NOT
close packed; layer
sequence AABB,
Mo in half of the Mo in half of the
trigonal prismatic
sites of every other
layer.
Lattice: Hexagonal - P
Motif: 2 Mo at (
2
/
3
,
1
/
3
,
3
/
4
), (
1
/
3
,
2
/
3
,
1
/
4
)
4 S at (
2
/
3
,
1
/
3
,
1
/
8
), (
2
/
3
,
1
/
3
,
3
/
8
), (
1
/
3
,
2
/
3
,
5
/
8
), (
1
/
3
,
2
/
3
,
7
/
8
)
2 M S i it ll
59
2 MoS
2
in unit cell
Coordination: Mo 6 (Trigonal Prismatic) :
S 3 (base pyramid)
Layered AB
2
structure types
filled
empty
60
CHEM 713
31
More on layered AB
2
structure types and layer sequencies
A
B
B
c
c
CdI
2
empty
B
B
A
a
c
61
MoS
2
A
A
B
b
More on layered AB
2
analogous
to CdI
A
A
B
to CdI
2
NbSe
2
B
B
A
A
62
analogous
to MoS
2
A
B
B
B
CHEM 713
32
More on layered AB
2
CdI
2
layer
63
|-MoTe
2
Distortion leads to Mo-Mo bond
formation, driven by the d
2
configuration.
Ternary Solids
Perovskites, ABO
3
Lattice: Primitive Cubic
1 CaTiO
3
per unit cell
Motif (A): Ca at (1/2, 1/2, 1/2); Ti at (0, 0, 0);
3 O at (1/2 ,0, 0), (0, 1/2, 0), (0, 0, 1/2)
Ca: 12 (cuboctahedral coordination)
Ti: 6 (octahedral coordination)
O: 6 (4 Ca +2 Ti)
TiO
6
octahedra share only vertices
Remember ReO
3
?
64
Remember ReO
3
?
CHEM 713
33
La
2
CuO
4
{K
2
NiF
4
structure}: Doped La
2
CuO
4
{La
2-x
Sr
x
CuO
4
} was the
first (1986) High-T
c
Superconducting Oxide (T
c
~ 40 K),
La
2
CuO
4
- the first High-T
c
Superconductor
for which Bednorz &
Mller were awarded a
Nobel Prize Nobel Prize.
La
2
CuO
4
may be
viewed as if constructed
from an ABAB...
arrangement of
Perovskite cells known
65
Perovskite cells, known
as an AB Perovskite .
La
2
CuO
4
- the first High-T
C
Superconductor
Alternative descriptions
66
CHEM 713
34
One may view the structure as based on:
1. Sheets of elongated CuO
6
octahedra, sharing only vertices;
2. Layered networks of CuO
4
6-
, connected only by La
3+
ions.
La
2
CuO
4
- the first High-T
C
Superconductor
Comparison of La
2
CuO
4
/Nd
2
CuO
4
C t t l tif f t li k dC O Common structural motif of vertex-linked CuO
4
squares.
This motif occurs in all the
high T
C
copper oxides.
Differences are in the
structure of the 'filling' in
67
the 'sandwich' of Cu-O
layers.
- Intergrowth Structures
YBa
2
Cu
3
O
7
- the 1:2:3 Superconductor
The first material to superconduct at above liquid N
2
temperature, T
C
>77 K.
YBa
2
Cu
3
O
7
can be viewed as an Oxygen-Deficient Perovskite
68
CHEM 713
35
YBa
2
Cu
3
O
7
- the 1:2:3 Superconductor
Two types of Cu sites:
Layers of CuO
5
square pyramids
(elongation =>essentially vertex-
linked CuO
4
squares again)
Chains of vertex-linked CuO
4
squares
indicatedin a
69
indicated in a
Polyhedral Representation
Cooper Pairs
In Ogg's theory it was his intent
That the current keep flowing, once sent;
So to save himself trouble
The first man to suggest the paring of electrons was R. A. Ogg,
an experimental chemist. No-one believed him.
Superconductivity
The Meissner Effect
So to save himself trouble,
He put them in double,
and instead of stopping, it went.
70
The Meissner Effect
Superconductors are diamagnetic to the
total exclusion of all magnetic fields.
This is a classic hallmark of
superconductivityand can be used to
levitate a magnet.
CHEM 713
36
Spinels - AB
2
O
4
e.g., MgAl
2
O
4
1. Take eight cubes based on CCP of A.
2. Add B
4
O
4
cubes to half of T
d
holes, i.e., AB
4
O
4
3. Add AO
4
cubes to other half of T
d
holes, i.e.,
AB
4
O
4
+AO
4
.
4 STOICHIOMETRY of mother cube =
A
O
B
T
T
T T
CCP O atoms, A atoms in 1/8 of the T
d
holes, B atoms in 1/2 of the O
h
holes.
4. STOICHIOMETRY of mother cube =
AB
4
O
4
+AO
4
=A
2
B
4
O
8
=AB
2
O
4
T
71
Eight sub-cells inside fcc array of A atoms
FRONT BACK
Fe
3
O
4
magnetite is ferromagnetic
More on Spinels
Oxidation
state
Normal
spinel
Inverse
spinel
II, III MgAl
2
O
4
MgIn
2
O
4
Atomic positions:
Mg (0, 0, 0),
Al (x, x, x); x =0.625
O (x x x); x =0 375
II, III
IV, II
II, I
VI, I
2 4
Co
3
O
4
GeNi
2
O
4
ZnK
2
(CN)
4
WNa
2
O
4
2 4
Fe
3
O
4
TiMg
2
O
4
NiLi
2
F
4
Ionic radii:
Mg
2+
72pm Fe
2+
78pm Co
2+
75pm
72
O (x, x, x); x =0.375
Mg
2+
72pm
Al
3+
54pm
Fe
2+
78pm
Fe
3+
65pm
Co
2+
75pm
Co
3+
61pm
CHEM 713
37
Rule 1: A coordinated polyhedron of anions is formed about each cation, the cation-
anion distance determined by the sum of ionic radii and the coordination number by
the radius ratio.
Rule 2: The Electrostatic Valency Principle
An ionic structure will be stable to the extent that the sumof the strengths of the
Pauling rules for ionic crystals - J. Am. Chem. Soc. 51, 1010 (1929)
An ionic structure will be stable to the extent that the sum of the strengths of the
electrostatic bonds that reach an ion equal the charge on that ion.
When M
m+
is surrounded by n X
x
: ebs = m/n and x = Eebs
with ebs =electrostatic bond strength of MX bond
Rule 3: The presence of shared edges, and particularly shared faces decreases the
stability of a structure. This is particularly true for cations with large valences and
73
small coordination number.
Rule 4: In a crystal structure containing several cations, those of high valency and
small coordination number tend not to share polyhedral elements.
Rule 5: The Principle of Parsimony
The number of different kinds of constituents in a crystal tends to be small.
Crystalline Defects
Schottky defects
Entropy and defects in crystal lattices
74
Frenkel Defects
How will these defects affect density?
In ionic conductors, e.g. in battery
applications (LiCoO
2
), small ions
migrate from site to site via either
or both mechanisms.

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