ChE 209 Materials Science and Engineering

Chapter 5 The Synthesis of Materials and Imperfections

34

Chapter 5 The Synthesis of Materials

And Imperfections

Gas to Solid Synthesis

1. Vapor deposition - involves the condensation of a vapor onto a cooled

substrate. Heating a solid powder (sublimation) or a liquid (evaporation)
achieves the vapor. The vapor deposition is one of the principal
techniques for preparing amorphous thin films of materials, ex. Silicon
and germanium.

2. Chemical vapor deposition - is a process whereby the vapor-phase

molecular species react, either homogenously in the gas phase or
heterogenously at the solid-gas interface at the surface of the substrate,
producing a film with a composition different from that of the starting
materials. The vapor molecules can be decomposed by means of heat
(pyrolysis) or absorption of UV light (photolysis).

Ex. Production of thin films of polycrystalline silicon by the thermal

decomposition of silane:

heat
SiH4 (g)  Si (s) + H2 (g)

Another energy source that can be used to promote CVD is associated

with electrical plasma, a gas of ionized atoms and electrons. This is called
plasma-enhanced chemical vapor deposition. It is commonly used to
produce thin films of amorphous or polycrystalline silicon, depending on
the conditions, from silane.

3. Sputtering - is a process by which some of the atoms of an electrode,

usually a cathode, are ejected as a result of bombardment by heavy
positive ions. It is used to produce a clean surface or to deposit a uniform
film of metal on an object in an evacuated enclosure.

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 ChE 209 Materials Science and Engineering
Chapter 5 The Synthesis of Materials and Imperfections
35

Atoms into gas state

Transport to substrate
Deposit on substrate

Liquid to Solid Synthesis

Bulk materials are often made starting from the liquid phase, either by
solidification of a melt to form single crystals when the cooling rate is
very low or to form non-crystalline materials when the cooling rate is
sufficiently fast that crystallization is prevented.

1. Crystal growth from the melt - Single-crystal materials (ultrapure)

can be produced in three methods: crystal is pulled out of the melt,
crystallization takes place in a crucible container and crystallization occurs
within a solid rod of material. The crystal-growth-technology is used in
electronics industry, where the requirements for material purity and
crystal perfection are extremely rigid.

2. Liquid quenching - involves super cooling of a liquid below its normal

freezing point. If a liquid is cooled quickly enough so that crystallization is
bypassed, a structurally disordered solid phase is formed.

3. Crystallization from solution - Preparation of crystals from solution

involves dissolving the material to be crystallized in a solvent and then
causing crystallization to occur, either by reducing the solubility of the
solute or by increasing the concentration of the solute in the solution by
removing the solvent. In both cases, a supersaturated solution is
produced from which crystals are formed. The process of crystallization
from a melt can be divided into two stages: nucleation and growth of
nuclei into crystals. In general, these are the steps in the solidification of
metals and alloys. The nucleation involves the clustering of atoms to form
nuclei. For a nucleus to be stable so that it can grow into a crystal, it must
reach a critical size. A cluster of atoms bonded together which is less than
the critical size is called an embryo, and one that is larger than the critical
size is called a nucleus. Because of their

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 ChE 209 Materials Science and Engineering
Chapter 5 The Synthesis of Materials and Imperfections
36

instability, embryos are continuously being formed and redissolved in the

molten metal due to the agitation of the atoms. The stable nuclei then
grow in size by the transport or movement and rearrangement of atoms.

The Formation of Stable Nuclei in Liquid Metals

The two main mechanisms by which nucleation of solid particles in
liquid metal occurs are homogenous nucleation and heterogenous
nucleation

Homogenous Nucleation - It is the simplest case of nucleation.

Homogenous nucleation in a liquid melt occurs when the metal itself
provides the atom to form nuclei.

The two kinds of energy changes involved in homogenous nucleation are:

(1) the volume (or bulk) free energy (Gv) released by the liquid to solid
transformation and
(2) the specific free energy () required to form the new solid surfaces of
the solidified particles.

The total free energy change (GT) = (4/3)r3 (Gv) + 4r2

Heterogenous Nucleation - occurs in a liquid on the surfaces of its

container, insoluble impurities or other structural material which lowers
the critical free energy required forming a stable nucleus. In practice,
heterogenous nucleation is observed since the liquid is usually poured into
a mold that is always at a much lower temperature than the liquid and the
liquid always contains suspended particle impurities or nonmetallic
inclusions that provide surfaces on which nucleation will start.

Growth of Crystals in Liquid Metal and Formation of a Grain Structure

After stable nuclei have been formed in a solidifying metal, these nuclei grow
into crystals. When the solidification of the metal is finally completed, the
crystals join together in different orientations and form crystal boundaries at
which changes in orientation take place over a distance of a few atoms.
Solidified metal containing many crystals is said to be polycrystalline. The
crystals in the solidified metal are called grains and the surfaces between
them, grain boundaries.

Equiaxed grains - crystals grow equally in all directions

Columnar grains - long, thin coarse grains, which are created when a metal
solidifies relatively slowly in the presence of a steep temperature gradient.

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