Diffusion

Surface diffusion is the motion of adparticles, such as atoms or molecules, over the surface
of a solid substrate. The diffusing particles might be the same chemical species as the
substrate (the case referred to as a self-diffusion) or another one (the case of hetero-
diffusion). In most cases, the adparticle becomes mobile due to thermal activation and its
motion is described as a random walk. In the presence of a concentration gradient (in the
more general case, of the gradient of the chemical potential), the random walk motion of
many particles results in their net diffusion motion in the direction opposite to the direction
of the gradient. The diffusion process is affected by many factors, such as interaction
between diffusing adspecies, formation of surface phases, presence of defects, etc.
 Diffusion
• Diffusion refers to the net flux of any
species, such as ions, atoms, electrons,
holes, and molecules.
• In materials processing technologies, (a)
control over the diffusion of atoms,
ions, molecules, or other species is key.

(b) (c)

(a) A copper–nickel diffusion couple before a high-temperature heat treatment. (b) Schematic
representations of Cu (red circles) and Ni (blue circles) atom locations within the diffusion
couple. (c) Concentrations of copper and nickel as a function of position across the couple.
• Chemical analysis will reveal
condition
a similar to that represented in
Figure namely, pure copper and nickel at
(a)
the two extremities of the
couple, separated by an alloyed region.

• Concentrations of both metals vary with

position as shown in Figure c.

• This indicates that copper atoms have (b)

migrated or diffused into the nickel, and
that nickel has diffused into copper.

• This process, whereby atoms of one

metal diffuse into another, is termed
interdiffusion, or impurity diffusion. (c)
• Diffusion also occurs for pure metals, but
all atoms exchanging positions are of the
same type; this is termed self-diffusion

(a) A copper–nickel diffusion couple after a high-temperature heat

treatment, showing the alloyed diffusion zone. (b) Schematic
representations of Cu (red circles) and Ni (blue circles) atom
locations within the couple. (c) Concentrations of copper and
nickel as a function of position across the couple.
Stability of Atoms and Ions
Imperfections and, even atoms or ions in
their normal positions in the crystal
structures are not stable or at rest.
Instead, the atoms or ions possess thermal
energy, and they will move.
An atom may move from a normal crystal
structure location to occupy a nearby
vacancy. An atom may also move from one
interstitial site to another. Atoms or ions
may jump across a grain boundary, causing
the grain boundary to move.
The rate of atom or ion movement is related
to temperature or thermal energy by the
Arrhenius equation:
𝑒=
𝑡𝑎𝑅𝑐exp(− ) 𝑄 The Arrhenius plot of ln(rate) versus 1/T can
𝑜
𝑇𝑅 be used to determine the activation energy
for a reaction.
where co is a constant, R is the gas constant , T is the
absolute temperature (K), and Q is the activation
energy (cal mol) required to cause Avogadro’s
number of atoms or ions to move.
 Mechanisms for Diffusion
Interdiffusion
• Diffusion different atoms
different
of directions is in
interdiffusion. known as
• At high temperatures, nickel atoms
gradually diffuse into the copper, and
copper atoms migrate into the nickel.
• Again, the nickel and copper atoms
eventually are uniformly distributed.

Diffusion of copper atoms into nickel. Eventually, the copper

atoms are randomly distributed throughout the nickel.
• Two important mechanisms by which
atoms or ions can diffuse.

• Vacancy Diffusion: In self-diffusion

and diffusion involving substitutional
atoms, an atom leaves its lattice site to
fill a nearby vacancy (thus creating a
new vacancy at the original lattice
site). The number of vacancies, which
increases as the temperature increases,
influences the extent of both self-
diffusion and diffusion of substitutional
atoms.
• Interstitial Diffusion: When a small
interstitial atom or ion is present in the
crystal structure, the atom or ion moves
from one interstitial site to another.
Interstitial diffusion occurs more
easily than vacancy diffusion.
Interstitial atoms that relatively
Schematic representations of (a) vacancy diffusion and
are smaller can diffuse (b) interstitial diffusion.
faster.
 Activation Energy for Diffusion
• A diffusing atom must squeeze past the
surrounding atoms to reach its new site.
• The atom is originally in a low-energy,
relatively stable location.
• In order to move to a new location, the atom
must overcome an energy barrier. The energy
barrier is the activation energy Q.
• The thermal energy supplies atoms or ions
with the energy needed to exceed this barrier.
• The diffusion couple is used
indicate
term a combination
to of an atom of a given
element (e.g., carbon) diffusing in a host
material (e.g., BCC Fe).
• A low-activation energy indicates easy
diffusion.
• In self-diffusion, the activation energy The activation energy Q is required to squeeze atoms past
one another during diffusion. Generally, more energy is
equal
is to the energy needed to create a required for a substitutional atom than for an interstitial
vacancy and to cause the movement of the atom.
atom.
 Types of Diffusion
• Volume diffusion: The atoms move through the crystal from one regular or interstitial site
to another. Because of the surrounding atoms, the activation energy is large and the rate of
diffusion is relatively slow.

• Atoms can also diffuse along boundaries, interfaces, and surfaces in the material. Atoms
diffuse easily by grain boundary diffusion, because the atom packing is disordered and
less dense in the grain boundaries. Because atoms can more easily squeeze their way
through the grain boundary, the activation energy is low.

• Surface diffusion is easier still because there is even less constraint on the diffusing
atoms at the surface.
Random Walks
Consider the thermal motion of an adatom on an
ideal crystal surface (Fig.). On the atomic scale,
the surface comprises a periodic array of
adsorption sites, which correspond to the positions
of minimum energy (position 1 in Fig. a). Due to
thermal excitations, an adatom can hop from one
adsorption site to the next. The adatom motion
along the surface can be visualized as a random
site-to-site hopping process (random-walk
motion), for which the mean-square'displacement
of the hopping atom in time t is given by

< Δ𝑟2> = 𝑎𝜈
2𝑡

where a is the jump distance (i.e., the adsorption

site spacing) and ν the frequency of hops. Note
that νt gives the number of hops. For a single
adatom, < Δ𝑟2> is averaged over many repeated
observation periods of duration t.
Figure: One-dimensional schematic diagram
showing (a) a substrate (open circles) and adatom
(hatched circle) in an adsorption site (labeled 1) and
in a transition (saddle point) state (labeled 2). z is
the distance normal to the surface and z is the
coordinate along the surface, (b) Schematic
potential energy diagram for adatom motion along
the surface,
The time-independent ratio of the mean-square displacement < Δ𝑟2> to time t is known as
the diffusion coefficient (or diffusivity), D:

< Δ𝑟2> 𝑎
𝜈2
𝐷= =
𝑧
𝑡 𝑧
where z is the number of neighboring sites which the atom can hop to. It is apparent that z
= 2 for one-dimensional diffusion (as shown in Fig. b, where the atom can hop either to the
left or to the right neighboring sites),
z = 4 for surface diffusion on a square lattice, and z = 6 for surface diffusion on a
hexagonal lattice.

Figure: One-dimensional schematic diagram

showing (a) a substrate (open circles) and adatom
(hatched circle) in an adsorption site (labeled 1)
and in a transition (saddle point) state (labeled 2).
z is the distance normal to the surface and z is the
coordinate along the surface, (b) Schematic
potential energy diagram for adatom motion
along the surface,
Atom hopping from site to site requires surmounting
the potential barrier, i.e., this is a thermally activated
process. If the oscillation frequency of the atom in the
well (which is essentially an attempt frequency to
overcome the barrier) is ν0 and the barrier height is
Ediff, the hopping frequency can be expressed as
𝜈= 𝑣 0 𝑓 𝑓 𝑖𝐸
𝑑 )
𝑘𝐵 𝑇
exp(−
where kB is the constant and T
temperature. As one can see in Figure,
Boltzmann the the activation
energy of diffusion Ediff is the difference in potential
energy of the adatom in the equilibrium adsorption
site (position l) and in the transition saddle point
(position 2). Ediff is far less than the desorption energy
Edes (typically Ediff ~ 5-20 % of Edes).

For chemisorbed species, >> kB T and

Ediff
diffusion mechanism is referred the to as hopping (or
jumping) diffusion. If Ediff is less than kB T, the atoms
transfer freely across the surface as a two-
dimensional gas. This type of motion, called mobile
diffusion, comprises a rather rare case detected only
for a few physisorbed species and will be left out of
the scope of further consideration.
(c) Schematic diagram of the adatom
potential energy as a function of z in
positions 1 and 2 as in (a). The activation
energy of surface diffusion Ediff equals the
energy difference of the minima of the
curves 1 and 2. The desorption energy
Edes is shown for comparison
 Regimes
There are four different general schemes in which diffusion may take place. Tracer diffusion
and chemical diffusion differ in the level of adsorbate coverage at the surface, while intrinsic
diffusion and mass transfer diffusion differ in the nature of the diffusion environment. Tracer
diffusion and intrinsic diffusion both refer to systems where adparticles experience a
relatively homogeneous environment, whereas in chemical and mass transfer diffusion
adparticles are more strongly affected by their surroundings.
Tracer diffusion describes the motion of
individual adparticles on a surface at relatively
low coverage levels. At these low levels (< 0.01
monolayer), particle interaction is low and
each particle can be considered to move
independently of the others. The single atom
diffusing in figure 1 is a nice example of tracer
diffusion.

Figure: Model of a single adatom diffusing across a square

surface lattice. Note the frequency of vibration of the adatom
is greater than the jump rate to nearby sites. Also, the model
displays examples of both nearest-neighbor jumps (straight)
and next-nearest-neighbor jumps (diagonal).
https://en.wikipedia.org/wiki/File:Surface_diffusion_hopping.gif
Chemical diffusion describes the process at higher level of coverage where the effects of
attraction or repulsion between adatoms becomes important. These interactions serve to
alter the mobility of adatoms. In a crude way, figure serves to show how adatoms may
interact at higher coverage levels. The adatoms have no "choice" but to move to the right
at first, and adjacent adatoms may block adsorption sites from one another.

Figure. Model of six adatoms diffusing

across a square surface lattice. The
adatoms block each other from moving to
adjacent sites.
https://en.wikipedia.org/wiki/File:Chemical_surface_diffusio
n_slow.gif