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STRUCTURES OF SOLIDS

SOLIDS can be divided into two categories.

 Crystalline  Amorphous
Crystalline has long range order

Amorphous materials have short range order

TYPES OF CRYSTALLINE SOLIDS


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

Dispersion Dipole-dipole H-bonds Metallic bond

O2, P4, H2O, Sucrose

Metallic

Atoms

Na, Cu, Fe

Ionic

Positive and negative ions

Ion-ion attraction

NaCl, CaF2, MgO

Network

Covalent Atoms

SiO2(Quartz) C (Diamond)

STRUCTURES OF CRYSTALLINE SOLID TYPES

Na+ Cl-

Molecular Solids

Covalent Solids

Ionic solids

Metallic solids
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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.
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Crystal = Lattice + Motif


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

ONE DIMENTIONAL LATTICE


a

ONE DIMENTIONAL UNIT CELL


UNIT CELL : Building block, repeats in a regular way

TWO DIMENTIONAL LATTICE

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TWO DIMENTIONAL UNIT CELL TYPES b a { b, U { 90 a a a { b, U = 90 b a b a { b, U = 90

a = b, U = 90 a a a

a = b, U =120 a
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TWO DIMENTIONAL UNIT CELL POSSIBILITIES OF NaCl

Na+ Cl-

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Five 2D lattices

a{b K { 90r, K { 120r

a=b K=90r a{b K=90r

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 )
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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

7 UNIT CELL TYPES + 4 LATTICE TYPES = 14 BRAVAIS LATTICES


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Isometric or Cubic

19

Tetragonal

20

Hexagonal

21

Rhombohedral

22

Orthorhombic

23

Monoclinic

24

Triclinic

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Summary of Crystal Structures

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

F K a

E b

c a b

Simple Cubic Structure (SC)


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

Close-packed directions are cube edges.

Coordination No. = 6 (# nearest neighbors) for each atom as seen


(Courtesy P.M. Anderson)

(c) 2003 Brooks/Cole Publishing / Thomson Learning

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.

Calculations Using Unit Cells


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:

a2 +a2 = (4r)2 Pythagoreans


Theorem

Simplifying 2a2 =16r2 a2=8r2a a

= r (8)

Body Centered: We need a better 3-D view in order to derive a formula!

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.

(c) 2003 Brooks/Cole Publishing / Thomson Learning

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

Atomic Packing Factor (APF)


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 =

volume atom 4 T(0.5a) 3 1 3 a3 volume unit cell

Here: a = Rat*2 Where Rat is the handbook atomic radius

Body Centered Cubic Structure (BCC)


Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

ex: Cr, W, Fe (E), Tantalum, Molybdenum

Coordination # = 8

Adapted from Fig. 3.2, Callister 7e.

2 atoms/unit cell: (1 center) + (8 corners x 1/8)


(Courtesy P.M. Anderson)

Calculations Using Unit Cells


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)

Remember: simple cubic = 1 atom; body centered = 2 atoms; face-centered = 4 atoms

Example 3.3 Calculating the Packing Factor


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

a03 Since, for FCC unit cells, a 0 ! 4r/


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

(4 atoms/cell)( Tr ) 3 Packing Factor ! 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.

Face Centered Cubic (FCC)


2 a 0 ! 4r
r 2r r a0 a0

Calculations Using Unit Cells


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:

a2 +a2 = (4r)2 Pythagoreans


Theorem

Simplifying 2a2 =16r2 a2=8r2a a

= r (8)

Body Centered: We need a better 3-D view in order to derive a formula!

Calculations Using Unit Cells


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 )

Now we get to do practice problems!

Body Centered Cubic (BCC)


3a 0 ! 4r
2a0
a0

3a0

Atomic Packing Factor: BCC


3a

a
2a

a 2 4 3

Close-packed directions: length = 4R = 3 a T ( 3a/4 ) 3 a3 volume atom volume

atoms unit cell APF =


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

unit cell APF for a body-centered cubic structure = 0.68

Face Centered Cubic Structure (FCC)


Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: (6 face x ) + (8 corners x 1/8)


(Courtesy P.M. Anderson)

Atomic Packing Factor: FCC


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

R atoms unit cell

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

Atomic weight (g/mol)

V! nA VcNA Volume/unit cell


(cm3/unit cell)

Avogadro's number (6.023 x 10 23 atoms/mol)

Characteristics of Selected Elements at 20C


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)

V! nA VcNA Volume/unit cell


(cm3/unit cell)

Avogadro's number (6.023 x 10 23 atoms/mol)

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)

V ! nA VcNA Volume/unit cell


(cm3/unit cell)

Avogadro's number (6.023 x 10 23 atoms/mol)

Example problem on Density Computation

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:

n= 4 Vc= a3 = (2R2)3 = 16 R3 2 NA = 6.023 x 1023 atoms/mol

V = n A / Vc NA

V = 4 x 63.5 g/mol / 16 2(1.28 x 10-8 cm)3 x 6.023 x 1023 atoms/mol

Ans = 8.98 g/cm3


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

Example 3.4 Determining the Density of BCC Iron


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

Avogadros number NA = 6.02 v 1023 atoms/mol

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) =

3.6 Polymorphism and Allotropy


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.

Allotropic or Polymorphic Transformations


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.

POLYMORPHISM AND ALLOTROPY

BCC (From room temperature to 912 oC)

Fe
FCC (at Temperature above 912 oC)

912 oC Fe (BCC) Fe (FCC)

X-RAYS TO CONFIRM CRYSTAL STRUCTURE


Incoming X-rays diffract from crystal planes, following Braggs law: nP = 2dsin(U) de
1
te c
s ay r X-

to r

extra distance travelled by wave 2

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

reflections must be in phase to detect signal


Adapted from Fig. 3.2W, Callister 6e.

spacing d between planes

x-ray intensity (from detector)

d=nP/2sinUc

U Uc

7.3.2 Laue equation and Braggs Law


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

Max Von Laue

Laue equation

(Based on diffraction by 1D lattice)

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

Expanded to 3D lattice case a(S-S0) = a(cosE-cosE0) = hP b(S-S0) = b(cosF-cosF0) = kP c(S-S0) = c(cosK-cosK0) = lP

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

n=2 Virtual reflection plane

2d(hkl) sinUn = nP (n=1, 2, 3, )

Lattice plane indices

2dhkl sinU = P

(dnhnknl = dhkl/n)

Diffraction indices or virtual reflection plane indices.

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

X-Ray Diffraction & Bragg Equation


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.

Sir William Henry Bragg (1862-1942), William Lawrence Bragg (1890-1971)

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".

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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.

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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.

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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 !Incident angle U ! Reflected angle P ! Wavelength of X-ray


U U 2U

Total Diffracted Angle ! 2U

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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

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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.
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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

Scattering of X-rays from adjacent lattice points A and B


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
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Constructive interference of waves scattered from the same plane


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.

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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
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Labelling the reflection planes


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
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n-th order diffraction off (hkl) planes


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

X-ray structure analysis of NaCl and KCl


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

Experimental arrangements for x-ray diffraction


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
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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

Types of X-ray camera


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

X-RAY DIFFRACTION METHODS

X-Ray Diffraction Method

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

V(particles in unit cell) x 100% ! packing efficiency V(total in unit cell)

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

V(particles in unit cell) x 100% ! packing efficiency V(total in unit cell)

Body-Centered Cubic Crystal Structure (II)

 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

 Corner and center atoms are equivalent

SINGLE LAYER PACKING

SQUARE PACKING

CLOSE PACKING

Close-packing-HEXAGONAL coordination of each sphere


91

TWO LAYERS PACKING

92

THREE LAYERS PACKING

93

94

Hexagonal close packing

Cubic close packing

95

Cubic close packing

Hexagonal close packing

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)

74% Space is occupied Coordination number = 12

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NON-CLOSE-PACKED STRUCTURES
a) Body centered cubic ( BCC ) b) Primitive cubic ( P)

68% of space is occupied Coordination number = 8

52% of space is occupied Coordination number = 6


97

Structure Primitive Cubic Bodycentered Cubic Hexagonal close packed Cubic close packed

Coordination number 6 8

Stacking pattern AAAAA ABABAB

Nonclose packing

12 12

ABABAB ABCABC
98

Close packing

Primitive cubic Body centered cubic Face centered cubic

Coordination number

12

99

100

ALLOTROPES

Existence of same element in different crystal structures. eg. Carbon

Diamond

Graphite

Buckminsterfullerene

101

TYPE OF HOLES IN CLOSE PACKING

TETRAHEDRAL HOLES

OCTAHEDRAL HOLES

102

LOCATION OF OCTAHEDRAL HOLES IN CLOSE PACKING

103

LOCATION OF TETRAHEDRAL HOLES IN CLOSE PACKING

104

IONIC CRYSTAL STRUCTURES

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

105

Hole Occupation - RADIUS RATIO RULE


Radius of the positive ion Radius ratio
=

Radius of the negative ion

Radius ratio

Coordinate number

Holes in which positive ions pack

0.225 0.414 0.414 0.732 0.732 1

4 6 8

Tetrahedral holes Octahedral holes Cubic holes


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IONIC CRYSTAL TYPES

Ionic crystal type

Co-ordination Structure type number A X

AX

6 8 6 8 6

6 8 3 4 2

NaCl CsCl Rutile(TiO2) Fluorite (CaF2) ReO3


107

AX2

AX3

STRUCTURE TYPE - AX CLOSE PACKED STRUCTURES a) ROCK SALT STRUCTURE (NaCl)

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

b) SPHALERITE OR ZINC BLEND (ZnS) STRUCTURE

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

c) NICKEL ARSENIDE (NiAs)

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)
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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

COMPARISON OF WURTZITE AND ZINC BLENDE

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

STRUCTURE TYPE - AX2


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

STRUCTURE TYPE - AX2


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

ALTERNATE REPRESENTATION OF FLUORITE STRUCTURE

AntiFlourite structure (or Na2O structure) positions of cations and anions are reversed related to Fluorite structure
116

RUTILE STRUCTURE, TiO2

HCP of O2- ( distorted hcp or Tetragonal) Ti4+ in half of octahedral holes

117

STRUCTURE TYPE - AX2 NON-CLOSE PACKED STRUCTURE


LAYER STRUCTURE ( eg. Cadmium iodide ( CdI2 ))

HCP of Iodide with Cd in Octahedral holes of alternate layers CCP analogue of CdI2 is CdCl2
118

COMPARISON OF CdI2 AND NiAs

119

HCP ANALOGUE OF FLOURITE (CaF2) ?


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

Unknown HCP analogue of Fluorite

120

HOLE FILLING IN CCP

121

SUMMARY OF IONIC CRYSTAL STRUCTURE TYPES


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)
122

Examples of CCP Structure Adoption


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

Examples of HCP Structure Adoption


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
124

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

125

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
126

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

INVERSE SPINEL  A2+ ions and half of B3+ ions


occupy octahedral holes  Other half of B3+ ions occupy tetrahedral holes  Formula unit is B(AB)O4
128