1D Nanostructures
METHODS OF GROWTH
SPONTANEOUS GROWTH
EVAPORATION (DISSOLUTION) – CONDENSATION GROWTH
Defects Homogeneous nucleation
Step 2 limited growth (Adsorption limited)
J: Condensation rate or Flux of species
a: accommodation factor or sticking coefficient
s: supersaturation defined as P-Po/Po
Po: equilibrium vapor pressure of crystal at temperature T
P: vapor pressure or concentration of the growth species
m: atomic weight of growth species k: Boltzmann constant
T: temperature in Kelvin
Role of – sticking coefficient
High – high growth rate
is surface orientation dependent – can lead to anisotropy
Role of – supersaturation
Low – good for anisotropic growth
Medium – good for bulk growth
High – good for homogeneous nucleation (powder growth)
Step 3 limited growth (Surface diffusion limited)
Step 4 limited growth (Surface growth limited)
Kossel, Stranski, Volmer (KSV) Model
Periodic Bond Chain (PBC) model
Examples of evaporation-condensation growth
Examples of dissolution-condensation growth
ZnO nano tetrapods
2 nm
ZnO nanostructures by evaporation of Zn
W18O49monoclinic nano and microrods Tungsten Oxide
Tungsten Oxide –
Nanobelts
30 µm
VLS (SLS) GROWTH
Wagner’s observations in Silicon nanowire (whisker) growth
(1960s)
REQUIREMENTS FOR VLS
(1) The catalyst or impurity must form a liquid solution with the crystalline material to be
grown at the deposition temperature,
(2) The distribution coefficient of the catalyst or impurity must be less than unity at the
deposition temperature.
(3) The equilibrium vapor pressure of the catalyst or impurity over the liquid droplet
must be very small. Although the evaporation of the catalyst does not change the
composition of the saturated liquid composition, it does reduce the total volume of the
liquid droplet. Unless more catalyst is supplied, the volume of the liquid droplet reduces.
Consequently, the diameter of the nanowire will reduce and the growth will eventually
stop, when all the catalyst is evaporated.
(4) The catalyst or impurity must be inert chemically. It must not react with the chemical
species such as by-products presented in the growth chamber.
(5)The interfacial energy plays a very important [Link] wetting characteristics
influence the diameter of the grown nanowire. For a given volume of liquid droplet, a
small wetting angle results in a large growth area, leading to a large diameter of
nanowires.
(6)For a compound nanowire growth,one of the constituents can serve as the
catalyst.
(7) For controlled unidirectional growth, the solid-liquid interface must be well defined
crystallographically. One of the simplest methods is to choose a single crystal substrate
with desired crystal orientation.
SILCON CARBIDE RODS
SILCON CARBIDE RODS
SiC whiskers
SiC micro and
nano-whiskers
Crack
SEM image of SiC
nano-whiskers
Silicon Carbide nanowires
SiC core-sheath nanocables
TEMPLATE BASED SYNTHESIS
•Nanowires •Polycrystalline
•Nanorods •Amorphous
•Nanotubes
•Polymers
•Metals
•Semiconductors
•Oxides
REQUIREMENTS OF TEMPLATES
1. Controlled pore size, morphology, pore distribution, density
2. Compatibility with processing conditions (chemically and
thermally inert except for template directed synthesis
3. Solutions, melts, etc should wet pore walls
4. Deposition must start at one end and grow along the length
(for nanotubes, growth must be radial)
5. Diffusion limited process to permit surface relaxation and
maximal packing density
6. Easy to handle (robust)
7. Easy to remove template after deposition
TYPES OF TEMPLATES
•Anodized Alumina Membrane
•Nanochannel array glass
•Radiation track etched mica
•Mesoporous materials
•Porous silicon by electrochemical
etching
•Zeolites
•Carbon nanotubes
NERNST EQUATION