CRYSTAL CHEMISTRY

Wh i l h i ?
Reading:
description and classification of crystals
b di iti t t l ti hi
What is crystal chemistry?
Reading:
West 7, 8
bonding; composition-structure relationships
the conditions in which particular type of crystal structure is observed
structure propertyrelations structure-property relations
Common ways to describe crystals: Common ways to describe crystals:
unit cell approach (specify size, shape and atomic positions)
close-packing approach (good for metals alloys ionic structures covalent close-packing approach (good for metals, alloys, ionic structures, covalent
networks, molecular and supermolecular solids)
space-filling polyhedron approach space g poy ed o app oac
65
CLOSE-PACKED CRYSTAL STRUCTURES
Consider the close-packing of incompressible (hard) spheres: Consider the close-packing of incompressible (hard) spheres:
In 2D, regular close-packing requires an hexagonal array (HCP)
Most efficient way
to pack spheres of single size
6 nearest neighbors
Coordination number (CN): 6
In 3D, regular close-packing involves stacking 2D HCP arrays
CCP
Regular
(crystalline)
ki
Irregular
packing
packing
66
HEXAGONAL CLOSE-PACKED STRUCTURE
An HCP crystal is a close-packed structure with the stacking sequence ABABAB An HCP crystal is a close-packed structure with the stacking sequence ...ABABAB...
To construct:
1
st
layer: 2D HCP array (layer A)
2
d
l HCPl i h h h l di l i i i 1
t
l (B) 2
nd
layer: HCP layer with each sphere placed in alternate interstices in 1
st
layer (B)
3
rd
layer: HCP layer positioned directly above 1
st
layer (repeat of layer A)
ABABABAB
AA
B
A
B
A
A
HCP is two interpenetrating simple hexagonal
lattices displaced by a
1
/3 +a
2
/3 +a
3
/2
67
HCP STRUCTURE
not a Bravais lattice not a avais lattice
Orientation alternates
with each layer with each layer
each sphere touches 12 equidistant nearest neighbors (CN =12)
Six in plane, six out-of-plane
structure has maximum packing fraction possible for single-sized spheres (0.74) p g f p f g p ( )
68
HCP STRUCTURE
unit cell is a simple hexagonal lattice with a
two-point basis
(000)
a
ideal ratio c/a of
8/ 3 1.633 =
(0,0,0)
(2/3,1/3,1/2) a
{0002} planes are close packed
Plan view
ranks in importance with FCC and BCC
Bravais lattices
69
HCP STRUCTURE
about 30 elements crystallize in the HCP form
70
CUBIC CLOSE-PACKED STRUCTURE
ACCP crystal is a close-packed structure with the stacking sequence ABCABC A CCP crystal is a close-packed structure with the stacking sequence ...ABCABC...
To construct:
1
st
layer: 2D HCP array (layer A)
2
d
l HCPl i h h h l di l i i i 1
t
l (B) 2
nd
layer: HCP layer with each sphere placed in alternate interstices in 1
st
layer (B)
3
rd
layer: HCP layer placed in the other set of interstitial depressions (squares, C)
4
th
layer: repeats the 1
st
layer (A)
ABCABCABC ABCABCABC
stacking g
of HCP layers
along
body diagonals
A
B
C
It t t th t th CCP t t i j t It turns out that the CCP structure is just
the FCC Bravais lattice!
71
CCP STRUCTURE
CN = 12 packing fraction 0 74 CN = 12, packing fraction 0.74
{111} planes are close packed
4 atoms in unit cell
Plan view Plan view
72
most common are HCP and CCP
CLOSE-PACKED STRUCTURES
most common a e C and CC
an infinite # of alternative stacking sequences exist
Example: silicon carbide has over 250 polytypes
e.g., 6H-SiC
stacking sequence ABCACB
73
STACKING FAULTS
Stacking faults are one or two layer interruptions in the stacking sequence that
destroy lattice periodicity
e.g., an <110> projection of an FCC lattice:
A
B
C
A
A
B
C
B
[111]
-
missing
l
A
B
C
A
B
B
C
A
B
C
[001]
-
[110]
-
[110]
plane
of atoms
perfect FCC
ABCABCABC
faulted FCC
ABCBCABC
C
C
[110]
The stacking fault is an example of a planar defect
2
stacking fault energy ~100 mJ m
-2
results also in perpendicular linear defects called dislocations
74
EXAMPLE
InAs nanowires - <110> projection
Caroff, P. et al. Nature Nanotechnology 4, 50 - 55 (2009)
75
CCP and HCP have very similar lattice energies y g
no clear cut trends
76
Nature 353, 147 - 149 (12 Sep 1991)
G A (CC ) Rare Gases: Ne, He, Ar, Kr, Xe (CCP)
77
gold nanocrystals
X. M. Lin
78
ANOTHER VIEW OF CLOSE PACKING
79
. It was
reviewed by a panel of 12 referees; the panel reported in 2003 after 4 years of reviewed by a panel of 12 referees; the panel reported in 2003, after 4 years of
work, that it was 99% certain of the correctness of the proof, but couldnt
verify the correctness of all of the computer calculations. Hales and Ferguson
(his student) received the Fulkerson Prize for outstanding papers in the area of (his student) received the Fulkerson Prize for outstanding papers in the area of
discrete mathematics in 2009.
http://en.wikipedia.org/wiki/Kepler_conjecture 80
PACKING FRACTIONS
The fraction of the total crystal volume that is occupied by spheres
CCP (and HCP)
2 a
radius =
The fraction of the total crystal volume that is occupied by spheres
3
3
atoms
4 2
4 ( )
3 4
2 0.7405
6
V
V
a
fraction
a
t
t

= = = =
2 a
4
radius =
cell
6 V a
2 a
a
74%
3
4
( )
a
t
BCC
3
4
a
radius =
SC
3
( )
3 2
0.5236 fraction
a
t
= =
3
4 3
2 ( )
3 4
06802
a
fraction
t
4
52%
3
3 4
0.6802 fraction
a
= =
68%
52%
81
82
b f / i ll
DENSITY CALCULATION
1
atoms
m nA
V N V

| |
= =
|
\ .
n: number of atoms/unit cell
A: atomic mass
V
C
: volume of the unit cell
cell A C
V N V
\ .
V
C
: volume of the unit cell
N
A
: Avogadros number
(6.02310
23
atoms/mole)
Calculate the density of copper.
R
Cu
= 0.128 nm, Crystal structure: FCC, A
Cu
= 63.5 g/mole
n = 4 atoms/cell,
3 3 3
(2 2 ) 16 2
C
V a R R = = = , ( )
C
3
8 3 23
(4)(63.5)
8.89 /
[16 2(1.28 10 ) (6.023 10 )]
g cm

= =
[16 2(1.28 10 ) (6.023 10 )]
8.96 g/cm
3
in the literature
83
INTERSTICIAL SITES IN CP STRUCTURES
Alarge number of ionic structures can be regarded as built of CP layers of anions A large number of ionic structures can be regarded as built of CP layers of anions
with the cations placed in interstitial sites
for every anion, there is 1 Octahedral site and 2 Tetrahedral sites y ,
84
Octahedral holes Octahedral holes
di t di t coordinates: coordinates:
00 00
00 00 00 00
00 00

= O site
cavities have <100> cavities have <100>
i t ti i t ti orientation orientation
85
Tetrahedral holes in CCP Tetrahedral holes in CCP TT
++
sites: sites:
+ +




TT
--
sites: sites:




cavities have <111> orientation cavities have <111> orientation
86
Holes in HCP Holes in HCP
O sites: O sites: O sites: O sites:
2/3,1/3,1/4 2/3,1/3,1/4
2/3,1/3,3/4 2/3,1/3,3/4 , , , ,
TT
++
sites: sites:
1/3 2/3 1/8 1/3 2/3 1/8
(1/3,2/3,1/2)
1/3,2/3,1/8 1/3,2/3,1/8
0,0,5/8 0,0,5/8
(0,0,0)
TT
--
sites: sites:
0,0,3/8 0,0,3/8
a
2
a
1
, , , ,
1/3,2/3,7/8 1/3,2/3,7/8
87
LOCATION OF OCTAHEDRAL HOLES
88
LOCATION OF TETRAHEDRAL HOLES
(3/8 of a unit cell directly
above/below each anion)
89
SIZE OF OCTAHEDRAL CAVITY
Only cations smaller than the diameter of the cavity can fit y y
without forcing the anion lattice to expand
2 2 a r r +
from cell edge
M ti
2 2
M X
a r r = +
from face diagonal
M = cation
X = anion
2 2
X
a r =
.
The cation radius must be
< 41% of the anion radius
90
SIZE OF TETRAHEDRAL CAVITY
The tetrahedral holes are twice as The tetrahedral holes are twice as
numerous but six times smaller in volume
The cation radius must be
< 23% of the anion radius
91
EUTACTIC STRUCTURES
Structures in which the arrangement of ions is the same as in a close packed array Structures in which the arrangement of ions is the same as in a close packed array
but the ions are not necessarily touching
Within certain loose limits (given by the radius ratio rules), cations
too large to fit in the interstices can be accommodated by an
expansionof theanionarray expansion of the anion array
anions dont like to touch anyway
modern techniques show that, in many cases, anions (cations) are
not as large (small) as previously thought g ( ) p y g
we still describe eutactic structures as CCP or HCP lattices
with ions in some fraction of the interstitial sites with ions in some fraction of the interstitial sites
92
CRYSTALS THAT CAN BE DESCRIBED IN
TERMS OF INTERSTITIAL FILLING OF A TERMS OF INTERSTITIAL FILLING OF A
CLOSE-PACKED STRUCTURE
93
SOME EUTACTIC CRYSTAL STRUCTURES
Variables: Variables:
1) anion layer stacking sequence: CCP or HCP array?
2) occupancy of interstitial sites
94
95
NaCl (ROCK SALT, HALITE) STRUCTURE
(CCP 100%O t H l Fill d) (CCP, 100% Oct. Holes Filled)
Space Group = Fm3m
Lattice = FCC
Basis = Cl (0,0,0), Na (,,)
Coordination = 6, 6
Cation Coord. Octahedron
Anion Coord Octahedron Anion Coord. Octahedron
Connectivity Edge sharing octahedra
with faces parallel to {111}
4 NaCl in unit cell
96
POLYHEDRAL REPRESENTATION
shows the topology and indicates interstitial sites shows the topology and indicates interstitial sites
tetrahedra and octahedra are the most common shapes
Rock Salt:
Array of edge sharing NaCl
6
octahedra
h h d h ll d
Rock Salt:
Each octahedron shares all 12 edges
Tetrahedral interstices
Galena (PbS) 97
ROCK SALT - OCCURANCE
Very common (inc. 'ionics', 'covalents' & 'intermetallics' )
lk l h l ( l ) Most alkali halides (CsCl, CsBr, CsI excepted)
Most oxides / chalcogenides of alkaline earths
M n nit id s bid s h d id s ( Z N TiC N H) Many nitrides, carbides, hydrides (e.g. ZrN, TiC, NaH)
98
COMPLEX ION VARIANT OF ROCK SALT
space group = Pa3
sulfur dimers oriented along <111>
99
(CCP T H l Fill d)
ZINC BLENDE (ZnS, SPHALERITE)
(CCP, T+ Holes Filled)
Space Group = F43m
Lattice = FCC
B i S (0 0 0) Z () Basis = S (0,0,0), Zn (,,)
Coordination = 4, 4
Cation Coord. Tetrahedron
Anion Coord. Tetrahedron
Connectivity Corner sharing Tetra.
4 ZnS in unit cell
100
ZINC BLENDE GaAs
bonding is less ionic than in rock salt
common for Be, Zn, Cd, Hg chalcogenides (i.e., ZnS, ZnSe, ZnTe)
common for III-V compounds (B, Al, Ga, In with N, P, As, Sb)
101
DIAMONDSTRUCTURE
S h l it b t ith id ti l t i ll iti Same as sphalerite, but with identical atoms in all positions
Space Group = F43m
Lattice = FCC
B i C (0 0 0) C () Basis = C (0,0,0), C (,,)
Coordination = 4
Connectivity Corner sharing Tetra. y g
8 C atoms per unit cell
102
FLUORITE (CaF
2
) &ANTIFLUORITE (Na
2
O)
Fluorite : CCP of Ca
2+
, 100% Tetra. Holes Filled with F
-
Anti-fluorite : cation and anion positions are reversed
Ca
2+
Space Group = Fm3m
Lattice = FCC
Basis = Ca
2+
(0 0 0) F
-
() & () Basis = Ca
2+
(0,0,0), F (,,) & (,,)
Coordination = 8, 4 (fluorite)
Cation Coord. Cubic
Anion Coord. Tetrahedral
Connectivity Edge sharing FCa
4
tetrahedra or edge sharing CaF
8
cubes
4 CaF
2
in unit cell
103
ALTERNATIVE REPRESENTATIONS
Ca
2+
Displacing the unit cell by of a body diagonal emphasizes the cubic cation coordination:
F
-
104
FLUORITE / ANTIFLUORITE
Ca
2+
origin of the term fluorescence
(Stokes, 1852)
fluorite common for fluorides of large,
divalent cations and oxides of large
tetravalent cations (M
2+
F andM
4+
O ) tetravalent cations (M F
2
and M O
2
)
antifluorite common for
oxides/chalcogenides of alkali earths (M
2
O)
CaF
2
oxides/chalcogenides of alkali ea ths (
2
O)
105
FLUORESCENT MINERALS
http://en.wikipedia.org/wiki/Fluorescence
= fluorite
106
COMPARING NaCl, ZnS, Na
2
O
NaCl ZnS Na
2
O
107
108
Li
3
Bi EXAMPLE
109
NiAs STRUCTURE
(HCP, 100% Oct. Holes Filled)
2
Space Group = P6
3
/mmc
Lattice = Primitive hexagonal
Basis = As (0,0,0) & (2/3,1/3,1/2)
Ni (1/3,2/3,1/4) & (1/3,2/3,3/4)
Coordination = 6, 6
Cation Coord. Octahedron
Anion Coord Trigonal prism Anion Coord. Trigonal prism
Connectivity Edge/face sharing Oct.
or edge-sharing trigonal prisms
2 NiAs in unit cell
110
Alternative unit cell with Ni at the origin:
111
Transition metals with
NiAs
Transition metals with
chalcogens, As, Sb, Bi
e.g. Ti(S,Se,Te);
Cr(S,Se,Te,Sb); ( , , , )
Ni(S,Se,Te,As,Sb,Sn)
112
WURTZITE (ZnS) STRUCTURE
(HCP T H l Fill d) (HCP, T+ Holes Filled)
Space Group = P6
3
mc
Lattice = Primitive hexagonal
B i S (0 0 0) & (2/3 1/3 1/2) Basis = S (0,0,0) & (2/3,1/3,1/2)
Zn (0,0,5/8) & (2/3,1/3,1/8)
Coordination = 4, 4
Cation Coord. Tetrahedron
Anion Coord. Tetrahedron
Connectivity Corner sharing Tetra.
2 ZnS in unit cell
113
ZnO
Projections perpendicular to close-packed planes
114
115
Very different next-nearest neighbor coordinations & beyond
116
HCP VERSION OF CaF
2
?
N t t k ith ll T t it (T d T ) fill d i HCP No structures are known with all Tetra. sites (T+ and T-) filled in HCP
- i.e. there is no HCP analogue of the Fluorite /Anti-Fluorite structure
Why?
The T+ and T- interstitial
sites above and below a layer
of close-packed spheres in
HCP are too close to each HCP are too close to each
other (distance = 0.25c) to
tolerate the coulombic
repulsion generated by filling
with like-charged ions.
Face-linking is unfavorable
117
RUTILE STRUCTURE (TiO
2
)
(distorted HCP, 50% Oct. Holes Filled) ( , )
Ti
O
Space Group = P4 /mnm
(0,0,0)
Space Group = P4
2
/mnm
Lattice = Primitive tetragonal
Basis = Ti (0,0,0) & (,,)
O (0 3 0 3 0) (0 7 0 7 0) (0 8 0 2 0 5) (0 2 0 8 0 5) O (0.3,0.3,0), (0.7,0.7,0), (0.8,0.2,0.5), (0.2,0.8,0.5)
Coordination = 6, 3
Cation Coord. Octahedral
Anion Coord. Trigonal planar
Connectivity chains of edge-sharing Oct.
along axis, linked by vertices
2 TiO
2
per unit cell
118
ANATASE STRUCTURE (TiO
2
)
(di t t d CCP 50%O t H l Fill d) (distorted CCP, 50% Oct. Holes Filled)
a = 3.776
b 3 776
Volume anatase TiO
2
cell: 136.25
3
b = 3.776
c = 9.486
Ti
O
2
rutile TiO
2
cell: 62.07
3
Space Group = I4
1
/amd
Lattice = body-centered tetragonal
Coordination = 6, 3
Cation Coord. Octahedral
Anion Coord. Trigonal planar
Connectivity chains of edge sharing Oct Connectivity chains of edge-sharing Oct.
along axis, linked by vertices and edges
4 TiO
2
per unit cell
119
RUTILE AND ANATASE
chains of edge sharing oct.,
linked at corners
greater density of edge sharing
a bit less stable linked at corners a bit less stable
120
CdI
2
STRUCTURE
(HCP ith Cd i O t H l f lt t l ) (HCP, with Cd in Oct. Holes of alternate layers)
A layered crystal
Cd
I
Space Group = P3m1
Lattice = Primitive trigonal
B i Cd (0 0 0) Basis = Cd (0,0,0)
I (2/3,1/3,1/4) & (1/3,2/3,3/4)
Coordination = 6, 3
Cation Coord. Octahedron
Anion Coord. Trigonal pyramid
Connectivity sheets of edge-sharing Oct.
1 CdI
2
per unit cell
121
Alternative
unit cell
with Cd at
the origin: the origin:
CdI
6
units NiAs
6
units
6 6
122
CdI
2
- OCCURANCE
Iodides of moderately polarizing cations; bromides and
chlorides of strongly polarizing cations; f g y p g ;
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 Z S C T e.g. TiS
2
, ZrSe
2
, CoTe
2
123
CdCl
2
STRUCTURE
The CCP analogue of CdI
2
(CCP, with Cd in Oct. Holes of alternate layers along [111])
Space Group = R32/m
CdCl
6
octahedra
Chlorides of moderately polarizing cations
e.g. MgCl2, MnCl2
Di-sulfides of quadrivalent cations
e.g. TaS2, NbS2 (CdI2 form as well)
124
Formula
Type and fraction
of sites occupied
CCP HCP
AB All octahedral
NaCl
Rock Salt
NiAs
Nickel Arsenide
Half
tetrahedral
(T+ or T-)
ZnS
Zinc Blende
ZnS
Wurtzite
N O A ti Fl it
A
2
B All tetrahedral
Na
2
O Anti-Fluorite
CaF
2
Fluorite
not known
A
3
B
All octahedral
&t t h d l
Li
3
Bi not known A
3
B
& tetrahedral
Li
3
Bi not known
AB
2
Half octahedral
(Alternate layers
full/empty)
CdCl
2
(Cadmium Chloride) CdI
2
(Cadmium Iodide)
full/empty)
Half octahedral
(Ordered
framework
arrangement)
TiO
2
(Anatase)
CaCl
2
TiO
2
(Rutile)
arrangement)
AB
3
Third octahedral
Alternate layers
2
/
3
full/empty
YCl
3
BiI
3
125
PEROVSKITE STRUCTURE ABO
3
(CaTiO
3
)
(CCP of Ca & O , 25% Oct. Holes Filled by Ti)
B C ll
A-Cell
Space Group = Pm3m
Lattice = Primitive cubic
B i Ti (0 0 0) C ()
An extremely important class of ABX
3
compounds:
B-Cell
Basis = Ti (0,0,0), Ca (,,),
O (,0,0), (0,1/2 ,0) & (0,0,)
Coordination = Ca-12 ; Ti-6; O-6
Ca Coord. Cuboctahedron
compounds:
Magnetoresistance
Ferroelectricity
Multiferroics
d
Ti Coord. Octahedron
O Coord. distorted octahedron (4 Ca, 2 Ti)
1 CaTiO
3
per unit cell
Superconductivity
Catalysis (fuel cells)
Spin transport
126
PEROVSKITE CONNECTIVITY
B-Cell
3D network of corner-sharing
octahedra
Network of face-sharing
cuboctahedra
octahedra
cuboctahedra
127
Perovskites: the most widely studied oxide structure Perovskites: the most widely studied oxide structure
Wide range of chemistries possible
- thousandsof examplesknown thousands of examples known
Cubic, tetragonal, and orthorhombic symmetries are common
- high T
c
cuprate superconductors
Colossal Magneto Resistance(LaSrMnO )
Unique properties of perovskites
- Colossal Magneto-Resistance (La,SrMnO
3
)
- fast ion conduction (Li
+
, O
2-
), batteries, fuel cells
- mixed electronic/ionic conduction, fuel cells
- oxidation/reductioncatalysts oxidation/reduction catalysts
- ferroelectric / piezoelectric ceramics (BaTiO
3
, Pb(ZrTi)O
3
)
- important mineral structure in lower mantle (MgSiO
3
, pyroxene)
- frequency filters for wireless communications : Ba(Zn
1/3
Ta
2/3
)O
3
q y (
1/3 2/3
)
3
128
Perovskite Structure: ABX
3
A
X
Tolerance factor (t):
A X
r r +
2( )
A X
B X
t
r r
=
+
B
t Effect Likely structure
A-Cell
t Effect Likely structure
> 1 A cation too large to fit in
interstices
Hexagonal
perovskite
0.9 - 1.0 ideal Cubic perovskite
0.71 - 0.9 A cation too small Orthorhombic
perovskite perovskite
< 0.71 A cation same size as B cation Possible close packed
lattice
129
PEROVSKITES
Most perovskites contain distorted octahedra and are not cubic These distortions give Most perovskites contain distorted octahedra and are not cubic. These distortions give
perovskites a rich physics.
symmetry at 25C
BaTiO
3
: Ba
2+
r = 1.56
Ti
4+
r = 0.68
O
2-
r = 1.26
t = 1.03 - tetragonal
symmetry at 25 C
O r 1.26
KNbO
3
: K
+
1.65
Nb
5+
0.78
t = 1.01 - orthorhombic
LiNbO
3
: Li
+
1.06
Nb
5+
0.78
t = 0.81 trigonal
LiNbO
3
: ferroelectricity, Pockels effect, piezoelectricity, photoelasticity,
nonlinear optical polarizability nonlinear optical polarizability
130
131
Reading: West 15
C m
-2
V m
-1
V m
1
132
DI- , PARA- , AND FERROELECTRICS
dipole moment: p = qd = E
response of atom to applied E field
P E
dipole moment: p = qd = E
polarization: P = p/V
p pp
P =
0

e
E
P : polarization (C/m
2
)

0
: vacuum permittivity 8.85 x 10
-12
C
2
N
-1
m
-2
l b l ( l )
p

e
: electric susceptibility (unitless)
E : electric field (V/m, or N/C)
p
dielectric polarization paraelectric polarization
ferroelectric polarization
linear: P = E nonlinear residual (zero field) polarization linear: P =
0

e
E
no P without E
nonlinear
no P without E
residual (zero-field) polarization
reversible direction of residual P
very large susceptibilities
133
WHY IS BaTiO
3
FERROELECTRIC
ferroelectric phase transition
~0.1 displacement
> 120C cubic, not FE
< 120C tetragonal, FE
transition occurs at the
Curie temperature, T
c
134

c
o
n
s
t
a
n
t

r
=
e
+ 1
d
i
e
l
e
c
t
r
i
c

135
FERROELECTRIC HYSTERESIS LOOPS
saturation polarization, P
s
remnant polarization, P
R
dipoles aligned up
coercive field E coercive field, E
C
dipoles aligned down
136
ORDERED ELECTRIC DIPOLE PHASES
ferroelectric (BaTiO
3
)
parallel ordering below T
c
antiferroelectric (PbZrO
3
)
antiparallel ordering below T antiparallel ordering below T
c
E field can induce
ferroelectric state
ferrielectric (Bi
4
Ti
3
O
12
) ferrielectric (Bi
4
Ti
3
O
12
)
net spontaneous polarization in only certain direction(s)
137
CURIE TEMPERATURE
Thermal energy destroys the ordered electric dipole state The temperature above Thermal energy destroys the ordered electric dipole state. The temperature above
which this order-disorder phase transition occurs is the Curie temperature, T
c
.
Above T
c
, the material is often paraelectric.
ordered
F / AF
randomized
orientation
P
Note:
These curves
P
omit the
spikes in P
at T
c
138
PHASE DIAGRAMS
139
K
2
NiF
4
STRUCTURE (La
2
CuO
4
)
Many complexstructures are composed of simple familiar buildingblocks
Doped La
2
CuO
4
was the first (1986) High-T
c
Superconducting Oxide (T
c
~ 40 K)
B d & Mll d d N b l P i
Many complex structures are composed of simple, familiar building blocks.
The high-T
c
copper oxide superconductors are an example.
Bednorz & Mller were awarded a Nobel Prize
La
2
CuO
4
may be viewed as if constructed from an ABAB... arrangement of
Perovskite cells - known as an AB Perovskite!
B
A
B
2 La
2
CuO
4
per unit cell
140
ALTERNATE VIEWS OF La
2
CuO
4
We may view the structure as based on: y
1. Sheets of elongated CuO
6
octahedra, sharing only vertices
2. Layered networks of CuO
4
6-
, connected only by La
3+
ions
141
COMMON STRUCTURAL FORM
Cations form
FCC with O
2-
FCC with O
2
interstitials
Common structural motif of vertex-linked CuO
4
squares
This motif occurs in all the high-T superconducting copper oxides This motif occurs in all the high-T
C
superconducting copper oxides
The structures differ in the structure of the 'filling' in the 'sandwich
of copper oxide layers - known as Intergrowth Structures
142
YBa
2
Cu
3
O
7
: THE 1,2,3 SUPERCONDUCTOR
the first material to superconduct at LN
2
temperature, T
c
> 77 K
YBa
2
Cu
3
O
7
can be viewed as an Oxygen-Deficient Perovskite
143
T t p s f C sit s:
POLYHEDRAL REPRESENTATION OF YBCO
Two types of Cu sites:
1) Layers of CuO
5
square pyramids
2) Chains of vertex-linked CuO
4
squares
CuO
2
BaO BaO
CuO
BaO
CuO CuO
2
Y
CuO
2
144
SPINEL STRUCTURE AB
2
O
4
(MgAl
2
O
4
)
(CCP, Mg in 1/8
th
of Tetra. Holes and Al in 50% of Oct. Holes)
a = 8.08
Space Group = Fd3m
extremely flexible structure, adopted
by over 100 compounds
Lattice = FCC
Coordination = Mg-4; Al-6; O-4
Mg Coord. Tetrahedron
Al Coord. Octahedron
normal spinel: 8 A in Tetra., 16 B in Oct.
inverse spinel: 8 A in Oct., 8 B in Oct. and
Al Coord. Octahedron
Connectivity chains of Edge-sharing AlO
6
octahedra, linked by MgO
4
tetra.
8 MgAl
2
O
4
per unit cell (56 atoms)
8 B in Tetra.
intermediate cations distributions also
occur.
145
146
SPINELS - OCCURANCE
Aluminium spinels: Aluminium spinels:
Spinel MgAl
2
O
4
, after which this
class of minerals is named
Gahnite - ZnAl
2
O
4
H i F Al O Hercynite - FeAl
2
O
4
Iron spinels:
Magnetite - Fe
3
O
4
Franklinite - (Fe,Mn,Zn)(Fe,Mn)
2
O
4
Franklinite (Fe,Mn,Zn)(Fe,Mn)
2
O
4
Ulvspinel - TiFe
2
O
4
Jacobsite - MnFe
2
O
4
Trevorite - NiFe
2
O
4
Ch i s i ls: Chromium spinels:
Chromite - FeCr
2
O
4
Magnesiochromite - MgCr
2
O
4
Others with the spinel structure: p
Ulvspinel - Fe
2
TiO
4
Ringwoodite - Mg
2
SiO
4
, an abundant
olivine polymorph within the Earth's
mantle from about 520 to 660 km mantle from about 520 to 660 km
depth, and a rare mineral in
meteorites
147
CRYSTAL FIELD STABILIZATION ENERGY
In transition metal compounds d electron effects such as crystal field In transition metal compounds, d electron effects such as crystal field
stabilization energy (CFSE) can be important in determining structure.
crystal field splitting diagrams
e.g. MF
2
compounds (high spin rutile)
crystal field splitting diagrams

oct
=

tetra
=
No CFSE

tetra
= (4/9)
oct
CFSE
oct
= (0.4 #t
2g
0.6 #e
g
)
oct
148
CATION SITE PREFERENCES IN SPINELS
The larger CFSE of metal ions in octahedral sites is sometimes an important
f d l ( l )
Normal - [A]
tet
[B
2
]
oct
O
4
Inverse - [B]
tet
[A,B]
oct
O
4
factor in determining spinel structures (normal vs inverse).
= fraction of A in oct. sites
= 0 is normal, = 1 is inverse
In the absence of CFSE effects: 2,3 spinels tend to be normal (MgAl
2
O
4
)
4,2 spinels tend to be inverse (TiMg
2
O
4
)
l E f h f ll In 2,3 spinels, CFSE favors the following:
1) Chromium spinels (Cr
3+
) are normal
2) Magnetite (Fe
3
O
4
) is inverse b/c 2) Magnetite (Fe
3
O
4
) is inverse b/c
Fe
3+
has zero CFSE, while Fe
2+
prefers oct.
3) Mn
3
O
4
is normal b/c Mn
2+
has no CFSE 149
CORUNDUM STRUCTURE (-Al
2
O
3
)
(HCP 2/3 f O t H l fill d) (HCP, 2/3 of Oct. Holes filled)
Space Group = R3c
Lattice = Primitive trigonal
Coordination = 6, 4
Cation Coord Octahedron Cation Coord. Octahedron
Anion Coord. distorted tetrahedron
Connectivity edge, face-sharing Oct.
6 Al
2
O
3
per unit cell
Ruby (Cr), sapphire (Fe, Ti, Cr), Fe
2
O
3
150