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Chapter 13

Part 3

December 6, 2002

SOLIDS

Solids are either amorphous or crystalline.

AMORPHOUS SOLIDS:

- Considerable disorder in structure

Example: rubber, glass

CRYSTALLINE SOLIDS:

- Classified as Metallic, Ionic, Molecular, dependent

on the type of interaction (bond) that holds their atoms,

ions or molecules in place.

- Highly regular structure in the form of a lattice: a

three dimensional array of points representing the

centers of the components (such as atoms, ions or

molecules ) in the repeating pattern of the crystal

1

LATTICE

A unit cell, when stacked together repeatedly without

any gaps, can reproduce the entire 3D crystal.

their shape. People did not know atomic positions

within the crystal.

as a diffraction grating for X- rays …

spacing between atoms in the lattice, on the order of

the Bohr radius.

2

In 1912 Knipping observed X-ray diffraction patterns

X-Ray

Diffraction Pattern

When electromagnetic radiation passes through

a crystal…

in all directions. The waves constructively interfere

in certain directions and destructively interfere in

certain directions.

3

BRAGG DIFFRACTION LAW

nλ = 2d sinθ n is the order of diffraction

n = 1,2,3, …

Constructive

Demo, green and red lasers Interference

θ

λ light wavelength

1.8 µm

comparable to

laser wavelength

The laser wavelength is 0.53µm, ~5000 times longer than X-ray wavelength.

4

Demo

Diffraction of a laser

beam by the 2D

patterns

Simple Cubic (sc) Unit Cell

- Eight equivalent points at the

corners of a cube

- Eight equivalent points at the

corners of a cube and one at the

center

- Eight equivalent points at the

corners of a cube and six on the

center of the cube faces

5

Packing Spheres into Lattices

The most efficient way to pack hard spheres is

CLOSEST PACKING

is surrounded by six others.

lattices.

First Layer

6

For the second layer, spheres can fit into two

types of “dimples” formed by three spheres in

the first layer.

two sets of dimples

into half of the dimples of the same type.

7

Fill the Second Layer

the dimples in the first layer.

Occupied

Dimple

Unoccupied

Dimple

the dimples in the first layer.

8

The third layer is formed by choosing one of the

two sets of dimples.

NOTE:

the

inverted

triangle

1 2 2

1 1 2

1 1

9

THIRD LAYER OPTION ONE!

LAYERS ONE AND THREE ARE ON TOP OF EACH OTHER

CALLED HEXAGONAL CLOSEST PACKING (HCP)

BECAUSE THE ABA ARRANGEMENT GIVES

A HEXAGONAL UNIT CELL.

10

Again, the third layer has choices of two sets of

dimples.

NOTE: the

inverted

triangle

1 2 2

1 1 2

2 2

OVER THE SPHERES OF THE FIRST LAYER.

11

FILL THE THIRD LAYER OPTION 2

GREEN SPHERES DO NOT LIE DIRECTLY OVER

THE BLACK SPHERES OF THE FIRST LAYER.

A

B

C

THE ABC ARRANGEMENT OF LAYERS.

B

C

A

CUBIC CLOSEST-PACKED (CCP) …

12

BECAUSE CCP GIVES A CUBIC UNIT CELL

FACE- CENTRED CUBIC UNIT CELL.

HCP CCP

NOTICE the flip...

- the number of nearest neighbors that a lattice point has

in a crystalline solid. CN = 12 for both HCP &CCP

13

COORDINATION NUMBER FOR SIMPLE CUBIC UNIT

How do we count

nearest neighbors?

CN = 6

COORDINATION NUMBER

for the three types of cubic unit cells

(ccp same as hcp) CN = 12

14

EFFICIENCY OF PACKING

SPHERES IN A UNIT CELL

f =

v

volume of the unit cell

V

= spheres

V unitcell

Vunit cell = a3 cubic unit cell of edge length a

COUNTS 1 FOR

ATOM IN CELL

CELLS IN THE LATTICE

COUNTS FOR

CELL FACE 1/2 ATOM ON A

FACE.

15

Atoms are shared between adjacent unit

cells in the lattice

COUNTS FOR

CELL EDGE 1/4 ATOM ON A

FACE.

COUNTS AS

CELL CORNER 1/8 FOR ATOM

ON A

CORNER.

What is the number of spheres in the cell?

A sphere on 8 corners and 6 faces.

between adjacent unit cells

16

WHAT FRACTION OF SPACE IS OCCUPIED IN

A FACE CENTERED CUBIC UNIT CELL?

4

V 4( π r )3

f = spheres

= 3

v

V unitcell

a3

a

Spheres touch each other on the

surface of the cell. a

FACE DIAGONAL = r + 2r + r = 4r

r

a2 + a2 = (4r)2; 2a2 = 16r 2

2r

a2 = 8r 2 a = r 8

4 * 4 πr3

fv = 3 = 0.740

(r 8 )3 r

SIMPLE CUBIC BODY CENTERED CUBIC FACE CENTERED CUBIC

4r

2r

3

r 8

# of spheres in the unit cell

1 2 4

Fraction of volume occupied by spheres

52.4% 68.0% 74.0%

17

Calculating the density of a unit cell

mass

Density =

volume

NA Avogadro’s number!

Cu crystallizes as a fcc

cell

3 −8 3 − 23 3

−1

63.54gmol

The mass of a Cu atom is m = = 1.055 × 10 g − 22

6.022 × 10 mol

23 −1

4 × (1.055 × 10 −22 g )

Density = −23 3

= 8.89 gcm −3

4.75 × 10 cm

4 atoms per unit cell! The measured density is 8.92gcm-3.

18

Summary

Closest Packing

Cubic

Cubic Closest

Unit Packed

Cells (ccp)

(sc) cubic (bcc) cubic (fcc)

Hexagonal

Closest

Packed

(hcp)

Hexagonal

unit cell

19

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