Background of ceramics

Materials Science at the Nanoscale

Kyu Hyoung Lee

Materials Science at the Nanoscale

Nanoscale
- A nanometer is one millionth of a millimeter

- 100,000 times smaller than the diameter of a human hair

Nanotechnology
- The design, characterization, and application of structures, devices,

and systems by controlled manipulation of size and shape of materials

at the nanometer scale
- Atomic, molecular, and macromolecular scale
- To produce materials with at least one novel/superior property
Materials Science at the Nanoscale
Nanomaterials
- Nanoscale materials
- A set of substances where at least one dimension is less than 100 nm
- At the nanoscale scale, physical and chemical properties of materials
differ significantly from those at a larger scale

Properties of nanomaterials
- There may be more to be discovered
- Known origins that cause physical properties to change
(a) large fraction of surface atoms
(b) large surface energy
(c) spatial confinement
(d) reduced imperfections
Materials Science at the Nanoscale

Nanomaterials
- Reduced melting point

 Huge fraction of surface atoms in the total amount of atoms

 Significantly lower melting point or phase transition temperature

Tb : Bulk melting point, Tm : Particle melting point

rs : radius, H : molar latent heat of fusion

 : surface energy solid / liquid

 : density of solid / liquid
Materials Science at the Nanoscale

Nanomaterials
 Surface atoms
 Dangling or unsatisfied bonds exposed to the surface

 Surface atoms or molecules are under an inwardly directed force

 Smaller bond distance between the surface atoms or molecules
 Significant in nanoparticles : Reduced lattice constants

Inward
shift
Materials Science at the Nanoscale

Nanomaterials
- Ultra hard

 Reduced probability of defects

 Mechanical properties : theoretical values

 Two possible mechanisms in nanowires
(a) Increased internal perfection
- Smaller the cross-section  Low probability of imperfections
(dislocations, micro-twins, impurity precipitates, etc)
- Thermodynamically, imperfections in crystals are highly energetic
 can be eliminated

- Imperfections in bulk materials  stresses (temperature gradient)

Materials Science at the Nanoscale

Nanomaterials
- Ultra hard

 Two possible mechanisms in nanowires

(b) Increased surface perfection

- Smaller structures have less surface defects
- Materials by a bottom-up approach
 A typical dependence of strength on the diameter (NaCl whisker)
 AFM and TEM : direct evidence for the mechanical behavior
(nanostructures and nanomaterials)
Materials Science at the Nanoscale

Nanomaterials
- Electrical conductivity

 Decreases with a reduced dimension (increased surface scattering)

 Increases due to the better ordering and ballistic transport

- Magnetic properties
 Ferromagnetism disappears and transfers to superparamagnetism
(huge surface energy)
-Optical properties

 Semiconductor Blue Shift in adsorption and emission

(increased band gap by quantum size effects)

 Metallic nanoparticles : color changes (surface plasmons resonances)

Materials Science at the Nanoscale

Semiconductor nanocrystals
- The bandgap depends on particle size (>10 nm, quantum size effect)
- Control size  control bandgap

- LEDs, laser, solar cells, and biological label

CdSe nanocrystals
- Bulk CdSe has a direct bandgap ~1.73 eV
- Bandgap of 2~10nm in diameter CdSe nanocrystals is 1.73~3.1eV
 Visible light wavelength: 380~750nm (1.65 - 3.26 eV)
 Materials for optoelectronics
Materials Science at the Nanoscale

Quantum confinement effect

- Particle in a box
- Restricted to the region 0 ≤ x ≤ a

 Probability that the particle is found outside = 0

∞ ∞
Band structure of Si nanoclusters
Energy
(eV) Conduction Band

Bulk Band Gap

= 1.1 eV

0 x a Valence Band

0 1 2 3 4 5
j(0) = j(a) = 0 Diameter (nm)