(Sici) 1097-0207 (20000110 30) 47 1 3 341 Aid-Nme774 3.0.co 2-Z PDF

INTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN ENGINEERING
Int. J. Numer. Meth. Engng. 47, 341}358 (2000)
On modelling thermal oxidation of Silicon I: theory

Vinay S. Raos and Thomas J. R. Hughes*,t
Division of Mechanics and Computations, Stanford ;niversity, Stanford, CA 94305, ;.S.A.
SUMMARY
This work focuses on a new mathematical framework to model the process of thermal oxidation in silicon.
The mathematical model is derived from the fundamental conservation equations of mechanics. The mass
balance law provides the description of the oxidant transport and the Si}SiO interface motion, and
momentum balance provides the framework to model the displacements and stresses 2 in the bulk and the
oxide. The displacements de"ne the geometry of the "nal oxide structure. The large expansion is treated
within a mathematically exact formulation following a split of the deformation gradient. A thermodyn-
amically consistent constitutive equation for silicon dioxide is suggested to represent recent experimental
data. Copyright ( 2000 John Wiley & Sons, Ltd.
KEY WORDS: thermal oxidation; continuum mechanics; balance laws; di!usion; reaction; viscoelasticity
1. INTRODUCTION
Modern integrated circuits are manufactured by fabricating a large number of basic devices like
transistors and capacitors on a wafer of semiconducting material like silicon. The devices are
isolated from one another using structures made of silicon dioxide. Silicon dioxide is also used as
dielectrics in transistors. These silicon dioxide structures are constructed on the wafer by thermal
oxidation wherein oxygen reacts with silicon to form silicon dioxide at temperatures ranging from
700 to 12003C or by using vapour deposition techniques wherein oxide is deposited directly on
the wafer. Thermal oxidation is used in cases where high-quality oxide structures are required.
Quality is determined by the homogeneity of material properties.
Oxidation of silicon is accompanied by large volume expansion. Molar volume of silicon
dioxide is 2)2 times that of silicon. Large expansion leads to large strains and, when these strains
are constrained, large stresses. Stresses on the silicon wafer can a!ect the device performance by
altering the impurity concentrations and increasing leakage currents. It is thus important to
analyse the oxidation process to study the mechanical consequences of the process such as change
in geometry and stress evolution.
The oxidation process proceeds as follows: the silicon wafer is covered with a mask which only
exposes the regions on the wafer that are to be oxidized. The wafer is then heated and oxygen (or
*Correspondence to: Thomas J. R. Hughes, Department of Mechanical Engineering, Stanford University, Durand
Building, Stanford, CA 94305-4040, U.S.A. E-mail: hughes@am-sun2.stanford.edu
sCurrent address: Schlumberger Cambridge Research Limited, Cambridge, U.K.
tProfessor.
Contract/grant sponsor: Defence Advanced Research Projects Agency; contract/grant number: DABT63-93-C-0053
CCC 0029-5981/2000/020341}18$17.50 Received 1 April 1999

Copyright ( 2000 John Wiley & Sons, Ltd.
342 V. S. RAO AND T. J. R. HUGHES
steam) is introduced into the chamber. The exposed silicon areas react with the oxygen forming
silicon dioxide, and the reaction is accompanied by volume expansion. The oxidant di!uses
through the existing oxide to react with the silicon at the Si}SiO interface. This generates new
2
silicon dioxide and the interface moves into the silicon domain.
One of the earliest and most signi"cant developments in modelling the process was the
development of the Deal}Grove model [1]. This provided the "rst model for the oxidant di!usion
through the oxide. It was based on a hypothesis of one dimensionality. The model gave a good
representation of the process and provided a quantitative description of the di!usion dominated
and reaction dominated regimes. The Deal}Grove model, however, does not describe the thin
oxide cases well. The model also assumes that the oxidant concentration in the silicon region is
zero which has been shown to be incorrect. Various corrections to the model have been suggested.
Huang et al. [2] propose a two-species di!usion model where one species, oxygen, di!uses
through the oxide to react with silicon at the Si}SiO interface and the second species, atomic
2
silicon, di!uses through the oxide in the opposite direction to react with oxygen at the SiO }O
2 2
interface. Dunham and Navi [3] attribute shortcomings in the Deal}Grove model to the
assumption that di!usion is the only mode of oxidant transport. They add the convective term to
the di!usion equation to correct this de"ciency.
There are two aspects to the stress equilibration problem. One is the cause of the strain in the
material and the other is, given the strain, the stress response of the material.
It is known from experiments and from molecular studies (see Ra!erty [4] and references
therein) that oxidation is accompanied by a 120 per cent expansion. This expansion causes
stresses. An intuitive understanding of the stress "eld can be obtained by the following thought
experiment. Consider a thin, planar silicon wafer in which oxidation of the upper layer results in
expansion. In an unconstrained case at equilibrium, the expansion of the upper layer will cause
the wafer to strain perpendicular to the cross-section causing compressive stresses in the oxide
and tensile stresses in the bulk. To balance moments at the ends, the wafer curves away from the
oxide. The stresses and the expansion process govern the shape of the structure that is formed. An
accurate description of expansion is crucial in determining the shape of the oxide.
Kao [5] conducted a series of experiments in which silicon cylinders were oxidized. Complete
oxidation con"rmed the volume increase to be 120 per cent. The experiments were conducted at
various temperatures giving similar results and thus indicating that temperature e!ects were not
in#uential in the total expansion. The expansion following the oxidation is large compared to
purely thermal expansion. There are many theories explaining the stress generation due to
expansion. The simplest one is due to Pilling and Bedworth [6] in which the shape change
associated with planar oxidation is explained entirely within the small deformation context and
attributed to the shear strain in silicon dioxide. This model yields stresses that are too high.
Another theory was suggested by Vermilyea [7] in which the idea of a &kink site' proposed earlier
by Mott is extended. The kink site immediately preceding the oxide creates an empty space
allowing the oxide to expand freely. This only explains the one-dimensional aspect of the strain.
The computer program, SUPREM [8], has been developed using a similar one-dimensional
theory of expansion. The expansion is incorporated as a velocity boundary condition at the
Si}SiO interface. The velocity is perpendicular to the boundary, and thus, a planar wafer will
2
grow in a planar fashion according to this model. From the experiments of Yu [9] it is clear that
unconstrained planar wafer oxidation leads to higher dimensional e!ects like bending. This
e!ectively proves the invalidity of the existing one-dimensional models. As mentioned previously,
the expansion accompanying the reaction is large compared to thermal expansion. Large
Copyright ( 2000 John Wiley & Sons, Ltd. Int. J. Numer. Meth. Engng. 47, 341}358 (2000)
ON MODELLING THERMAL OXIDATION OF SILICON I: THEORY 343
deformations need a kinematically di!erent model from the one employed in SUPREM [8]. The
theory of "nite deformation kinematics is presented in Truesdell and Toupin [10], Marsden and
Hughes [11] and Gurtin [12]. In the context of the "nite deformation theory a suitable expansion
model is also required.
Modelling of the material behaviour of silicon dioxide has gone from being a purely elastic
modelling of Hsueh and Evans [13], to &incrementally elastic' in the early versions of SUPREM,
to the linear viscous model of Chin [14], to the non-linear viscous model of Eyring [15] in the
recent versions of SUPREM. Each model is valid within a certain regime but not beyond. It is
accepted now, and has been shown by Yu et al. [9], that the oxide behaves as a viscoelastic
material. Their experimental set-up involves oxidation of a lightly doped silicon substrate
in dry or steam ambients. Laser scanning techniques are used to measure the curvature in the
wafer following oxidation. A variety of experiments were carried out using the set-up. The
stresses were measured at room temperature, during thermal cycling and during isothermal
annealing. The experiments validate the pioneering work and hypotheses of EerNisse [16]
regarding #ow of oxide at elevated temperatures. Silicon dioxide exhibits a signi"cant viscous
#ow at higher temperatures. The thermal cycling experiment involves an oxidized wafer subjected
to rapid thermal ramping. The rate of temperature increase is much higher than the charac-
teristic relaxation times of the material, hence the term &rapid'. Upon reaching 9003C the
specimen is held for six hours and then cooled rapidly. The isothermal annealing shows the stress
relaxation characteristics of the oxide when held at a constant temperature hence indicating
viscoelasticity. The stress relaxation is considerably faster at higher temperatures indicating a
lower viscosity.
This work has been undertaken to model the entire process within the framework of the
balance laws of continuum mechanics and thus to correctly reproduce the physics. The paper
describes the development of a new equation to describe the di!usion}reaction process from
which the interface motion description can be derived. A general and thermodynamically
consistent viscoelastic constitutive model has been proposed for silicon dioxide. The kinematics
of the process are described by the non-linear "nite deformation theory to accommodate the large
rotations and strains associated with non-planar expansions. The expansion formulation is
embedded in the constitutive theory by way of the multiplicative split of the deformation gradient.
In Section 2 the oxidation process is described in detail and the modelling assumptions are
stated. Sections 3 and 4 deal with the two basic processes that make up the thermal oxidation of
silicon, namely, the di!usion}reaction process and the stress equilibration process. The coupling
of the equations described in Sections 3 and 4 is discussed in Section 5. Finally, the conclusions
are given in Section 6. It also outlines the di!erences between the current model and the
traditional thermal oxidation models.
2. PROCESS DESCRIPTION
In this section the actual oxidation process is explained in steps and the main assumption made in
modelling this process is stated.
The silicon wafer to be oxidized is covered with a mask which is etched away in the regions
where the oxide is to be grown. The mask is made of a material that does not react with oxygen
nor does it let oxygen di!use through it. Silicon nitride is a commonly used mask. The wafer is
introduced into a chamber where it is heated to the desired temperature, usually between 700 and
12003C. The reaction rate and the material properties are dependent on the temperature and
determine the temperature at which oxidation will be carried out.
Oxidation is carried out in a chamber with oxygen or steam ambient where the oxidant
concentration can be controlled. At elevated temperatures oxygen reacts rapidly with silicon to
form silicon dioxide. This reaction is accompanied by the expansion of silicon dioxide. Molar
volume of silicon dioxide is 2)2 times that of silicon. Once the layer of oxide is formed, the oxygen
di!uses through it and reacts with silicon at the Si}SiO interface. This process is allowed to
2
continue until the desired shape of the oxide structure is obtained. The expansion of the oxide
causes stress to build up in the oxide as well as in the bulk. Modelling the "nal geometry and the
stresses in the materials are the goals of this study.
The oxidation modelling problem is looked at from a continuum mechanics perspective. Using
the continuum approach implies that the smallest length scale considered is considerably larger
than the intermolecular distances. The material is assumed to behave as a continuum rather than
an aggregate of molecules. The goal is to derive di!erential equations governing oxidation
phenomena. These equations are arrived at by starting from the fundamental balance principles
of mechanics.
The oxidation process hence is subdivided into the di!usion}reaction process and the mechan-
ical stress equilibration process. These processes are discussed in detail in the following sections.
3. DIFFUSION}REACTION PROCESS
In this section a model describing the di!usion}reaction process is derived from the mass balance
equation. The Si}SiO interface, where the reaction takes place, is described as a surface of
2
discontinuity. The density of oxidant is the "eld variable that varies discontinuously across the
interface. The interface will be an (n!1)-dimensional hypersurface in an n-dimensional body.
The equation will then be simpli"ed by applying approximations based on experimental observa-
tions.
Refer to Figure 1 in which a body occupies the region ) in R3 space. The di!using species is
assumed to di!use in )~. At the interface ! it reacts with the material that makes up )` and the
reaction leads to the formation of the material that makes up )~. Thus the interface between )~
and )` moves &into' the region )`.
The Extended Master Balance Law [11] provides a framework to formulate the di!u-
sion process. Mass balance is derived from the following statement of the Extended
Master Balance Law: Given o(x, t), a C1 scalar-valued function in )~X)`, except across
the surface of discontinuity !, a vector "eld c which is also C1, and a distributed source term b,
then,
P) o dv!P) b dv! P ) c ' n ds"P) A Lt #$ ' ov!b!$ ' cB dv

d Lo
dt L
P!
# (IoJ(v ' n!< )!Ic ' nJ) d!
n
(1)
where c is the boundary #ux, < is the interface speed along the normal n, I ) J denotes the jump
n
in the argument across the surface of discontinuity ! and d/dt denotes the time derivative. Note
that v, the particle velocity, and < are di!erent, in general.
n
Figure 1. Domain representing the body ) with a dis- Figure 2. Relating oxidant di!usion to mass transport
continuity
3.1. Application to oxidant diwusion
The idealization of the Si}SiO interface to a set of measure zero in the domain ) provides
2
a setting for the formulation of the oxidant di!usion problem. In reality this is not the case as the
reaction zone is often many atomic layers thick. Here again, we invoke the fact that length scales
in the continuum framework are much larger than the inter-atomic distances. This requires the
reaction model to be suitable for the approximation.
Consider a sequence of domains )1 (Figure 2) such that the surface of discontinuity ! always
i
lies within the domains. This implies
!3)1 , ∀i"1, 2, . . . , (2)

i
)1 L)1 , i'j (3)
i j
Now, )1 de"nes a control volume for the problem. De"ne T as the in#ux of oxidant into the
i
domain )1 . Applying the Extended Master Balance Law and making the assumptions that
i
convective e!ects are absent and the system is in steady state gives,
P) $ ' T d)#P! IT ' nJ d!#P! IoJ<n d!"0

1
i
(4)
As )1 P!, the volume integrals tend to zero. Equation (4) reduces to

i
P! IT ' nJ d!#P! IoJ<n d!"0 (5)
Equation (5) is the familiar Rankine}Hugoniot condition [17]. Equation (5) de"nes the interface
speed. This will be considered in detail in the following section.
It is interesting to compare equation (4) to the Deal}Grove model [1]. The latter is a pure
di!usion equation applicable in the silicon dioxide domain. The derivation above gives a much
more general framework for developing the di!usion and reaction model. If the convective e!ects
are found to be non-negligible they can be reintroduced according to equation (1). The jump
terms are crucial in enforcing what are called the segregation conditions at the reaction interface.
In a pure di!usion equation this cannot be done. The Rankine}Hugoniot condition provides the
exact form of the interface velocity without having to resort to ad hoc de"nitions. This develop-
ment is a signi"cant departure from the previously used models in oxidation simulation.
3.2. Reaction kinetics
In this section physical chemistry of the silicon}oxygen reaction to form silicon dioxide will be
studied. This will be incorporated into the jump speed condition derived from the oxidant
transport model.
At the Si}SiO interface, oxygen reacts with silicon to form silicon dioxide. This reaction is
2
written as
Si#O H SiO (6)

2 2
At equilibrium, the rate of the forward reaction is equal to the rate of reverse reaction. In physical
chemistry notation,
Rate of forward reaction"k [Si][O ]

& 2
Rate of backward reaction"k [SiO ]
" 2
where [ ) ] is the concentration of the argument, and k and k are the forward and backward
& "
reaction coe$cients. They may be dependent on temperature and pressure or on the presence of
catalysts.
In process modelling, k [Si]/k is considered a constant when compared to the concentration
& "
of oxygen. This is justi"ed as silicon is a solid thus [Si] is much larger than the concentration of
di!using gas, viz. oxygen. The coe$cient of reaction is de"ned as,
k "k [Si]/k (7)

s & "
Using equation (7) the rate of silicon dioxide formation is written as
[SiO ]"k [O ] (8)

2 s 2
Newly formed silicon dioxide at the interface continually rede"nes the Si}SiO interface and thus
2
the silicon dioxide domain. This can be modelled by applying the Extended Master Balance Law
to silicon dioxide.
Density can be written in terms of the number of molecules per unit volume (as opposed to the
mass per unit volume). The two quantities can be converted from one to the other by a factor of
the mass of one molecule.
The Rankine}Hugoniot condition derived from Extended Transport Theorem is given by
P! IT09 ' nJ d!#P! Io09 J<n d!"0 (9)
where T is the silicon dioxide #ux and o is the silicon dioxide density. The following (stronger)
09 09
condition satis"es equation (9):
< "!IT ' nJ/Io J (10)

n 09 09
The jump in the silicon dioxide density is given by
Io J"o`!o~ (11)
09 09 09
where o` is the concentration of silicon dioxide in the silicon region. This can be assumed to be
09
very small compared to o~ . In the process modelling literature, the latter is commonly denoted
09
by N . Equation (10) can be rewritten, using equations (11) and (8) as
1
< "k o /N (12)
n s i 1
The boundary conditions are de"ned by prescribing data on L)~ and L)`. If ! is a surface of
discontinuity that is frozen, the di!usion equation is solved in the two regions separately with
compatibility conditions along !.
The di!usion equation is elliptic. Boundary conditions must be prescribed on all the bound-
aries. This necessitates prescription of boundary conditions on L)~, L)` and two conditions on
the interface.
This point is clari"ed by looking at a one-dimensional problem. Solving the di!usion equation
on each segment gives rise to two constants for each segment. This places a requirement of four
conditions for a complete solution. Two conditions are speci"ed on the outer boundaries. There
are two more required at the surface of discontinuity. The two interface conditions are obtained
from the chemistry literature and are called #ux segregation and concentration segregation. Flux
segregation is speci"cation of the jump in normal #ux across the interface and the concentration
is the ratio of concentrations across the interface.
The boundary conditions are summarized as,
o"g` x3L)` (13)

g
T ' n"h` x3L)` (14)
h
o"g~ x3L)~ (15)
g
T ' n"h~ x3L)~ (16)
h
IT ' nJ"l x3! (17)
o`
"m x3! (18)
o~
Observing that IT ' nJ "IT ' nJ , and that [SiO ] in equation (8), when interpreted as a #ux of
! 09 ! 2
SiO molecules, is !IT ' nJ , we have l"!k o~ . Equation (17) is the #ux segregation
2 09 ! s !
condition. The concentration segregation condition is equation (18), where m is a given constant.
This gives the complete description of the di!usion}reaction process.
4. STRESS EQUILIBRATION
This section deals with the mechanical behaviour of the material under various loading condi-
tions. Mechanical behaviour includes the stress and strain response of the body to external
driving forces. Like in the previous sections, fundamental balance laws are used to derive the
governing equations. For a purely mechanical process the momentum balance law is su$cient.
A purely mechanical process implies isothermal conditions during the process. In Section 4.1 the
momentum balance law is described, in Section 4.2 the visoelastic constitutive equations which
govern the material behaviour of silicon dioxide are described and in Section 4.3 a general "nite
expansion formulation is presented.
4.1. Local momentum balance law
Let )LR3 be the reference placement of a continuum body B with smooth boundary L).
Label the material particles X3)XL). Denote by u( ), t), the motion of the body in time interval
[0, ¹ ] with material velocity V"Lu/Lt and deformation gradient F"Lu/L X. Denote the
current particle position by x"u(X, t). Consequently, u(X, t)"X#u(X, t), where u(X, t) is the
displacement.
The Lagrangian form of the balance equations then take the form,
u5 "V (19)
o V0 "DIV [P]#o B (20)

0 0
for the domain de"ned by )][0, ¹ ]. In the above equations, o is the material density, P is the
0
"rst Piola}Kirchho! or the nominal stress tensor and B is the body force vector. Superposed dots
signify material time derivatives. The symbol DIV [ ) ] denotes the divergence operator with
respect to the reference con"guration.
Equation (20) denotes the balance of momentum with the left-hand side term representing the
inertial force and the right-hand side denoting the internal and body forces.
This is the description of an isothermal mechanical process. The temperature being constant
does not imply the entropy being constant. Hence, it does not preclude dissipative processes. For
example, one could have a dissipative inelastic process occurring at "xed temperature, #.
The momentum balance law is given by equations (19) and (20), with the following initial and
boundary conditions:
u(X, 0)"u on )
0
V(X, 0)"V on )
0
u(X, t)"u6 on L)u
PN"h on L)
h
4.2. Constitutive equations
In the derivation of the constitutive equations, we start with the de"nition of the isothermal
internal energy of a material with internal variables, Q. Internal variables are used in the
description of inelastic processes and the theory behind them is described in Lubliner [18]. The
internal energy, e, at any material point X is given by
e"eN (X; F, Q) (21)
Substituting the expression in the Clausius}Planck inequality form of the Second Law of
Thermodynamics and computing the rate of change of internal energy using the chain rule, we get
A B A B
LeN LeN
P! : F0 ! : Q0 *0 (22)
LF LQ
The constitutive relations must be such that this energy dissipation inequality is satis"ed for all
admissible processes. For arbitrary elastic processes
Q0 "0 (23)
and all F0 are admissible. Hence the following constitutive equation is obtained:
P"LeN /LF (24)
The internal dissipation is thus given by
A B
LeN
! : Q0 *0 (25)
LQ
The arguments used in the above derivation are referred to as Coleman's method. For details see
Coleman [19] and Truesdell and Noll [20].
Material frame indi!erence, or objectivity, is a fundamental property the constitutive equations
must satisfy. Objectivity requires the internal energy de"nition to be
e"eN (X; C, Q) (26)
where C is the right Cauchy}Green tensor and is given by
C"FTF (27)
It is apparent that C is material frame invariant and symmetric, thus it has only six independent
terms. The second Piola}Kirchho! stress is given by
S"LeN /LE (28)
where E is the Lagrangian strain tensor given by
E"1 (C!1) (29)

2
Equivalent forms of stress power are given by the following equations:
P : F0 "S : E0 "s : d (30)
where S is the symmetric Piola}Kirchho! stress, s is the Kirchho! stress and d is the rate of
deformation tensor.
This set-up is used in the development of the constitutive model to describe the material
behaviour of silicon dioxide. It has been shown by Yu et al. [9] that silicon dioxide is
a viscoelastic material. The advantages of developing the constitutive equations based on the
above framework are obvious: the resulting constitutive equations will be thermodynamically
correct and indi!erent to rigid motions of the material frame of reference.
The development commences with postulating the existence of the Helmholtz free energy
function. The free energy is postulated with internal variables describing the energy dissipation in
the material. The Second Law of Thermodynamics will be used to arrive at expressions for stress.
An additional equation governing the evolution of internal variables is postulated in the next
subsection.
The Helmholtz free energy function is de"ned as
("eN !hg (31)
Applying the Clausius}Planck inequality and using equations (24), (28) and (25) the following
relations are obtained:
P"L(/LF (32)
S"L(/LE (33)
L(
! : Q0 *0 (34)
LQ
The subdomains )~ and )` can be composed of di!erent materials. In the development to
follow, it will be assumed that )~ is composed of an inelastic material, while )` is purely elastic.
Accordingly, we shall assume di!erent forms for the Helmholtz free energy (see [21, 22]):
("(~(E, Q)";~( J)#(1~(E1 )!Q : E1 #( (Q) in )~ (35)
I
1 1
("(`(E)";`( J)#(`(E ) in )` (36)
The elastic part of the stored energy is assumed to be decoupled into a volumetric part, ; and a
deviatoric part, (1. Following Flory [23], the deformation gradient is decoupled multiplicatively
into dilatational and isochoric parts as follows:
F1 "J~1@3F (37)
Note, the determinant of F1 is unity. This implies F1 is the part of deformation that exactly
preserves the volume. Now, de"ne C1 "J~2@3C and E1 "1 (C1 !1). The set of stress-like internal
2
variables is denoted by Q. Finally, ( is the equilibrium term explained later in this section.
I
The following identities arise out of a straightforward application of the chain rule
LJ J
" C~1 (38)
LC 2
LE1 LC1
" "J~2@3 [I!1 C ? C~1] (39)
LE LC 3
where, I is the symmetric fourth-order identity tensor. The second Piola}Kirchho! stress tensor is
evaluated using the above relations and equation (33). It is given by
C D
L(1~
S~"J;~@C~1#J~2@3 DEV !Q (40)
LE1
C D
L(1`
S`"J;`@C~1#J~2@3 DEV (41)
LE1
;@ denotes the derivative of ; with respect to its argument, i.e. J. It is the expression
for hydrostatic pressure. The deviator in the material con"guration is given by DEV [ ) ]. It is
given by
DEV [ ) ]"( ) )!1 [C : ( ) )]C~1 (42)

3
for a second-order contravariant tensor. It is easily seen that the expression of trace in the
reference con"guration is obtained by pushing the contravariant tensor forward, computing the
trace and pulling it back as shown below for any contravariant tensor H of order two
TR[H]"(FHFT : 1) (43)
Pushing forward the second Piola}Kirchho! stress tensor, one obtains the Kirchho! stress tensor
given by
CG H D
L(1~
s~"J;~@1#J~2@3 dev F !Q FT (44)
LE1
CG H D
L(1`
s`"J;`@1#J~2@3 dev F FT (45)
LE1
where dev [ ) ] is the deviator in the spatial con"guration given by
dev [ ) ]"( ) )!1 [1 : ( ) )]1 (46)

3
where 1 is the second-order identity tensor.
4.2.1. Evolution equation for the internal variables. Linear evolution equations are postulated
for the internal variables Q. In this section, Q will be replaced by Q signifying the ith viscoelastic
i
element.
This also enforces &standard solid' type of viscoelastic behaviour ([21, 22]):
G C DH
1 c L(1~
Q0 # Q " i DEV 2 (47)
i q i q LC1
i i
Q D "0 (48)
i t/0
where c 3[0, 1] is subjected to the restriction that,
i
N
+ c "1!c with c 3[0, 1) (49)
i = =
i/1
c "E /E (50)
i i 0
and q '0 is the relation time (not to be confused with the Kirchho! stress tensor). The evolution
i
equations are linear and can be solved analytically. In addition, it may be noted that
q PRN Q P0 implying very slow processes are elastic

i i
Figure 3. Generalized Maxwell model for solids
Of utmost importance in dissipative systems is the characterization of the equilibrium response.

At equilibrium the system must not dissipate energy. Using (47) it follows that at equilibrium:
Q0 "0 (51)
N Q"c DEV [L(1~/LE1 ] (52)
In addition, the driving thermodynamic forces must be zero:
L(1~
"0 (53)
LQ
L(
N I"E1 (54)
LQ
This fully de"nes ( as

I
( "!c(1~#Q : E1 (55)
I
The above arguments can be extended to the case where more than one viscoelastic elements is
present. For details see Reference [22].
Remark. This model has an attractive one-dimensional interpretation. Consider Figure 3. The
response of this system of springs and dashpots is analogous to the constitutive model presented
above. The combination of Maxwell viscoelastic elements in parallel to a spring makes it a model
for a solid (in"nite deformation implies in"nite stresses). The additional Maxwell elements can be
added to match a complicated response observed in experiments. This model has been used to "t
experiments of Yu [9] using constant dashpot and spring parameters.
The model can also be used to describe the behaviour in the elastic and viscous limits by
putting the appropriate spring and dashpot coe$cients to zero.
4.3. Expansion formulation
Consider a bar of length l subject to a temperature increase *h. The change in length of the bar,
*l, is given by
*l"la *h (56)
a is the coe$cient of expansion, de"ned as the increase in length per unit length of the bar for
a unit rise in temperature. Final length
¸"(1#a *h)l (57)
Use the above expression in generalizing to three dimensions. Consider an in"nitesimal cube of
edge length l subject to a temperature increase *h. The "nal length is given by equation (57). The
initial volume, < , and "nal volume < may thus be written as
* &
< "l3 (58)
*
< "((1#a *h)l)3 (59)
&
If a *t is small, equation (59) may be approximated as (dropping the higher-order terms in a *t)
< "(1#3a *h)< (60)
& *
This expression is commonly cited in the literature; see, e.g., Carlson [25] and Armero [26] in the
context of expansion accompanying temperature increase. But, for larger volume changes this
linearized form is clearly incorrect. In the following section an appropriate framework to handle
large volume changes will be constructed.
4.3.1. Multiplicative split. Consider the motion u of a body B occupying a placement )LR3
bounded by L). The deformation gradient is given by F"Lu/LX.
As shown in Figure 4 the motion can be considered to be a composition of two motions: pure
expansion followed by volume preserving motion. Mathematically, it can be written as
u(X)"u6 (uh(X)) (61)
This leads to a multiplicative split of the deformation gradient given by
F"F1 Fh (62)
Note that the intermediate con"guration is a free expansion. It need not be a physically realistic
state. It is simply a construct that will help in formulating the problem in the non-linear regime.
Within this set-up, for an isotropic expansion, the volumetric part of the deformation gradient
is given by
Fh"a1 (63)
the invariants of the e!ective left Cauchy}Green tensor, b, are given by
I (b1 )"I (b)/a2 (64)
1 1
I (b1 )"I (b)/a4 (65)
2 2
I (b1 )"I (b)/a6 (66)
3 3
Figure 4. Illustration of the multiplicative split
This setting was proposed for thermomechanical problems by Lu and Pister [27]. The multiplica-
tive split of the deformation gradient and the concept of the abstract stress free state was
proposed earlier (in the context of "nite plasticity) by Lee and Liu [28]. The formulation in
plasticity has gained wide recognition through the work of Simo [29, 30] and his coworkers.
Constitutive equations of an isotropic, hyperelastic material arising out of the free energy
function given by ("((b) are considered here. It has been shown in Section 4.3.1 that the
deformation can be locally decomposed into a stress free expansion part and an &e!ective' part
(using the terminology in Reference 27). The free energy function is to be evaluated using the
e!ective part of the deformation gradient F1 . As an example, consider a neo-Hookean model with
quadratic logarithmic volumetric response. This has been called the neo-Hookean model with an
extension to the compressive regime by Simo [31]. The stored energy function has the correct
volumetric and deviatoric split
((b1 )"1 (i log [ JM ])2#1 k[ JM ~2@3b1 : 1!1] (67)

2 2
Considering the volumetric term in equation (68)
1 (i log [ JM ])2"1 (i log [ J]!log [a3])2 (68)

2 2
and the deviatoric term,
1 k [ JM ~2@3b1 : 1!1]"1 k[( J/a3)~2@3a~2b : 1!1]

2 2
"1 k[ J~2@3b : 1!1] (69)
2
The deviatoric terms do not contain the expansion term at all. This formulation is conveniently
extended to the viscoelastic model.
5. COUPLED PROBLEM
In the previous two sections, the two processes that describe thermal oxidation were considered.
In reality they happen simultaneously. Hence the di!erential equations describing them are
simultaneously valid. If the equations are coupled, the solution of one set of di!erential equations
will a!ect the other. To determine the coupling the equations are studied in this section.
The di!usion}reaction equation is given by equation (4). The di!usive #ux, T, is de"ned as
T"D +o (70)
where o is the oxidant concentration and D is the di!usivity of the material.
In equations (4) and (71) the material dependent terms are D and < . < is directly proportional
n n
to the reaction rate coe$cient k from equation (12). In Ra!erty [4] the stress dependence of
s
D and k is discussed and their functional forms are given in terms of the Kirchho! stress, q, as
s
follows:
A B
p< 1
D(s)"D exp $ , p"
: s:1 (71a)
0 k# J
A B
p< 1
k (s)"k exp n 3 , p "
: n sn (71b)
s s0 k# n J '
In equations (71a) and (71b), D and k are the stress-free di!usivity and reaction constant
0 s0
respectively, < and < are the activation volumes for di!usion and reaction, k is Boltzmann's
$ 3
constant and # is the temperature. The components p and p are respectively, the hydrostatic
n
stress and normal stress along n corresponding to the Cauchy stress tensor, r"J~1s.
Equation (20) prescribes momentum balance. It is to be solved by incorporating the
constitutive relations given by equation (28). If the neo-Hookean stored energy function is
considered for the elastic part of the viscoelastic constitutive equations there are four material
dependent parameters. They are the bulk and the shear moduli in equation (67) and the two
parameters governing the evolution equation in equations (47) and (49). The four-parameter
model corresponds to a neo-Hookean stored energy function and a two parameter evolution
equation. There has been no mention of the dependence of these parameters on the oxidant
concentration. Hence the momentum balance equation can be solved without concentration
information.
It must be noted, however, that the interface location is required. The interface location
determines the silicon and silicon dioxide regions. Silicon dioxide behaves like a viscoelastic solid.
Hence the interface location determines the constitutive law to be applied.
The system of equations proposed in this paper (see Box 1) is coupled. But the coupling is such
that the momentum equations can be solved given the interface position. The computed stresses
are used to de"ne the di!usivity and reaction rate coe$cient for the di!usion problem which can
then be solved.
6. CONCLUSIONS
The mathematical model presented in this paper for thermal oxidation is signi"cantly di!erent
from previously used formulations. The equations are derived from fundamental conservation
Box 1. Summary of the IBVP for thermal oxidation
Find Mu, P, oN: )][0, ¹ ] > R3]GL(3)]R` such that

o uK !DIV[P]!o B"0 on )][0, ¹ ],
0 0
where
L(
P"F
LE
("(~(E, Q)";~(J)#(1~(E1 )!Q : E1 #( (Q) on )~
I
("(`(E)";`( J)#(1`(E1 ) on )`
with initial conditions
u(X, 0)"u (X) on )
0
u5 (X, 0)"V on )
0
and boundary conditions
u(X, t)"u6 (t) on L)u
PN"h on L)
h
and
$ ) T"0 on ()~X)`)][0, ¹ ]
where
A B
J~1(PFT) : 1<
T$"D$ exp $ +o on )$
0 k#
with interface conditions:
A B
n ' ( J~1PFT)n<
IT ' nJ "!k exp 3 o~
! s0 k# !
o~
! "m,
o`
!
and boundary conditions
o"g$ on L)$
g
T ' n"h$ on L)
$
h
principles of continuum mechanics. The di!usion}reaction equation is the generalisation of the

classical Deal}Grove model. The jump terms in the derivation permit the application of the
segregation conditions. The Si}SiO interface motion speed is derived rather than postulated.
2
The di!usion equation can be extended to the convection regime within the theory and the
correct jump conditions can be obtained.
The stress generation and equilibration is the second aspect of thermal oxidation. The paper
deals with the constitutive modelling of silicon dioxide as well as the expansion modelling.
Finite deformation kinematics have been adopted for modelling the geometric response. This
means that large deformations can be accurately modelled. The increased range of applicability
stems from the fact that the strain measures are no longer linear. Large deformations near the
mask lead to large rotations. In small deformation theory the modelling of rotations is inaccurate.
The viscoelastic constitutive equations have been presented by assuming a &standard solid'
model. The model has proper limiting conditions for very fast and very slow processes. It can be
modi"ed to model purely viscous response. The evolution equations are linear and hence can be
solved analytically. They permit the addition of Maxwell elements thus enabling "ts to complex
response observed in experiments. The constitutive model is thermodynamically consistent and
satis"es the properties of material frame indi!erence.
The expansion modelling is done in a kinematically consistent manner so that the constitutive
response is exact in the limiting cases of free, unconstrained expansion or the fully constrained
(zero strain) case. Unlike the traditional attempts at oxidation modelling, where expansion was
a one-dimensional e!ect, expansion is not incorporated as an interface condition. The current
expansion model, in the isotropic case, correctly predicts the three-dimensional e!ects of expan-
sion. This can be shown by the wafer curvature experiment where the SUPREM models do not
predict any curvature while the current theory predicts the correct curvature.
Numerical examples based on the new theory presented herein are included in Part II of this
paper.
ACKNOWLEDGEMENTS
The authors would like to thank Prof. R. W. Dutton, Prof. Edwin Kan and Dr. Peter Gri$n for
many rewarding discussions. We would also like to acknowledge the "nancial support for the
research provided by the Defence Advanced Research Projects Agency under contract DABT63-
93-C-0053 to Stanford University.
REFERENCES
1. Deal BE, Grove AS. General relationship for the thermal oxidation of silicon. Journal of Applied Physics 1965;
36(2):3370}3378.
2. Huang SF, Gri$n PB, Plummer JD, Rissman P. Modeling stress e!ects on thin oxide growth kinetics. Personal
Communication.
3. Navi M, Dunham ST. Viscous compressible model for stress generation/relaxation in SiO . Journal of the Electro-
2
chemical Society 1997; 144(1):367}371.
4. Ra!erty CS. Stress e!ects in silicon oxidation-simulation and experiments. Ph.D. ¹hesis, Stanford University, 1989.
5. Kao DB. Two dimensional oxidation e!ects in silicon-experiments and theory. Ph.D. ¹hesis, Stanford University,
June 1986.
6. Pilling NB, Bedworth RE. Journal of the Institute of Metallurgy 1923; 29:529}530.
7. Vermilyea DA. On the mechanism of the oxidation of metals. Acta Metallurgica 1957; 5:492.
8. Technology Modeling Associates, Inc., Sunnyvale, CA. ¹S;PREM-4 ¹wo-Dimensional Process Simulation Program,
<ersion 6.4, ;ser1s Manual, October 1996.
9. Yu CL, Flinn PA, Bravman JC. In-situ measurement of viscous #ow of thermal silicon dioxide thin "lms at high
temperature. Personal Communication.
10. Truesdell CA, Toupin WR. ¹he Classical Field ¹heories. Number III/1 in Handbuch der Physik. Springer: Berlin,
1960.
11. Marsden JE, Hughes TJR. Mathematical Foundations of Elasticity. Dover: New York, 1994.
12. Gurtin ME. An Introduction to Continuum Mechanics. Academic Press: New York, 1981.
13. Hsueh CH, Evans AG. Oxidation induced stress and some e!ects on the behavior of oxide "lms. Journal of Applied
Physics 1983; 54(11):6672}6686.
14. Chin D. Two-dimensional oxidation. Ph.D. ¹hesis, Stanford University, 1983.
15. Eyring H. Viscosity, plasticity and di!usion as examples of absolute reaction rates. Journal of Chemical Physics
1936; 4:283}291.
16. EerNisse EP. Stress in thermal SiO during growth. Applied Physics ¸etters 1979; 35(1):8.
2
17. LeVeque R. Numerical Methods for Conservation ¸aws. BirkhaK user: Basel, 1992.
18. Lubliner J. Plasticity ¹heory. MacMillan: New York, 1990.
19. Coleman BD. Thermodynamic of materials with memory. Archive for Rational Mechanics and Analysis 1964; 17:1}46.
20. Truesdell CA, Noll W. ¹he Nonlinear Field ¹heories of Mechanics. Number III/3 in Handbuch der Physik. Springer:
Berlin, 1965.
21. Simo JC. On a fully three-dimensional "nite strain viscoelastic damage model: formulation and computational
aspects. Computer Methods in Applied Mechanics and Engineering 1985; 60:153}173.
22. Simo JC, Hughes TJR. Computational Inelasticity. Springer: New York, 1998.
23. Flory RJ. Thermodynamic relations for high elastic materials. ¹ransactions of the Faraday Society 1961; 57:829}838.
24. Holzapfel GA, Simo JC. A new viscoelastic constitutive model for continuous media at "nite thermomechanical
changes. International Journal of Solids and Structures 1996, 33(20-22):3019}3034.
25. Carlson DE. ¸inear ¹hermoelasticity. Number VI/2a in Handbuch der Physik. Springer: Berlin, 1972.
26. Armero F. Numerical analysis of dissipative dynamical systems in solid and #uid mechanics with a special emphasis
on coupled problems. Ph.D. ¹hesis, Stanford University, November 1993.
27. Lu SCH, Pister KS. Decomposition of deformation gradient and representation of the free energy function for
isotropic solids. International Journal of Solids and Structures 1975; 11(7-8):927}934.
28. Lee EH, Liu DT. Finite strain elastic}plastic theory particularly for plane wave analysis. Journal of Applied Physics
1967; 38:19.
29. Simo JC. Framework for "nite strain elastoplasticity based on the multiplicative decomposition and hyperelastic
relations. part i: Formulation. Computer Methods in Applied Mechanics and Engineering 1988; 66:199}219.
30. Simo JC. Framework for "nite strain elastoplasticity based on the multiplicative decomposition and hyperelastic
relations. part ii: Computational aspects. Computer Methods in Applied Mechanics and Engineering 1988; 66:1}31.
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plasticity. Computer Methods in Applied Mechanics and Engineering 1985; 51:177}208.

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INTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN ENGINEERING

Int. J. Numer. Meth. Engng. 47, 341}358 (2000)

On modelling thermal oxidation of Silicon I: theory

CCC 0029-5981/2000/020341}18$17.50 Received 1 April 1999

P) o dv!P) b dv! P ) c ' n ds"P) A Lt #$ ' ov!b!$ ' cB dv

3.1. Application to oxidant diwusion

!3)1 , ∀i"1, 2, . . . , (2)

P) $ ' T d)#P! IT ' nJ d!#P! IoJ<n d!"0

As )1 P!, the volume integrals tend to zero. Equation (4) reduces to

P! IT ' nJ d!#P! IoJ<n d!"0 (5)

3.2. Reaction kinetics

Si#O H SiO (6)

Rate of forward reaction"k [Si][O ]

k "k [Si]/k (7)

[SiO ]"k [O ] (8)

P! IT09 ' nJ d!#P! Io09 J<n d!"0 (9)

< "!IT ' nJ/Io J (10)

The jump in the silicon dioxide density is given by

o"g` x3L)` (13)

4.1. Local momentum balance law

o V0 "DIV [P]#o B (20)

4.2. Constitutive equations

e"eN (X; F, Q) (21)

P"LeN /LF (24)

The internal dissipation is thus given by

e"eN (X; C, Q) (26)

where C is the right Cauchy}Green tensor and is given by

S"LeN /LE (28)

where E is the Lagrangian strain tensor given by

E"1 (C!1) (29)

P : F0 "S : E0 "s : d (30)

DEV [ ) ]"( ) )!1 [C : ( ) )]C~1 (42)

where dev [ ) ] is the deviator in the spatial con"guration given by

dev [ ) ]"( ) )!1 [1 : ( ) )]1 (46)

q PRN Q P0 implying very slow processes are elastic

Figure 3. Generalized Maxwell model for solids

Of utmost importance in dissipative systems is the characterization of the equilibrium response.

N Q"c DEV [L(1~/LE1 ] (52)

In addition, the driving thermodynamic forces must be zero:

This fully de"nes ( as

4.3. Expansion formulation

Figure 4. Illustration of the multiplicative split

((b1 )"1 (i log [ JM ])2#1 k[ JM ~2@3b1 : 1!1] (67)

1 (i log [ JM ])2"1 (i log [ J]!log [a3])2 (68)

1 k [ JM ~2@3b1 : 1!1]"1 k[( J/a3)~2@3a~2b : 1!1]

Box 1. Summary of the IBVP for thermal oxidation

Find Mu, P, oN: )][0, ¹ ] > R3]GL(3)]R` such that

principles of continuum mechanics. The di!usion}reaction equation is the generalisation of the

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