Thin Film Deposition

Techniques

Class 8
Chemical Vapor Deposition
• Depositing thin films over the surface of substrates and other MEMS and
microsystem components is a practice in micromachining
• Deposition adds thin films to the substrates instead of consuming
substrates as in oxidation
• The thin film materials includes metals like Al, Ag, Au, Ti, W, Cu, Pt, Sn and
compounds such as shape memory alloys NiTi and piezoelectric ZnO
• There are two classes of deposition used in micromachining. These are
Physical Vapor deposition and CVD
• PVD involves direct impingement of particles on the hot substrate surface.
• CVD involves convective heat and mass transfer as well as diffusion with
chemical reaction at the substrate surface
• CVD is a much complex process, but is a great deal more effective in terms
of the rate of growth and quality of deposition
Principle of CVD

• CVD involves the flow of a gas with diffused reactants over a hot
substrate surface. The gas that carries the reactants is called a carrier
gas
• While the gas flows over the hot solid surface, the energy supplied by
the surface temperature provokes chemical reactions of the reactants
that form films
• Thin films of desired composition can thus be created over the
surface of the substrate
• Various types of CVD reactors are built to perform the CVD processes
CVD Reactor
Chemical reactions in CVD
•  Chemical reactions that are used in depositing three common thin
films over the substrate have been discussed below
• Silicon dioxide: Chemical reactants used to deposit SiO2 include Si
• That carrier gas used are O2, NO, NO2
• The most common reactant used for CVD is silane ( Si) together with
O2
• The chemical reaction in this process I given by
• Si
• The chemical reaction takes place in a temperature range of 400 to C
•  Silicon Nitride (): Ammonia is a common carrier gas for depositing
silicon nitride on silicon substrates.
• There are three reactants that can produce silicon nitride films
• 3 Si
• 3 Si
• 3 Si+6
• The temperature for silane is 700 -900 degree, 850 for silicon
tetrachloride and 650-750 for dichlorosilane
• Polycrystalline Silicon : these films consists of single silicon crystals of
different sizes. Deposition of polycrystalline silicon is a pyrolysis
process which is a decomposition process using heat.
Si
This process takes place at a temperature of 600 to 650
Rate of deposition
• CVD is a process by which films of a desired substance are produced by chemical
reactions of the reactants and carrier gas at the hot substrate surfaces
• The rate of build up of these thin films is a concern.
• Let us now look at the situation shown below, where the reactant and the carrier
gas flow over the hot substrate surface with a velocity
• We will observe the velocity profile V(x) of the gas reactant mixture over the
substrate surface
• A boundary layer with thickness δ(x) exists at the solid gas interface whenever a
gas flows over the solid surface
• Because of this layer, an additional time is required for the reactant to diffuse
across this layer.
• The boundary layer is a retarding factor to the chemical reactions
• This layer affects the rate of deposition of the thin film over the substrate
•  Approximate thickness of the boundary layer δ(x) at a distance x
away from the leading edge of the substrate can be obtained from
δ(x)=
• Re(x) is the Reynolds number of the gas mixture.
• The Reynolds number can be expressed as Re(x) = where rho is
the mass density of the gas mixture, L is the characteristic length of
the flow, and μ is the dynamic viscosity of gases
• The diffusion flux of the reactant N, across the boundary layer with
units of atoms or molecules/unit time/area though the boundary
layer can be expressed by Fick’s law and is given by
N=
Where D is the diffusivity of the reactant in the carrier gas with units of
, are the respective concentrations of the reactant at the top of the
boundary layer G and at the surface of the substrates, s. Both have
units of molecules/
• The Reynolds number is the ratio of inertial forces to viscous
forcesand is a convenient parameter for predicting if a flow condition
will be laminar or turbulent.
• It can be interpreted that when the viscous forcesare dominant (slow
flow, low Re) they are sufficient enough to keep all the fluid particles
in line, then the flow is laminar.
• Even very low Re indicates viscous creeping motion, where inertia
effects are negligible.
• When the inertial forces dominate over the viscous forces (when the
fluid is flowing faster and Re is larger) then the flow is turbulent.
Dynamic Viscosity of gases used in CVD
•  Most CVD processes takes place at a very low gas velocity, the
corresponding Reynolds number Re is at a low value of about 100. the
low velocity of the gas flow allows a significant amount of reactant to
diffuse through the boundary layer and form the film by chemical
reaction at the hot surface of the substrate
• The following relation exist
• N = is the surface reaction rate constant and is expressed as
where =constant whose value depends on the reactant concentration,
is activation energy, k Boltzmann constant and T absolute temperature
The diffusion Flux of the reactant N may be expressed in terms of
surface reaction rate
N = where δ is the mean thickness of the boundary layer
•  The rate of growth of the thin film over substrate surface , r, in m/s
can be estimated by the expression
r = for δ ≥D
or
r = for δ≪ D
γ is the number of atoms per unit volume of thin film. The value of γ
may be estimated by a postulation that the thin film is densely packed
by atoms or molecules in spherical shapes with radius according to the
selected material
Value of γ can be determined by the following expression
γ = where a = the radius of atoms in meters. The units for γ are atoms
or molecules/
Atomic radius of selected materials
Inference
•  CVD is affected by the following parameters
• 1. The temperature,
• 2. Pressure of the carrier gas,
• 3. The velocity of gas flow,
• 4. The distance in the direction of gas flow,
Enhanced CVD
• CVD process we just discussed involves elevated temperature, but
near atmospheric pressure. It is called APCVD
• There are other CVD techniques that are used for higher rate of
growth or for better quality of films
• Popular techniques are LPCVD and PECVD
LPCVD
•• The rate of growth of the film is inversely proportional to the thickness of the boundary layer δ but is
 directly proportional to diffusivity of the reactant in the carrier gas (D)
• The thickness δ of the boundary layer is inversely proportional to the square root of Reynolds number
Re
• Diffusivity varies inversely with pressure. Reynolds number depends on gas velocity V , viscosity μ and
density ρ

• Consider LPCVD. If the gas pressure reduce by 1000 times. We expect an increase in D by 1000 times
but with the same 1000 times reduction in density.
• The velocity of the gas with 1000 times reduction of pressure will reduce by 10 to 100 times
• These variation will result in a net reduction of Reynolds number by 10 to 100 times which means a
net increase of δ by
• Despite an increase of δ by 3 to 10times, 1000 times increase of D will result in an increase in the
diffusion flux N by 10 to 30 times
• It is therefore clear that reduction of gas pressure will definitely increase the rate of deposition.
• Deposition rate is inversely proportional to gas pressure
• LPCVD operates in vacuum at about 1 torr (I mm of Hg).
Plasma – enhanced (PECVD)
• Both APCVD and LPCVD require the substrates and the carrier gas to
be at elevated temperatures for sufficient activation energies to allow
chemical reaction to take place
• This high temperature can damage substrates especially metallized
substrates
• PECVD uses RF plasma to transfer energy to the reactant gases, and
thus allows substrates to remain at lower temperature than that in
APCVD and LPCVD
• RF source can em radiation in the band 3 KHz – 300 GHz
PECVD reactor
Comparison of three CVD processes