Why Solids?

most elements solid at room temperature atoms in ~fixed position - simple case crystalline solid Crystal Structure

Why study crystal structures? description of solid comparison with other similar materials - classification correlation with physical properties

Crystals are everywhere!

More crystals

Solid State

 Crystalline

Solids: highly regular arrangement of their components. Crystalline solid produces the beautiful characteristic shapes of crystals.
solids: considerable disorder in their structures. Although glass is a solid, a great deal of disorder exists in its structure.

Amorphous

Types of Solids

Crystalline Solids

Amorphous Solids

They have long range order They lack in long range order They have sharp melting points They dont have sharp melting point

They are anisotropic Cleavage of crystal occurs along certain planes

They are isotropic They give a rough surface on cutting along any direction

Lattice: A 3-dimensional system of points designating the centers of components (atoms, ions, or molecules) that make up the substance. Unit Cell: The smallest repeating unit of the lattice.

simple cubic body-centered cubic face-centered cubic

Definitions
1. 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 with: 3 sides - a, b, c 3 angles - , ,

Seven unit cell shapes

Cubic Tetragonal Orthorhombic Monoclinic Triclinic Hexagonal Rhombohedral a=b=c a=b c a b c a b c a b c a=b c a=b=c = = = = = =90 = =90 = =90 =90, 90 90 = =90, =120 = = 90

2D example - rocksalt (sodium chloride, NaCl)

We define lattice points ; these are points with identical environments

Choice of origin is arbitrary - lattice points need not be atoms - but unit cell size should always be the same.

This is also a unit cell it doesnt matter if you start from Na or Cl

- or if you dont start from an atom

This is NOT a unit cell even though they are all the same - empty space is not allowed!

In 2D, this IS a unit cell In 3D, it is NOT

 Rare due to low packing density (only Po has Close-packed directions are cube edges.

this structure)

Coordination # = 6 (# nearest neighbors)

APF =

Volume of atoms in unit cell* Volume of unit cell

*assume hard spheres APF for a simple cubic structure = 0.52 volume atoms a R=0.5a unit cell APF = 4 1 3 a3 volume
unit cell

atom (0.5a) 3

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

20

 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 ( ), Tantalum, Molybdenum

Coordination # = 8

Click once on image to start animation (Courtesy P.M. Anderson)

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

21

 APF for a body-centered cubic structure = 0.68

3a

a
2a
R
atoms unit cell

a 4 2 3 a3

Close-packed directions: length = 4R = 3 a volume atom volume unit cell

( 3 a/4 ) 3

APF =

22

 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

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

23

 APF for a face-centered cubic structure = 0.74

maximum achievable APF

Close-packed directions: length = 4R = 2a

2a
Unit cell contains: 6 x 1/2 + 8 x 1/8 a
atoms unit cell

= 4 atoms/unit cell

4 4 3

( 2 a/4 ) 3

volume atom volume unit cell

APF =

a3

24

FCC Stacking Sequence

ABCABC... Stacking Sequence 2D Projection B A A sites B sites C sites B C B C B B B

C
B

A FCC Unit Cell C B

25

 ABAB... Stacking Sequence 3D Projection A sites 2D Projection Top layer

B sites A sites

Middle layer Bottom layer

Adapted from Fig. 3.3(a), Callister & Rethwisch 8e.

Coordination # = 12 APF = 0.74 c/a = 1.633

26

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn

What is percent area filled for each case??

area of circle Area of triangle

1 2 r 2 % Area filled = (2r )( 3r ) 2

2 3

90.7

Area of circle Area of square

% Area filled = r2/(2r)2 = 78.5

Area of circle = r2

Area of triangle = bh/2

Area of square = l2

At start all sites equivalent

Filled hollows Empty Hollows

After placing first atom in second layer, two sites now present

At start all sites equivalent

Filled hollows Empty Hollows

After placing first atom in second layer, two sites now present

A B

A site

C site

When placing atoms in third layer, we have two choices Similar to forming second layer, we can only choose 1 site.

A B

A site

Filling the A site gives an ABABABAB packing pattern Resulting in hexagonal close packing (hcp)

A C B

C site Filling the C site gives an ABCABCABC packing pattern Resulting in cubic close packing (ccp)

Hexagonal close packed

Cubic close packed

No matter what type of packing, the coordination number of each equal size sphere is always 12

We will see that other coordination numbers are possible for non-equal size spheres

Metals usually have one of three structure types: ccp (=fcc, see next slide), hcp or bcc (body centred cubic)

Sc Y La

Ti Zr Hf
hcp ccp = fcc bcc

V Nb Ta

Cr Mo W

Mn Tc Re

Fe Ru Os

Co Rh Ir

Ni Pd Pt

Cu Ag Au

Zn Cd Hg

The reasons why a particular metal prefers a particular structure are still not well understood

ccp = fcc ?
Build up ccp layers (ABC packing) Add construction lines - can see fcc unit cell

c.p layers are oriented perpendicular to the body diagonal of the cube

Tetrahedral T+

Octahedral O

Tetrahedral T-

Ball & Stick view of polyhedra

90 109.5

Ideal: Positions of maximum repulsion!

Solid view of polyhedra

Useful to describe: corner-sharing, edge-sharing, face-sharing polyhedra

Octahedral Sites

Coordinate , , Distance = a/2

Coordinate 0, , 0 [=1, , 0] Distance = a/2

In a face centred cubic anion array, cation octahedral sites at: , 0 0, 0 0, 0 0

Tetrahedral sites

Relation of a tetrahedron to a cube:

i.e. a cube with alternate corners missing and the tetrahedral site at the body centre

Can divide the f.c.c. unit cell into 8 minicubes by bisecting each edge; in the centre of each minicube is a tetrahedral site

So 8 tetrahedral sites in a fcc

Sizes of interstitials
fcc / ccp
Spheres are in contact along face diagonals octahedral site, bond distance = a/2 radius of octahedral site = (a/2) - r tetrahedral site, bond distance = a 3/4 radius of tetrahedral site = (a 3/4) - r

So the face of the unit cell looks like:

Calculate unit cell side in terms of r: 2a2 = (4r)2 a = 2r 2 Volume = (16 2) r3

Face centred cubic - so number of atoms per unit cell =corners + face centres = (8 1/8) + (6 1/2) = 4

Packing fraction
The fraction of space which is occupied by atoms is called the packing fraction, , for the structure
= space occupied by atoms available space

For cubic close packing:

4 3 r 3 16 2r 3

3 2

074 .

The spheres have been packed together as closely as possible, resulting in a packing fraction of 0.74

Example 1 Diamond Structure

Carbon atoms in all fcc positions Carbon atoms in half of tetrahedral positions (e.g. T+) Carbon coordinated to 4 other carbon atoms all are tetrahedral Looking at tetrahedra in the structure helps us see the diamond shape

Diamond Structure
Silicon, germanium and -tin also adopt this structure (all group 4 elements)

Melting Point (C) Conductor? Carbon Silicon

Germanium -Tin

3550 1410
940 230

Insulator Semiconductor
Semiconductor Conductor radius

Example 2 - Zinc Blende (ZnS: Sphalerite)

Sulphur atoms in all fcc positions Zinc atoms in half of tetrahedral positions (e.g. T+) Comparison with Diamond Very important in semiconductor industry (e.g. GaAs)

Ball and stick model shows us the 4-fold coordination in both structures

Example 3 Fluorite/Antifluorite structure

Antifluorite, Na2O Oxygen atoms in all fcc positions Sodium atoms in ALL tetrahedral sites

Fluorite, ZrO2 Zr atoms in all fcc positions O atoms in ALL tetrahedral sites

Note formulae: blue atoms (fcc) 4 per unit cell red atoms (tetrahedral) 8 per unit cell

NaCl Crystal Structure

Face-centered cubes of both ions offset by a half a unit cell in one direction. Many alkali metals have this same geometry. What is the coordination number (nearest neighbor)?

CsCl Crystal Structure

Chloride ions form simple cubes with cesium ions in the center The cesium ion is able to fit in to center hole. How? Other crystal structures.

Summary
Close packing occurs in a variety of metals
We can envisage layers, positions denoted by A, B and C, so that hexagonal close packing is represented by ABABA and cubic close packing is represented by ABCABCA

ccp is equivalent to face-centred cubic

Small ions can occupy interstitial sites in a close packed structure - both tetrahedral (4) and octahedral (6) sites exist

Factors affecting the formation of the amorphous state When primary bonds are 1D or 2D and secondary bonds aid in the formation of the crystal

The crystal structure is very complex

When the free energy difference between the crystal and the glass is small Tendency to crystallize would be small Cooling rate fast cooling promotes amorphization fast depends on the material in consideration Certain alloys have to be cooled at 10 6 K/s for amorphization Silicates amorphizes during air cooling

CRYSTALS

Molecular
Molecule held together by primary covalent bonds Intermolecular bonding is Van der walls

Non-molecular
COVALENT IONIC METALLIC

CLASSIFICATION OF SOLIDS BASED ON BONDING

COVALENT

IONIC

METALLIC

METALLIC
Positive ions in a free electron cloud Metallic bonds are non-directional Each atoms tends to surround itself with as many neighbours as possible! Usually high temperature (wrt to MP) BCC (Open structure)

The partial covalent character of transition metals is a possible reason for many of them having the BCC structure at low temperatures

FCC BCC HCP

Al, Fe (910 - 1410C), Cu, Ag, Au, Ni, Pd, Pt Li, Na, K , Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Fe (below 910C), Be, Mg, Ti, Zr, Hf, Zn, Cd

Others La, Sm Po, -Mn, Pu

CLOSE PACKING

FCC

FCC

Note: Atoms are coloured differently but are the same

HCP
+ +

Shown displaced for clarity

HCP

Note: Atoms are colored differently but are the same

Unit cell of HCP (Rhombic prism)

Atoms: (0,0,0), (, ,)

CV
h

6 a 4 6 a 12

CV

h CF VC c a 2h a 2 2 3

2 a 3 1.632

IDEAL c/a

PACKING FRACTION / Efficiency

Packing Fraction

Volume occupied by atoms Volume of Cell

SC* BCC* CCP HCP a = 2r
c 4r 2 3

Relation between atomic radius (r) and lattice parameter (a) Atoms / cell Lattice points / cell No. of nearest neighbours Packing fraction

a = 2r

3a

4r

2a 4r

1 1 6

2 2 8
3 8

4 4 12
2 6

2 1 12
2 6

6
= 0.52

= 0.68

= 0.74

= 0.74

* Crystal formed by monoatomic decoration of the lattice

FCC
TETRAHEDRAL

VOIDS OCTAHEDRAL

way along body diagonal {, , }, {, , } + face centering translations

At body centre {, , } + face centering translations

Vtetrahedron

1 Vcell 24

Voctahedron

1 Vcell 6

Note: Atoms are coloured differently but are the same

FCC- OCTAHEDRAL

Site for octahedral void

{, , } + {, , 0} = {1, 1, } {0, 0, }

Face centering translation

Equivalent site for an octahedral void

Note: Atoms are coloured differently but are the same

FCC voids

Position way from each vertex of the cube along body diagonal <111> ((, , ))
Body centre: 1 (, , ) Edge centre: (12/4 = 3) (, 0, 0)

Voids / cell

Voids / atom

Tetrahedral

Octahedral

Size of the largest atom which can fit into the tetrahedral void of FCC CV = r + x
e Radius of the new atom

6 e 4

e 2r

x r

3 1 ~ 0.225 2

Size of the largest atom which can fit into the Octahedral void of FCC

2r + 2x = a

2a 4r

x r

2 1 ~ 0.414

HCP
TETRAHEDRAL

VOIDS OCTAHEDRAL

Coordinates : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 13 , 18 ), ( 2 3 , 13 , 7 8 )

Coordinates: ( ,), (,,)

These voids are identical to the ones found in FCC

Note: Atoms are coloured differently but are the same

The other orientation of the tetrahedral void

Octahedral voids occur in 1 orientation, tetrahedral voids occur in 2 orientations

Note: Atoms are coloured differently but are the same

Note: Atoms are coloured differently but are the same

Octahedral voids

Tetrahedral void

Note: Atoms are coloured differently but are the same