Introduction to Nanoscience

LECTURE 10 Nanomaterials, Surface and Structure II

G.L. Hornyak Copyright: CRC Press 2009

Agenda

Crystal Systems Packing Fraction and Densities

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CRYSTAL SYSTEMS

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Cubic Systems

Bravais Lattice Systems

FCC (Bottom Left) and HCP (Bottom Right)

Tetragonal Hole (Left); Octahedral Hole (Right)

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HCP and FCC

A A B A B C

The highest density of packing of spheres follows the rule of C.F. Gauss:

3 2

= 0.74
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The Unit Cell, Coordination and Packing Fraction

The Unit Cell is an irreducible representation of the crystal structure of a pure material. It is defined by a set of parameters called lattice parameters. Lattice parameters include: cell dimensions a,b,c and crystallographic angles ,,. There are 14 Bravais lattices. Adding unit cells together result in, eventually, a macroscopic crystal. Coordination number (CN or Z) is the number of nearest neighbors an atom has within the unit cell. Packing fraction f is the fraction of space occupied by atoms in the unit cell compared to the whole volume of the cell.

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Lattice Constants
Lattice constants (or parameters) are characteristics of the unit cell that define its volume (a,b,c) and the angles between them (,,). Factors affecting lattice structure and constants: Crystal type (affects bond length) Atom size Temperature and pressure Chemical composition Particle size?

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Coordination Number
Coordination number is: Large for metals (typically 8 12) Intermediate for ionic compounds (typically 6) Low for molecular solids (covalent, 4)
Therefore, metals are the most dense covalent solids the least.

Bond length varies with CN: Coordination Number Relative Radius 12 1.00 8 0.97 6 0.96 4 0.88
This should serve as an indication of things to come!
Source: D.E. Shriver, P.W. Atkins and C.H. Langford; Inorganic Chemistry, W.H. Freeman & Co., New York (1990)

Nano Phenomenon #37 It takes only a couple unit cells to make a nanometer. Unit cells are at the small frontier of the nanometer. Nano Phenomenon #38 Lattice constants are influenced by particle size unsaturated coordination of surface atoms causes distortions in the lattice.
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Cubic Systems
Metal atom bonds = non-directional. Hard sphere models adequately illustrate the packing. Cubic systems are the simplest to visualize a = b = c and = = There are three basic kinds: Simple (or primitive) cubic (sc) Body-centered cubic (bcc) Face-centered (or closest-packed) cubic (fcc) Many metals are configured as bcc and fcc (others as hcp). Only polonium is sc.
Metals (and ionic compounds) are polymorphic (due to T & P). Copyright: CRC Press 2009

Atomic Radius and Lattice Constants

SC
r dbody

BCC

FCC

dface ao = 2r dbody = ao3 = 4r dface = ao2 = 4r

Atoms are touching along these vectors.

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Example 10.1
Q: Allotropic transformations: At lower temperatures, iron has a bcc structure (< 911C). At higher temperatures (> 913C), it metamorphs into the fcc structure. What is the change in volume of a bcc iron transition to fcc iron at temperature given that abcc = 0.2863 nm and afcc = 0.3591 nm.
Vbcc = a
3 bcc

= (0.2863 nm) = 0.02347 nm3

3

Vfcc = a 3 = (0.3591 nm) = 0.04631 nm3 fcc

However, a bcc cell has 2 atoms while an fcc has 4 per unit cell:

Vfcc 2 Vbcc 0.04631 2 (0.02347) V = = x100 = 1.34% Vfcc 0.04695

Iron contracts upon heating.

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High resolution TEM of Ti and Al multilayers grown by E-beam deposition. The TiH is hcp but transforms to an an fcc atomic arrangement. The Al remains as an fcc lattice. The multilayers have a common [111] growth direction.
Source: Metallurgy Division of the Materials Science and Engineering Laboratory (MSEL), National Institute of Standards and Testing (NIST) (2008).

Hexagonal Close Packed Systems

co

CN = 12 Polytype: ABABABAB a=bc = = 90 = 120 ao = 2r c = 1.633a (ideally) Many metals crystallize as hcp structures.

ao = 2r

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Example 10.2
Q: Packing fraction of hcp: Calculate f for a hexagonal close packed structure where a = 2r, c = 1.633a, Vhcp = a2c(sin60). What is the theoretical density of Mg (r = 0.160 nm)?
f hcp
f hcp =

(# Atoms unit cell) V =

Vhcp
=
4 3 3 rhcp hcp 8 3

Atom

(2)
2 hcp

3 rhcp 3

(2r ) (1.633 2r ) sin 60

3

1.633 (2rhcp ) 0.866

= 0.74

Density of Mg:

Vhcp Mg = 1.633 (2rMg ) sin60 = 1.633 (2 0.160 nm) 0.866 = 0.04634 nm3

Mg

(# Atoms per unit cell) M =

Vhcp N
A

Mg

2 24.31g mol1

)
mol-1

(0.04634nm ) (6.022x10
3

23

10 7 nm 3 3 = 1.74g cm cm

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Tetragonal Systems
Metal bonds are non-directional resulting in simple crystal structures. However, ionic, covalent and metal compounds are more complex. Covalent bonds, for example, are directional. Tetragonal systems are like cubic systems with one axis extended (a = b c and = = = 90). There are two kinds of tetragonal lattices: simple and body-centered. Bodycentered tetragonal bct is an extended bcc system. Diamond cubic (dc) is a special version of an fcc crystal in which one-half of the tetrahedral holes are filled with additional atoms. Si, Ge, Sn and diamond are configured in the dc crystal types. Zinc Blende (e.g.ZnS) is similar to diamond cubic with Zn2+ filling one-half the tetrahedral holes.
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Example 10.3
Q: Determine the packing fraction f for a dc cell. Visualization is not easy for this cell. The white circles represent voids.
dbody = ao3 = 8r There are 8 atoms per dc cell:

dbody

# Atoms VAtom f = and 8r = ao 3 Vdtc

f =

3 4 # Atoms 3 rSi

3 o

3 4 8 3 rSi

(8r

Si

= 0.34

ao

The packing fraction is much lower than for any of the metals. dc structures are therefore quite open.
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Example 10.4
Q: Calculate the packing fraction for Indium a metal that crystallizes in a tetragonal body-centered bct configuration: a = 0.3253 nm, c = 0.4956 nm and r = 0.1626 nm.
# Atoms are like bcc = 2

4 r 3 x VIn f = = 2 3 2 ac VCell = 2 (4.189) (0.1626 nm)

2 3

(0.3253 nm) (0.4956 nm)

d Body = a 2 + a 2 + c2 = 4r

= 0.687

Atoms touch along the body diagonal where:

and c = 1.52a
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Q: What is the theoretical density of indium? of -, -Fe? Atomic mass In =

114.818 gmol-1, a and c are as before; # atoms = 2 and 4 respectively. Indium:

Example 10.5

# Atoms M In In = VUnitCell N A

3 2 114.818 g mol1 10 7 nm 3 = = 7.27 g cm a 2c 6.022x1023 cm

The accepted density of indium is 7.31 gcm-3.

bcc Iron (-Fe):

Fe =

# Atoms M Fe Vbcc N A

The accepted density of iron is 7.874 gcm-3.

fcc Iron (-Fe):

10 7 nm 3 3 = = 7.90 g cm 3 0.2863) 6.022x1023 cm ( 2 55.845 g mol1

Fe

Since iron contracts upon heating, its density should increase.

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10 7 nm 3 # Atoms M In 3 = = = 8.01 g cm 3 Vfcc N A (0.3591) 6.022x1023 cm 4 55.845 g mol1

Summary
Once again we are dealing with a concept or characteristic that exists at the frontier boundary of the nanoscale. Although this section was fairly descriptive and fundamental to materials science, it is essential to the understanding of what is to come later on in the course.

More Nano Phenomena

37. Unit cells exist at the frontier of the nanoscale 38. Lattice parameters are influenced by size.

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