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CVD Notes

This document summarizes key concepts in CVD kinetics: (1) CVD deposition rate is limited by the slowest step in the reaction sequence: diffusion of reactants to the surface, absorption, surface reaction, desorption of products, or diffusion away from the surface. (2) Deposition rate depends strongly on temperature. At low T it follows an Arrhenius equation, while at high T it is proportional to T1.5-2.0 due to diffusion limitations. (3) A model describes deposition rate as proportional to reactant concentration and inversely proportional to the smaller of the surface reaction rate or mass transfer coefficient.

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111 views

CVD Notes

This document summarizes key concepts in CVD kinetics: (1) CVD deposition rate is limited by the slowest step in the reaction sequence: diffusion of reactants to the surface, absorption, surface reaction, desorption of products, or diffusion away from the surface. (2) Deposition rate depends strongly on temperature. At low T it follows an Arrhenius equation, while at high T it is proportional to T1.5-2.0 due to diffusion limitations. (3) A model describes deposition rate as proportional to reactant concentration and inversely proportional to the smaller of the surface reaction rate or mass transfer coefficient.

Uploaded by

Ayesha Tariq
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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EE143

N.Cheung
Notes on CVD Kinetics

Deposition depends on the sequence of


events:
(1) Diffusion of Reactants to surface
(2) Absorption of Reactants at surface
(3) Chemical reaction at surface
(4) Desorption of products from surface
(5) Diffusion of products from surface.
* (1) and (5) are mass-transfer mechanisms.
The slowest event will be the rate- determing step.
(1) Temperature Dependence of Deposition rate.

(i) From the above Si deposition example, for low T, rate R e- E/kT (Surface
Reaction limited)
where E = 25 - 100 kcal/mole for most CVD processes ( or 1- 4 eV/atom).
(ii) For high temperature, R Tn (1.5 < n (experimental) < 2.0) (Mass Transport
limited)

For mass-transport limited reactions, R D (diffusion constant) and D T3/2/ P for


gaseous diffusion.
n1 v n2 v
v
dn
Proof: F = 4 - 4 = 4 ( dx) where = mean free path of gas collision.
v
dn
F = Ddx D = 2
kT
Since P and v T
D T3/2/P

(2) Growth Rate Model


[Note] This model is a special case of the Grove-Deal model for thermal oxidation. Here ,
we dont have to consider the diffusion througfh the oxide layer.

In this model, fluxes of products are ignored (i.e., their mass-transfer coefficients >>
those of reactant).
Let F1 = flux from bulk of gas to substrate surface.
hG (CG - CS)
where hG = mass-transfer coefficient.
CG, CS = reactant conc. at bulk of gas and substrate surface respectively.
Let F2 = flux consumed in film-growth reaction.
= kS CS where kS = surface-reaction rate coefficient.
Steady state F1 = F2 = F
CG
kShG
CS = 1 + k /h and F = k + h CG
S G
S
G
2

Since CG = Y CT where Y = mole fraction of reactant.


CT = total # of molecules/cm3 in gas mixture.
dy
F
(thickness
growth
rate)
=
where = atomic density of film.
dt

kShG CT
CT
1
dy
Y= 1

Y
dt = k + h
1

S
G
(k + h )
s
G
Comments:
dy
(a) dt is determined by the smaller of hG and kS (i.e., mass-transfer control or surfacereaction control).
dy
(b) dt Y (mole fraction of reactant in bulk of gas mixture)
and

(3) Boundary Layer Theory for Stagnant Gas Layer

The boundary layer thickness (x) is shown in the figure below and L is the length of the
substrate (e.g. substrate or wall of reactor).
The gas velocity u is a function of x and y and is equal to zero at plates surface and is
equal to U in the free gas stream.
Let = viscosity of gas. Then frictional force / unit area along the x-direction =

u
y

Let us consider a volume element of unit depth (i.e., into the paper) , height (x) and
width dx.
u
u
Total friction force on element = (1 dx) = dx = decelerating force
y
y
Total accelerating force on element.
du
du dx
du
= (x)dx dt = (x)dx dx dt = (x)dx dx u
where is the gas mass density
u
du
Balanced forces : = (x)udx and u(x,y) can be solved exactly.
y
Approximate Solutions
u
U
u U
Let u U ;

y (x)
y x
x
then (x) A 1/2 - B parabolic dependence where A,B are constants.
U
L
1
2 L
2
(x) dx =
The average boundary layer thickness = L
3 UL = 3
0

L
ReL

ReL is called the Reynold Number of the reactor. When ReL is small ( 2000) ,
viscous flow dominates. When ReL very large ( 2000) , turbulent flow dominates.
The Exact Solutions:
The stagnant layer thickness with u= 0.99U is equal to :
x
(x) 5.0 U 1/2

See H. Blasius, NACA Tech. Mem., 1949, p. 1217.
In the CVD growth rate model, it was assumed that mass transport across stagnant
layer proceeds by diffusion,
CG - CS
DG
then. F1 DG
hG =
where DG = diffusivity

For mass-transfer limited deposition, model

dy
1
dt hG U

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