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Crystalline Amorphous

Crystalline has long range order

Crystal Type

Atomic

Particles

Atoms

Interparticle Forces

Dispersion

Physical Behaviour

Soft Very low mp Poor thermal and electrical conductors Fairly soft Low to moderate mp Poor thermal and electrical conductors Soft to hard Low to very high mp Mellable and ductile Excellent thermal and electrical conductors Hard and brittle High mp Good thermal and electrical conductors in molten condition Very hard Very high mp Poor thermal and electrical conductors

Examples

Group 8A Ne to Rn

Molecular

Molecules

Metallic

Atoms

Na, Cu, Fe

Ionic

Ion-ion attraction

Network

Covalent Atoms

SiO2(Quartz) C (Diamond)

Na+ Cl-

Molecular Solids

Covalent Solids

Ionic solids

Metallic solids

5

DIAMOND

QUARTZ

GRAPHITE

Unit Cell

The unit cell and, consequently, the entire lattice, is uniquely determined by the six lattice constants: a, b, c, , and . Only 1/8 of each lattice point in a unit cell can actually be assigned to that cell. Each unit cell in the figure can be associated with 8 x 1/8 = 1 lattice point.

7

Motif or Basis: typically an atom or a group of atoms associated with each lattice point

Lattice the underlying periodicity of the crystal Basis Entity associated with each lattice points

Lattice how to repeat Motif what to repeat

Lattice

Translationally periodic arrangement of points

Crystal

Translationally periodic arrangement of motifs

a

UNIT CELL : Building block, repeats in a regular way

10

a = b, U = 90 a a a

a = b, U =120 a

11

Na+ Cl-

12

Five 2D lattices

a{b K=90r

a=b K=120r

unit cell

Primitive Centered

There are literally thousands of crystalline materials, there are only 5 distinct planar lattices

LATTICE TYPES

Primitive ( P )

Body Centered ( I )

Face Centered ( F )

C-Centered (C )

14

Crystalline Solids

There are several types of basic arrangements in crystals, such as the ones shown above.

# of Atoms/Unit Cell

simple cubic unit cell = 1 atom body centered cubic = 2 atoms face-centered cubic = 4 atoms

Crystalline Solids

We can determine the empirical formula of an ionic solid by determining how many ions of each element fall within the unit cell.

BRAVAIS LATTICES

18

Isometric or Cubic

19

Tetragonal

20

Hexagonal

21

Rhombohedral

22

Orthorhombic

23

Monoclinic

24

Triclinic

25

The Choice of a Unit Cell: Have the highest symmetry and minimal size

F K a

E b

c a b

Rare due to low packing density (only Po Polonium -- has

this structure)

(Courtesy P.M. Anderson)

Figure 3.15 Illustration of coordinations in (a) SC and (b) BCC unit cells. Six atoms touch each atom in SC, while the eight atoms touch each atom in the BCC unit cell.

2) Finding the radius of the atom given the type of unit cell and the length of one side of the lattice.

(This can be a little more complicated to derive a nice formula.)

a By looking at the unit cells, we can determine how the length of one side, (a), is related to the radius, (r), of one atom Simple Cubic: a

= 2r

or

r = aeasy to see!

Face Centered:

Theorem

= r (8)

Example 3.2 Determining the Relationship between Atomic Radius and Lattice Parameters

Determine the relationship between the atomic radius and the lattice parameter in SC, BCC, and FCC structures when one atom is located at each lattice point.

Figure 3.14 The relationships between the atomic radius and the Lattice parameter in cubic systems (for Example 3.2).

Example 3.2 SOLUTION Referring to Figure 3.14, we find that atoms touch along the edge of the cube in SC structures.

a0

! 2r

In BCC structures, atoms touch along the body diagonal. There are two atomic radii from the center atom and one atomic radius from each of the corner atoms on the body diagonal, so

a0

4r ! 3

In FCC structures, atoms touch along the face diagonal of the cube. There are four atomic radii along this lengthtwo radii from the facecentered atom and one radius from each corner, so:

a0

4r ! 2

APF = Volume of atoms in unit cell* Volume of unit cell *assume hard spheres APF for a simple cubic structure = 0.52 atoms unit cell R=0.5a

close-packed directions contains (8 x 1/8) = 1 atom/unit cell

Adapted from Fig. 3.23, Callister 7e.

APF =

Atoms touch each other along cube diagonals.

--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

Coordination # = 8

(Courtesy P.M. Anderson)

There are 2 basic calculations involving unit cells: 1) Finding the density of an element given the type of unit cell and the length of one side of the lattice.

Density = mass/volume mass = (# of atoms in the unit cell)

x (1 mole)_____ x (formula mass) (1 mole) (6.02 x 1023 atoms)

volume = LxWxH = (length of one side)3 we will use a as the length of one side, so V= a3 Putting them togetherDensity= (# of atoms in the unit cell) 3

(a ) _(formula mass)_ (6.02 x 1023 atoms)

Calculate the packing factor for the FCC cell. Example 3.3 SOLUTION In a FCC cell, there are four lattice points per cell; if there is one atom per lattice point, there are also four atoms per cell. The volume of one atom is 4 r3/3 and the volume of the unit 3 cell is a0 . 4 3

4 3 (4)( Tr ) 3 ! Packing Factor ! 3 ( 4r / 2 )

T $ 0.74 18

Example: Cubic unit cell of CsCl, a=b=c E=F=K=90r Cs:(0,0,0) Cl: (1/2,1/2,1/2)

Single Crystal: Composed of only one particular type of space lattice. Polycrystalline matter: Clusters of multiple crystals.

2 a 0 ! 4r

r 2r r a0 a0

2) Finding the radius of the atom given the type of unit cell and the length of one side of the lattice.

(This can be a little more complicated to derive a nice formula.)

a By looking at the unit cells, we can determine how the length of one side, (a), is related to the radius, (r), of one atom Simple Cubic: a

= 2r

or

r = aeasy to see!

Face Centered:

Theorem

= r (8)

A body-centered lattice is slightly trickier than the face-centered lattice because our diagonal doesnt lie on the face of the cube. Instead, it lies within the body of the cube. We will also assume that the particles come in contact with each other unlike this drawing.

Solving for the triangle in blue c2 = a2 + b2 (4r)2 = a2 + b2 We dont have a value for b, but we can recognize that it is also a hypotenuse of a right triangle b2 = a2 +a2 Substituting (4r)2 = a2 + a2 + a2 Simplifying16r2 = 3a2

a a

(body-centered lattice)

Solving for a a

= r(5 )

3a 0 ! 4r

2a0

a0

3a0

3a

a

2a

a 2 4 3

Adapted from Fig. 3.2(a), Callister 7e.

Atoms touch each other along face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

Coordination # = 12

(Courtesy P.M. Anderson)

APF for a face-centered cubic structure = 0.74 The maximum achievable APF! 2a Close-packed directions: length = 4R = 2 a

(a = 22*R)

a

Adapted from Fig. 3.1(a), Callister 7e.

Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4 4 3 T( 2a/4 ) 3 a3 volume atom volume unit cell

Theoretical Density, V

Ex: Cr (BCC) A = 52.00 g/mol R = 0.125 nm n=2 @ a = 4R/3 = 0.2887 nm a 2 52.00 a 3 6.023 x 1023 g mol Vactual atoms mol Vtheoretical = 7.18 g/cm3 = 7.19 g/cm3

V=

volume unit cell

THEORETICAL DENSITY, V

Density = mass/volume mass = number of atoms per unit cell * mass of each atom mass of each atom = atomic weight/avogadros number

# atoms/unit cell

(cm3/unit cell)

At. Weight Element Symbol (amu) Aluminum Al 26.98 Argon Ar 39.95 Barium Ba 137.33 Beryllium Be 9.012 Boron B 10.81 Bromine Br 79.90 Cadmium Cd 112.41 Calcium Ca 40.08 Carbon C 12.011 Cesium Cs 132.91 Chlorine Cl 35.45 Chromium Cr 52.00 Cobalt Co 58.93 Copper Cu 63.55 Flourine F 19.00 Gallium Ga 69.72 Germanium Ge 72.59 Gold Au 196.97 Helium He 4.003 Hydrogen H 1.008 Density (g/cm3) 2.71 -----3.5 1.85 2.34 -----8.65 1.55 2.25 1.87 -----7.19 8.9 8.94 -----5.90 5.32 19.32 ----------Crystal Structure FCC -----BCC HCP Rhomb -----HCP FCC Hex BCC -----BCC HCP FCC -----Ortho. Dia. cubic FCC ----------Atomic radius (nm) 0.143 -----0.217 0.114 Adapted from -----Table, "Charac-----teristics of 0.149 Selected Elements", 0.197 inside front 0.071 cover, Callister 6e. 0.265 -----0.125 0.125 0.128 -----0.122 0.122 0.144 -----------

THEORETICAL DENSITY, V

# atoms/unit cell Atomic weight (g/mol)

(cm3/unit cell)

Example: Copper

Data from Table inside front cover of Callister (see previous slide): crystal structure = FCC: 4 atoms/unit cell atomic weight = 63.55 g/mol (1 amu = 1 g/mol) -7 atomic radius R = 0.128 nm (1 nm = 10 cm) Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical VCu = 8.89 g/cm3 Compare to actual: VCu = 8.94 g/cm3

THEORETICAL DENSITY

# atoms/unit cell Atomic weight (g/mol)

(cm3/unit cell)

Problem: Compute the density of Copper Given: Atomic radius of Cu = 0.128 nm (1.28 x 10-8 cm)

Atomic Weight of Cu = 63.5 g/mol Crystal structure of Cu is FCC

Solution:

V = n A / Vc NA

Experimentally determined value of density of Cu = 8.94 g/cm3

Determine the density of BCC iron, which has a lattice parameter of 0.2866 nm. Example 3.4 SOLUTION Atoms/cell = 2, a0 = 0.2866 nm = 2.866 Atomic mass = 55.847 g/mol Volume of unit cell = cm3/cell = a0 (2.866 v 10-8 cm)3 = 23.54 v 10-24

3

10-8 cm

Density V !

(number of atoms/cell)(atomic mass of iron) (volume of unit cell)(Avogadro' s number) ( 2)(55.847) V ! ! 7.882 g / cm 3 ( 23.54 v 10 24 )(6.02 v 10 23 )

Calculate Unit-Cell Dimension from Unit-Cell Type and Density: Pt crystallizes in a face-centered cubic (fcc) lattice with all atoms at the lattice points. It has a density of 21.45 g/cm3 and an atomic weight of 195.08 amu. Calculate the length of a unit-cell edge. Compare this with the value of 392.4 pm obtained from X-ray diffraction. STRATEGY: We can calculate the mass of the unit cell from the atomic weight. Knowing the density and the mass of the unit cell, we can calculate the volume of a unit cell and then the edge length of a unit cell. Mass of one Pt atom: 195.08 g Pt x 1 mol Pt = 3.239 x 10-22g Pt 1 mol Pt 6.022 x 1023Pt atoms 1 Pt atom Since there are 4 atoms of Pt per fcc unit cell, the mass per unit cell = 4 x 3.239 x 10-22 = 1.296 x 10-21 g Pt 1 unit cell Since d = m/V; the Volume of the unit cell is: V = m/d V = (1.296 x 10-21 g Pt/cell) /(21.45 g/cm3) V = 6.042 x 10-23 cm3 /cell But the Volume of the cell = a3; therefore, a = V1/3 a = ( 6.042 x 10-23 cm3)1/3 = 3.924 x 10-8 cm a = 3.924 x 10-10 m = 3.924 Angstrom = 392.4 pm This is exactly the number obtained by the x-ray 53 diffraction experiment.

Calculate Atomic Mass from Unit-Cell Dimension and Density: The unit cell length for Ag was determined to be 408.6 pm. Ag crystallizes in a fcc lattice with all atoms at the lattice points. Ag has a density of 10.50 g/cm3. Calculate the mass of a Ag atom, and, using the known atomic weight (107.87 amu), calculate Avogadro's #. STRATEGY: We can calculate the unit cell volume from a. Then, from the density, we can find the mass of the unit cell and then the mass of a single Ag atom. From this, we can find Avogadro's number. The Volume of the cell = a3: V = (408.6 x 10-12 m)3 V = 6.822 x 10-29 m3 The density of silver (in g/m3) is: d =10.50 g/cm3 x (1 cm/10-2m)3 = 1.050 x 107 g/m3 The mass of one unit cell is: m = d*V m = 1.050 x 107 g/m3 x 6.822 x 10-29 m3 m = 7.163 x 10-22 g Ag/cell Because there are 4 atoms in a fcc cell, the mass of a single Ag atom in the cell (7.163 x 10-22 g Ag/cell) / (4 atoms/cell) = 1.791 x 10-22 g Ag/atom The molar mass (Avogadro's number) = N 107.87 g Ag /mol Ag = 6.023 x 1023 atoms/mol 1.791 x 10-22 g Ag/atom OR: rho = Z*M / V*N 54 N = Z*M/rho*V = (4 atoms)(107.87 g/mol) =

Polymorphism The phenomenon in some metals, as well as nonmetals, having more than one crystal structures. When found in elemental solids, the condition is often called allotropy. Examples: Graphite is the stable polymorph at ambient conditions, whereas diamond is formed at extremely high pressures. Pure iron is BCC crystal structure at room temperature, which changes to FCC iron at 912oC.

Allotropy - The characteristic of an element being able to exist in more than one crystal structure, depending on temperature and pressure. Polymorphism - Compounds exhibiting more than one type of crystal structure.

Fe

FCC (at Temperature above 912 oC)

Incoming X-rays diffract from crystal planes, following Braggs law: nP = 2dsin(U) de

1

te c

s ay r X-

to r

Measurement of:

Critical angles, Uc, for X-rays provide atomic spacing, d.

1 g in 2 m co ys in -ra X

g in o tg ou U

Adapted from Fig. 3.2W, Callister 6e.

d=nP/2sinUc

U Uc

1. Laue equations Laue first mathematically described diffraction from crystals consider X-rays scattered from every atom in every unit cell in the crystal and how they interfere with each other to get a diffraction spot you must have constructive interference

Laue equation

Interference condition: the difference in path lengths of adjacent lattice points must be a multiple integral of the wavelength. AD-CB = hP AD = aS = acosE CB = aS0 = acosE0 a(cosE-cosE0) = hP, h=0, s1, s2 . Where, a lattice parameter E0angle between a and s0 E angle between a and s

For each h value, the diffraction rays from a 1D lattice E make a cone.

E0

This is the Laue Equation! where, a,b,clattice parameter E0,F0,K0angle between a,b,c and s0 E,F,K angle between a,b,c and s h,k,l indices of diffraction, integers

which may not be prime to each other and are different from Miller indices for crystal plane!

In the diffraction direction, the difference between the incident and the diffracted beam through any two lattice points must be an integral number of wavelengths. The vector from (000) to (mnp): Tmnp = ma + nb +pc The differences in wavelengths: ( =Tmnp (S-S0) =(ma + nb +pc) (S-S0) = ma (S-S0)+nb (S-S0)+pc (S-S0) =mhP+ nkP+plP =(mh+nk+pl)P

2. The Braggs Law Bragg discovered that you could consider the diffraction arising from reflection from lattice planes

s0

U O

P

s

U dhkl

Conditions to obtain constructive inferences, a. the scattered x-ray must be coplanar with the incident x-ray and the normal of the lattice plane. b. US=US0

(=AD+DB = 2d(hkl)sinUn Condition for diffraction: 2d(hkl) sinUn = nP (n=1, 2, 3, ) Un: n: the angle of reflection the order of the reflection

(dnhnknl = dhkl/n)

s0

U O U A D

s

dhkl

2dnhnknlsinUnh,nk,nl=P

However, the reflection order n is not measurable! Reformulated Bragg equations: 2dhkl sinU = P reflection indices

2dhkl sinU = P

(dnhnknl = dhkl/n)

The Bragg equation defines the direction of diffraction beams from a given set of lattice planes!

English physicists Sir W.H. Bragg and his son Sir W.L. Bragg developed a relationship in 1913 to explain why the cleavage faces of crystals appear to reflect X-ray beams at certain angles of incidence (theta, ).This observation is an example of X-ray wave interference.

o 1915, the father and son were awarded the Nobel prize for physics "for their

services in the analysis of crystal structure by means of Xrays".

66

Bragg Equation

Bragg law identifies the angles of the incident radiation relative to the lattice planes for which diffraction peaks occurs. Bragg derived the condition for constructive interference of the X-rays scattered from a set of parallel lattice planes.

67

BRAGG EQUATION

W.L. Bragg considered crystals to be made up of parallel planes of atoms. Incident waves are reflected specularly from parallel planes of atoms in the crystal, with each plane is reflecting only a very small fraction of the radiation, like a lightly silvered mirror. In mirrorlike reflection the angle of incidence is equal to the angle of reflection.

68

Diffraction Condition

The diffracted beams are found to occur when the reflections from planes of atoms interfere constructively. We treat elastic scattering, in which the energy of X-ray is not changed on reflection.

69

Bragg Equation

When the X-rays strike a layer of a crystal, some of them will be reflected. We are interested in X-rays that are in-phase with one another. X-rays that add together constructively in x-ray diffraction analysis in-phase before they are reflected and after they reflected.

U U 2U

70

Bragg Equation

These two x-ray beams travel slightly different distances. The difference in the distances traveled is related to the distance between the adjacent layers. Connecting the two beams with perpendicular lines shows the difference between the top and the bottom beams.

The line CE is equivalent to the distance between the two layers (d)

DE ! d sin U

71

Bragg Law

The length DE is the same as EF, so the total distance traveled by the bottom wave is expressed by: EF ! d sin U DE ! d sin U DE EF ! 2d sin U nP ! 2d sin U Constructive interference of the radiation from successive planes occurs when the path difference is an integral number of wavelenghts. This is the Bragg Law.

72

Bragg Equation

2d sin U ! nP

where, d is the spacing of the planes and n is the order of diffraction. Bragg reflection can only occur for wavelength

nP e 2d

This is why we cannot use visible light. No diffraction occurs when the above condition is not satisfied. The diffracted beams (reflections) from any set of lattice planes can only occur at particular angles pradicted by the Bragg law.

73

X-rays are incident at an angle set. on one of the planes of the U

There will be constructive interference of the waves scattered from the two successive lattice points A and B in the plane if the distances AC and DB are equal.

D U U A

C 2U B

74

If the scattered wave makes the same angle to the plane as the incident wave The diffracted wave looks as if it has been reflected from the plane We consider the scattering from lattice points rather than atoms because it is the basis of atoms associated with each lattice point that is the true repeat unit of the crystal; The lattice point is analoque of the line on optical diffraction grating and the basis represents the structure of the line.

75

Coherent scattering from a single plane is not sufficient to obtain a diffraction maximum. It is also necessary that successive planes should scatter in phase This will be the case if the path difference for scattering off two adjacent planes is an integral number of wavelengths

Diffraction maximum

2d sin U ! nP

76

To label the reflections, Miller indices of the planes can be used. A beam corresponding to a value of n>1 could be identified by a statement such as the nth-order reflections from the (hkl) planes. (nh nk nl) reflection Third-order reflection from (111) plane (333) reflection

77

Rewriting the Bragg law

d 2 sin U ! P n

which makes n-th order diffraction off (hkl) planes of spacing d look like first-order diffraction off planes of spacing d/n. Planes of this reduced spacing would have Miller indices (nh nk nl).

78

The GENERAL PRINCIBLES of X-RAY STRUCTURE ANALYSIS to DEDUCE the STRUCTURE of NaCl and KCl Bragg used an ordinary spectrometer and measured the intensity of specular reflection from a cleaved face of a crystal

found six values ofU for which a sharp peak in intensity occurred, corresponding to three characteristics wavelengths (K,L and M x-rays) in first and second order (n=1 and n=2 in Bragg law) By repeating the experiment with a different crystal face he could use his eqn. to find for example the ratio of (100) and (111) plane spacings, information that confirmed the cubic symmetry of the atomic arrangement.

79

Details of structure

Details of structure were than deduced from the differences between the diffraction patterns for NaCl and KCl. Major difference; absence of (111) reflection in KCl compared to a weak but detectable (111) reflection in NaCl. This arises because the K and Cl ions both have the argon electron shell structure and hence scatter x-rays almost equally whereas Na and Cl ions have different scattering strengths. (111) reflection in NaCl corresponds to one wavelength of path difference between neighbouring (111) planes.

80

Since the pioneering work of Bragg, x-ray diffraction has become into a routine technique for the determination of crsytal structure.

81

Bragg Equation

Since Bragg's Law applies to all sets of crystal planes, the lattice can be deduced from the diffraction pattern, making use of general expressions for the spacing of the planes in terms of their Miller indices. For cubic structures d! a h2 k 2 l 2

Note that the smaller the spacing the higher the angle of diffraction, i.e. the spacing of peaks in the diffraction pattern is inversely proportional to the spacing of the planes in the lattice. The diffraction pattern will reflect the symmetry properties of the lattice.

2d sin U ! nP

82

Bragg Equation

A simple example is the difference between the series of (n00) reflections for a simple cubic and a body centred cubic lattice. For the simple cubic lattice, all values of n will give Bragg peaks. However, for the body centred cubic lattice the (100) planes are interleaved by an equivalent set at the halfway position. At the angle where Bragg's Law would give the (100) reflection the interleaved planes will give a reflection exactly out of phase with that from the primary planes, which will exactly cancel the signal. There is no signal from (n00) planes with odd values of n. This kind of argument leads to rules for identifying the lattice symmetry from "missing" reflections, which are often quite simple.

83

There are many types of X-ray camera to sort out reflections from different crystal planes. We will study only three types of X-ray photograph that are widely used for the simple structures. 1.Laue photograph 2.Rotating crystal method 3.Powder photograph

84

Laue

Orientation Single Crystal Polychromatic Beam Fixed Angle

Rotating Crystal

Lattice constant Single Crystal Monochromatic Beam Variable Angle

Powder

Lattice Parameters Polycrystal (powdered) Monochromatic Beam Variable Angle

85

CLOSE-PACKING OF SPHERES

86

87

Example Problem: What is the packing efficiency in the simple cubic cell of CsCl? What is the percentage of empty space in the unit cell? The chloride ions are at the corners with the cesium in the middle of the unit cell. rCl- = 181 pm; rCs+ = 169 pm

Example Problem

What is the packing efficiency of NaCl? What is the percentage of empty space in the NaCl unit cell? ) rCl- = 181 pm; rNa+ = 98 pm; edge dist.NaCl = 562.8 pm

Hard spheres touch along cube diagonal cube edge length, a= 4R/3 The coordination number, CN = 8 Number of atoms per unit cell, n = 2 Center atom not shared: 1 x 1 = 1 8 corner atoms shared by eight cells: 8 x 1/8 = 1 Atomic packing factor, APF = 0.68

90

SQUARE PACKING

CLOSE PACKING

91

92

93

94

95

4 atoms in the unit cell (0, 2 atoms in the unit cell (0, 0, 0) 0, 0) (0, 1 /2, 1 /2) (1 /2, 0, 1 /2) (2/3, 1 /3, 1 /2) (1 /2, 1 /2, 0)

96

NON-CLOSE-PACKED STRUCTURES

a) Body centered cubic ( BCC ) b) Primitive cubic ( P)

97

Structure Primitive Cubic Bodycentered Cubic Hexagonal close packed Cubic close packed

Coordination number 6 8

Nonclose packing

12 12

ABABAB ABCABC

98

Close packing

Coordination number

12

99

100

ALLOTROPES

Diamond

Graphite

Buckminsterfullerene

101

TETRAHEDRAL HOLES

OCTAHEDRAL HOLES

102

103

104

Ionic structures may be derived from the occupation of holes by oppositely charged ions (interstitial sites) in the close-packed arrangements of ions.

105

Radius of the positive ion Radius ratio

=

Radius ratio

Coordinate number

4 6 8

106

AX

6 8 6 8 6

6 8 3 4 2

107

AX2

AX3

CCP Cl- with Na+ in all Octahedral holes Lattice: FCC Motif: Cl at (0,0,0); Na at (1/2,0,0) 4 NaCl in one unit cell Coordination: 6:6 (octahedral) Cation and anion sites are topologically identical

108

CCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-} filled) Lattice: FCC 4 ZnS in one unit cell Motif: S at (0,0,0); Zn at (1/4,1/4,1/4) Coordination: 4:4 (tetrahedral) Cation and anion sites are topologically identical

109

HCP with Ni in all Octahedral holes Lattice: Hexagonal - P Motif: 2Ni at (0,0,0) & (0,0,1/2) 2As at (2/3,1/3,1/4) & (1/3,2/3,3/4) 2 NiAs in unit cell Coordination: Ni 6 (octahedral) : As 6 (trigonal prismatic)

110

d) WURTZITE ( ZnS )

HCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-} filled ) Lattice: Hexagonal - P 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 Coordination: 4:4 (tetrahedral)

111

112

STRUCTURE TYPE - AX

NON CLOSE PACKED STRUCTURES CUBIC-P (PRIMITIVE) ( eg. Cesium Chloride ( CsCl ) )

Motif: Cl at (0,0,0); Cs at (1/2,1/2,1/2) 1 CsCl in one unit cell Coordination: 8:8 (cubic) Adoption by chlorides, bromides and iodides of larger cations, e.g. Cs+, Tl+, NH4+

113

CLOSE PACKED STRUCTURE eg. FLUORITE (CaF2)

CCP Ca2+ with F- in all Tetrahedral holes Lattice: fcc Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4) 4 CaF2 in one unit cell Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral) In the related Anti-Fluorite structure Cation and Anion positions are reversed

114

CLOSE PACKED STRUCTURE eg. FLUORITE (CaF2)

CCP Ca2+ with F- in all Tetrahedral holes Lattice: fcc Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4) 4 CaF2 in one unit cell Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral) In the related Anti-Fluorite structure Cation and Anion positions are reversed

115

AntiFlourite structure (or Na2O structure) positions of cations and anions are reversed related to Fluorite structure

116

117

LAYER STRUCTURE ( eg. Cadmium iodide ( CdI2 ))

HCP of Iodide with Cd in Octahedral holes of alternate layers CCP analogue of CdI2 is CdCl2

118

119

No structures of HCP are known with all Tetrahedral sites (T+ and T-) filled. (i.e. there is no HCP analogue of the Fluorite/AntiFluorite Structure). The T+ and T- interstitial sites above and below a layer of closepacked spheres in HCP are too close to each other to tolerate the coulombic repulsion generated by filling with like-charged species.

Fluorite

120

121

Formula Type and fraction of sites occupied All octahedral Half tetrahedral (T+ or T-)

CCP

Rock salt (NaCl) Zinc Blend (ZnS)

HCP

Nickel Arsenide (NiAs) Wurtzite (ZnS)

AX

AX2

All Tetrahedral Half octahedral (ordered framework) Half octahedral (Alternate layers full/ empty)

Fluorite (CaF2), Not known Anti-Fluorite (Na2O) Anatase (TiO2) Cadmium Chloride (CdCl2) Rutile (TiO2) Cadmium iodide (CdI2)

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Rock salt(NaCl) occupation of all octahedral holes Very common (in ionics, covalents & intermetallics ) Most alkali halides (CsCl, CsBr, CsI excepted) Most oxides / chalcogenides of alkaline earths Many nitrides, carbides, hydrides (e.g. ZrN, TiC, NaH) Fluorite (CaF2) occupation of all tetrahedral holes Fluorides of large divalent cations, chlorides of Sr, Ba Oxides of large quadrivalent cations (Zr, Hf, Ce, Th, U) Anti-Fluorite (Na2O) occupation of all tetrahedral holes Oxides /chalcogenides of alkali metals Zinc Blende/Sphalerite ( ZnS ) occupation of half tetrahedral holes Formed from Polarizing Cations (Cu+, Ag+, Cd2+, Ga3+...) and Polarizable Anions (I-, S2-, P3-, ...) e.g. Cu(F,Cl,Br,I), AgI, Zn(S,Se,Te), Ga(P,As), Hg(S,Se,Te) 123

Nickel Arsenide ( NiAs ) occupation of all octahedral holes 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) Cadmium Iodide ( CdI2 ) occupation half octahedral (alternate) holes Iodides of moderately polarising cations; bromides and chlorides of strongly polarising cations. e.g. PbI2, FeBr2, VCl2 Hydroxides of many divalent cations. e.g. (Mg,Ni)(OH)2 Di-chalcogenides of many quadrivalent cations . e.g. TiS2, ZrSe2, CoTe2 Cadmium Chloride CdCl2 (CCP equivalent of CdI2) half octahedral holes Chlorides of moderately polarising cations e.g. MgCl2, MnCl2 Di-sulfides of quadrivalent cations e.g. TaS2, NbS2 (CdI2 form as well) Cs2O has the anti-cadmium chloride structure

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PEROVSKITE STRUCTURE

Formula unit ABO3 CCP of A atoms(bigger) at the corners O atoms at the face centers B atoms(smaller) at the body-center

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PEROVSKITE

Lattice: Primitive Cubic (idealised structure) 1 CaTiO3 per unit cell A-Cell Motif: Ti at (0, 0, 0); Ca at (1/2, 1/2, 1/2); 3O at (1/2, 0, 0), (0, 1/2, 0), (0, 0, 1/2) Examples: NaNbO3 , BaTiO3 , Ca 12-coordinate by O (cuboctahedral) CaZrO , YAlO , KMgF 3 3 3 Ti 6-coordinate by O (octahedral) Many undergo small distortions: O distorted octahedral (4xCa + 2xTi) e.g. BaTiO3 is ferroelectric

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Problem (text) Cobalt(II) oxide is used as a pigment in pottery. It has the same type of crystal structure as NaCl. When exposed to Xrays (P=153 pm) reflections were observed at 42.38, 65.68, and 92.60. Determine the values of n to which these reflections correspond, and calculate the spacing between the crystal layers.

n = 2dsin

SPINEL STRUCTURE

Formula unit AB2O4 (combination of Rock Salt and Zinc Blend Structure) Oxygen atoms form FCC A2+ occupy tetrahedral holes B3+ occupy octahedral holes

occupy octahedral holes Other half of B3+ ions occupy tetrahedral holes Formula unit is B(AB)O4

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