Surface Processes

Since the production of thin films by vapor deposition or reaction in a gaseous-flow system is a key process
of semiconductor technology, film formation by condensation from the vapor phase is the focus in this course. It
is probably the most investigated process in microelectronics.
Film formation has following steps:
a) Initial step is the impingement of vapor atom/molecules on the substrate
b) Thermal accommodation
c) Adsorption-desorption
d) Sticking coefficient
e) Nucleation and growth
We have already covered (a), here we focus on b) to d).
Thermal Accommodation:
In general, vapor atoms arrive at the substrate surface with energies appreciably higher than kT, where T
is the substrate temperature. The question arises whether such a vapor atom can equilibrate rapidly enough with
the substrate so that it becomes adsorbed, or whether it will rebound without having given up all its incident
energy to the substrate. For the latter case, thermal accommodation coefficient, which is defined as
Ev−Er Tv−Tr
αT= = will be less than unity.
Ev−E Tv−E

Here,
Ev = incident kinetic energy of the vapor atom
Er = energy of the reflected atom before equilibration with the substrate
E = energy of the desorbed atom after it has equilibrated with the substrate
Tv ,Tr and T are corresponding temperatures
Clearly when Tr = T the accommodation coefficient is unity. It emerges as a measure of the extent to
which the arriving atoms reach thermal equilibrium with the substrate. The process consists of an arriving atoms
losing enough energy to phonons, when it first hits the substrate, and it no longer has sufficient energy to return
to infinity. It then loses more energy to the substrate and makes transition to lower energy levels, whilst at the
same time it dissipates its energy of translational motion parallel to the substrate by collisions with the surface
irregularities.
Theoretical investigations indicate that for the case of a “hit” atom impinging on a one-dimensional lattice,
the accommodation coefficient is less than unity only if the incident kinetic energy is larger than twenty five times
the energy necessary for desorption after equilibration with the substrate, It was also predicted that the likelihood
of complete thermal accommodation, i.e., αT = 1, increases if the ratio of the mass of the impinging atom to that
of the mass of the substrate lattice atom increases.
For the case of a three-dimensional substrate lattice, it was estimated that thermal accommodation is
essentially complete if Ev is smaller than the energy necessary for the desorption after equilibration with the
substrate. This must not be confused with the fact that an atom may re-evaporate after it has reached thermal
equilibrium as a result of normal thermal processes.
The time required for an incidental atom to lose its excess kinetic energy and to accommodate thermally
with the substrate is of the order of 2/ν, where ν is the frequency of the substrate lattice vibrations. Thus, the
impinged atoms lose essentially all their excess energy within a few lattice oscillations.
 It thus appears that, except for very light impinging atoms or very high incident energies, the incident
vapor immediately equilibrates thermally with the substrate. In the subsequent treatment the assumption of
immediate equilibration has therefore been made.
In case of molecule-surface interaction, transfer of energy between the solid and vibrational or rotational
states of the molecule is also important.
Adsorption/Desorption: (Atom-surface interaction)
Following thermal accommodation, gas atom is adsorbed on the solid surface. The adsorption is due to
there being an attractive force between the solid and the vapor and this force is characterized by defining an
adsorption energy for the adsorbent atoms or molecules on the surface. There are two types of adsorption.
Physical adsorption refers to the case where there is no electron transfer between the adsorbate and adsorbent and
the attractive forces are van der Waals and/ or electrostatic.
Chemisorption refers to the case where electron transfer, i.e., chemical bonding, takes place between the adsorbate
and adsorbent. The forces are then of the type occurring in the appropriate chemical bond.
In general the adsorption energy for physical adsorption are smaller.
An adsorbed atom sees an array of binding potential wells formed of substrate atoms. There is a finite
probability that the atoms diffuses along the surface by hopping from well to well. There is also a probability of
an atom escaping from the well to vacuum (desorption). To characterize the surface diffusion and desorption, we
assume that the surface atoms have a surface vibration frequency νs (νs ~ 1013 sec-1). The frequency of desorption
is defined as
νdes= νs exp(-ΔGdes/kT) (1)
Where ΔGdes is the change in free energy associated with desorbing an atom. As in all such formulae, the
frequency can be thought of as the number of attempts multiplied by the probability of success given by the
exponential factor. The resident time of an atom on the surface is
τo = 1/νdes = (1/νs)*exp(ΔGdes/KT) (2)
During the resident time, an atom moves from one surface site to a neighboring site (surface diffusion) with a
frequency,
νdiff = νs*exp(-ΔGs/KT) (3)
where ΔGS = energy required to move to a neighbouring site. The surface diffusivity DS is defined as
DS = λ2*νdiff = λ2* νs* exp(-ΔGs/KT) (4)
Where λ is the jump distance between two neighboring sites. In surface diffusion the sites are available,
whereas in bulk diffusion a site must be generated by formation of a vacancy. Desorption is much less likely than
surface diffusion; the difference lies in their activation energies. Desorption involves breaking bonds while
surface diffusion consists of motion only with no net change in number of paired bonds.
Adsorption Isotherm:
In the absence of condensation, the incident flux of vapor on a surface is related to the vapor pressure. For
a solid surface in equilibrium with its vapor, the incident flux Je required to maintain equilibrium vapor pressure
Pe. In thin film deposition, the flux J incident on a substrate from a source depends on the temperature, area and
distance of the source; the corresponding pressure P may be calculated using the relationship between P & J
discussed earlier. The ratio J/Je >1(supersaturation), condensation can occur, but since the departing flux from the
condensate is then <J the actual pressure of vapor on the condensate surface is smaller than P. When J<Je (under
saturation), adsorbate will condense to a surface coverage for which the departing flux is J and the vapor pressure
over the surface is P.

A graph of the amount of gas adsorbed by the solid against relative vapor pressure for a fixed
temperature is called an adsorption isotherm. Many tens of thousands of adsorption isotherm have been measured
on a wide variety of solids; and those are invariably for cases in which the super saturation less than unity (P<Pe).
We assume that J atom/s are striking unit area of the substrate and that all are thermally accommodated.
For simplicity, consider first the case when only a few adatoms are adsorbed at single sites dispersed over the
substrate and where the substrate is uniform, i.e. each site has the same adsorption energy. Under such conditions,
the interaction between different adatoms can be ignored and we can postulate an average life time, τo, for an
adatom before it re-evaporates from the surface. τo is assumed to be independent of the number of adatoms present.
From this model the number n1 per unit area, of adatoms present will satisfy the equation
dn1
= J-n1/τo (5)
dt

of deposition starts with n1 at t=0 this integrates to

n1 = J*τo*[1-exp (-t/ τo)] (6)
where t is time.
Normally we may assume that the experimental time t is much greater than τo for fairly weak
physical adsorption. Equation (6) can be approximated to
n1 ~ J*τo (7)
This relation usually applies when J<Je and may apply when J>Je. If adsorption energy is high, τo be large and n1
of equation (7) may be so large than the validity conditions of equation (5) are infringed. Equation (6) applies
only for an initial transient period over which it approximates to
n1 ~ J*t (8)
In deposition with J>Je, either equations (7) or (8) apply until the consumption of monomer by formation or
growth of clusters is no longer negligible.
Sticking Coefficient (s)
Sticking coefficient, s, is defined as the ratio of the number of atoms adhering to the substrate to the number of
atoms arriving. Commonly the sticking coefficient is less than unity and in cases where the adsorption energy of
atoms on the substrate is low and/or the substrate temperature is high, the coefficient may be a very small fraction.
s is a function of surface coverage, temperature, material and substrate nature. For example,
on clean silver surfaces, a gold deposit at 300oC showed an initial sticking coefficient of 0.6, rising to unity when
the gold film reached a thickness of approximately 250 Å.
Molecule surface adsorption:
So far, we were discussing mono-atomic species adsorbing on the surface. What happens if
molecules are incident on substrate Lennard Jones proposed a simple model to explain various outcomes.
Consider the interaction of B2 molecule with a flat surface. We can imagine that as the molecule approaches the
surface, the molecule interact via, a Lennard Jones potential such as the one indicated as the line which is labeled
molecular state in Fig.1.

However, following Lennard-Jones it will be assumed that the interaction energy was only a
function of Z, and not on the molecules other two coordinates X and Y. This is, of course, an approximation, but
it is a useful one. Now consider the potential for the interaction of two B separate atoms with the same surface.
Note that in the gas phase, it takes some energy, EDB2 to dissociate the B2molecule. As a result, at long distanced
from the surface the energy of two separate B atoms will be EDB2 higher than the energy of a B2 molecule. Now
when the two B atoms interact with the surface, they can form bonds. As a result, the energy of the two separate
B atoms will be lowered. L-J assumed that the energy of two separate B’s would follow the one dimensional
potential labelled as “dissociated state” in Fig1.
Notice that the energy of the molecular state and the energy of the dissociated state cross at
some point above the surface L-J noted that from quantum mechanics it there are two states of the system: a
molecular state and a dissociated state, the two states will interact to avoid the curve crossing. The ground state
of the system will follow the dark line in Fig, 1, where the molecule starts out in the molecular state, but as the
molecule comes close to the surface the molecule can cross an activation barrier and enter the dissociated state.
Therefore, L-J asserted that type of adsorption is decided by the height of the barrier.
In the lecture, we also discussed representing thermal accommodation overlapped with the
adsorption processes.