456

7.1

NATIVE FILMS

oxygen ions to form pairs of stable nonbridging hydroxyl groups. The reaction
is described schematically by
-

The presence of these hydroxyl groups also tends to weaken the silica network and render it more porous to diffusing species. Thus their behavior is
similar to that of interstitial impurities.
Figure 7.2 shows a schematic representation of fused silica glass together
with the various types of defect structures that may be present in it [5].

THERMAL OXIDATION OF SILICON

457

process for layers greater than 40 A thickness for dry oxidation, and 1000 A
for wet oxidation.
The chemistry of oxidation with d w oxygen is relatively straightforward. It
is assumed that the species diffusing through the growing layer is molecular
oxygen. The chemical reaction at the silicon surface is

Here one molecule of oxygen results in the formation of one molecule of SiOZ.
The overall process of oxidation of silicon with water vapor may also be
considered as one in which the oxidizing species diffuses through the oxide
and reacts with the silicon surface, so that

7.1.3 Oxide Formation

Oxidation of the silicon slice is conveniently carried out by subjecting it to
dry oxygen or water vapor, while it is maintained at an elevated temperature.
In water vapor, or wet oxidation schemes, an inert gas (or oxygen) is bubbled
through water which is usually held at 95C to avoid its excessive depletion.
Direct
-oxidation of the silicon surface results in forming an oxide layer which
ickness of the consumed silicon. The silica
is ap
-layer so formed contains about-2T2 x lon molecuTes ~ m - ~ z - S i O ~ .
The process of oxide formation require that the oxidizing species move
through the growing oxide layer in order to reach the silicon surface. Thus,
growth proceeds at an ever-decreasing rate as the thickness of the intervening
oxide layer increases. This diffusion-controlled regime dominates the growth
-

Here, however, two molecules of water vapor are used to form one molecule
of S O 2 . The hydrogen evolved by this reaction diffuses rapidly through the
growing oxide and leaves the system at the gas-oxide interface. The detailed
nature of this reaction, although somewhat more complex [6], is assumed to
proceed in the following manner:
1. Water vapor reacts with the bridging oxygen ions in the silica structure to
form nonbridging hydroxyl groups. This reaction, which results in weakening
the silicastructure, may be written as

2. At the oxide-silicon interface, the hydroxyl groups react with the silicon
lattice to form silica polyhedra and hydrogen. The reaction is

Bridging oxygen
Nonbridging oxygen
Silicon

3. Hydrogen is a rapid diffuser in S O 2 , and leaves after being formed by

this process. Some of this diffusing hydrogen reacts with bridging oxygen ions
in the silica structure to form hydroxyl groups, as'shown by

Network modifier
Hydroxyl group
Network former

%
Fig. 7.2 Structure of silica glass. Adapted from Revesz [7].

the silica struct_ure.

-thus further weakening
--

A somewhat more detailed picture of the role of hydrogen in silica is given

elsewhere [7]. However, the relatively simple model, outlined above, is suitable
for describing the basic mechanism of formation of these films.

7.1 THERMAL OXIDATION OF SILICON

458

NATIVE FILMS

7.1.4

Kinetics of Oxide Growth

The kinetics of oxide growth on silicon may be determined [8] with reference
to the model of Fig. 7.3. Assume that a silicon slice is brought in contact with
the oxidant, with concentration N , in the gas phase, resulting in a surface concentration of N o molecules cmp3 for this species. In typical oxidation systems,
the mass transfer coefficient is extremely high, so that the magnitude of N o is
essentially the solid solubility of the species at the oxidation temperature. At
1000C the solid solubility of these species is 5.2 x 1016 molecules ~ r n -for~
dry oxygen and 3x l0l9 molecules cmp3 for water vapor at a pressure of 1 atm.
The oxidizing species is assumed to diffuse in molecular form through the
silicon dioxide layer, resulting in a concentration N 1 at the surface of the silicon.
Transport of the species may occur by both drift and diffusion. Writing D as
the diffusivity and ignoring the effects of drift, the flux density of oxidizing
species arriving at the gas-oxide interface is given by j , where

j = kN1

459

(7.10)

where k is the interfacial reaction rate constant. These fluxes must be equal
under steady-state diffusion conditions. Combining Eqs. (7. 9) and (7. 10) gives

The reaction of the oxidizing species with the silicon results in the formation
of Si02. Writing n as the number of molecules * of the oxidizing impurity that
are incorporated into unit volume of the oxide, the rate of change of the oxide
layer thickness is given by

Solving this equation, subject to the boundary value that x = 0 at t = 0, gives

and x is the thickness of the oxide at a given point in time. This is sometimes
referred to as Henry's law.
On arrival at the silicon surface the species enters into chemical reaction
with it. If it is assumed that this reaction proceeds at a rate proportional to the
concentration of the oxidizing species, then

so that

Equation (7.14) reduces to

for small values of t , and to

for large values. Thus in the initial stages of growth, in which the reaction
Fig. 7.3 Model for oxidation kinetics.

*n = 2.2 x

~ r n -for~ dry oxidation, and 4.4 x

cmp3 for wet oxidation.

460

NATIVE FILMS

7.1 THERMAL OXIDATION OF SILICON

is kinetically controlled, the oxide thickness varies linearly with time. In later
stages the reaction is diffusion-limited and the oxide thickness is directly proportional to the square root of time.
Equation (7.13) is often written in the more compact form

Using this form, Eqs. (7.15) and (7.16) can be written as

for small values of t , and

for large values. For this reason, the term B/A is referred to as the linear rate
constant whereas the parabolic rate constant is given by B. Measured values
for these rate constants as a function of temperature are given [9] in Figs. 7.4
= 640 torr). The data of Fig.
and 7.5 for both dry and wet oxidation (pHZO
7.4 are shown for both (111) and (100) silicon. This orientation-dependence
effect will be considered in Section 7.1.4.2. Mathematical relations, describing
the behavior of these rate constants, are given in Table 7. 1 at the end of this
chapter.
Insight into the physical processes involved during the thermal oxidation
of silicon can be gleaned by study of these figures. Thus, Fig. 7.4 shows that
the logarithm of the linear rate constant falls inversely with T at a slope of
2 eV/molecule for dry oxygen, and 2.05 eV/molecule for wet oxidation. This
is in close agreement with the energy required to break Si-Si bonds, which is
1.83 eV/molecule. The logarithm of the parabolic rate constant (Fig. 7.5) also
falls inversely with T, but at a slope of 1.23 eV/molecule for dry oxidation.
The comparable activation energy for diffusion of oxygen in fused silica is
about 1.18 eV/molecule, as shown in Fig. 7.1. The corresponding value for wet
oxidation is 0.78 eV/molecule, which compares favorably with the activation
energy of diffusion of H 2 0 in fused silica (0.79 eV/molecule).
To an approximation, the linear rate constant varies directly with the concentration of oxidizing species at the surface, and thus with its partial pressure.
This has been experimentally verified for both wet and dry oxidation conditions.
Finally, the parabolic rate constant for wet oxidation is found to be much larger
than that for dry oxidation. This is primarily due to the significantly greater solid
solubility of water over oxygen in silica glass (about 3 decades larger), which
more than compensates for the slightly lower diffusivity as seen in Fig. 7.1.

Temperature 10001T (K-' )

Fig. 7.4 Linear rate constant versus temperature. From Deal [S]. Reprinted with permission of the publisher, The Electrochemical Society, Inc.

Temperature 1000IT (K-' )

Fig. 7.5 Parabolic rate constant versus temperature. From Deal [S]. Reprinted with
permission of the publisher, The Electrochemical Society, Inc.

!,

'

462

7.1.4.1

7.1

NATIVE FILMS

Initial Growth Phase

The theory for the kinetics of oxide formation has been found to apply very well
to growth in wet oxygen and steam. There is consistent evidence, however,
to indicate the presence of an extremely rapid initial growth phase with dry
oxygen, generally existing for the first 250 A of growth. Considerable effort
has been made to explain this rapid growth behavior, since oxides of this type
and thickness are critically important for use as gate insulators in MOS devices.
A number of theories have been proposed and are briefly summarized here.
One set of theories postulates the movement of charge species through the
oxide. For example, it has been proposed [lo] that the molecular oxygen, on
entering the oxide, dissociates to form a negative-charged 0; or 0,"-,and one
o r two holes respectively. The
- holes have considerably higher mobility than the
oxygen ion, and run ahead of it; the result is the formation of a space-charge
.region. The resulting field enhances the diffusion of t h e oxygen in the layer,
by providing an additional drift component. This enhancement occurs until the
oxide thickness exceeds the thickness of the space charge region. This region
of high space-charge density is near the gas-oxide interface, with the rest of
tlie oxide layer being almost space-charge neutral. Its thickness region is thus
on the order of the extrinsic Debye length, and is given by

where E is the relative permittivity of the oxide ( ~ 3 . 9 ) This

.
Debye length is
about 150 A in dry oxygen, but only 5 A for water vapor." In practice, an
accelerated oxidation rate is seen for a depth of about 230 f 30 A in dry oxygen
processing, but is unnoticed for wet oxygen or steam processing.
Equation (7.17) can be rewritten as

THERMAL OXIDATION OF SILICON

463

defect density is some four orders of magnitude larger than that obtained with
~ ,
Yet another
dry oxygen (lo2' cm-3 as compared to 1016 ~ m - respectively).
argument is that the basic assumption of Henry's law, as given by Eq. (7.9),
only holds for infinitely thick layers, and that the solubility of oxygen in Si02
is greatly increased when the oxide thickness is less than the mean spacing
between solute molecules.
A third set of theories postulate a two-stream oxidation process, with
enhanced growth resulting from the presence of a thin region of material in
which excess sites for oxidation are present [12]. Using this model, the experimental data were fitted to the theory by modifying Eq. (7.12) to the form

where L is a characteristic length, of value 70 f 10 A, for growth in the

800-1000C range. The pre-exponential term C has an Arrhenious type of temperature dependence, with an activation energy of 2.37 and 2.32 eV/molecule
for growth on lightly doped (100) and (111) silicon respectively.
Dissolved oxygen, due to indiffusion in the very early phase of growth, is
yet another possible candidate for the formation of a thin region of rapid oxide
~ A2/s at 1000C, so
growth [13]. The diffusivity of oxygen in silicon is 2 . 8 lo5
that indiffusion to a 50-A depth can occur within the first 10 ms of exposure of
bare silicon to oxygen. However, its extent falls off with oxide growth because
of a rapid reduction in this surface concentration as oxidation proceeds.
7.1.4.2

Doping Dependence Effects

in order to include this rapid oxidation phase. Here, T is a time displacement

which can be used to adjust the initial oxide layer (at t = 0).
A second set of theories, based on the structure of the oxide during the initial growth phase, have also been proposed [ll]. Transmission electron microscope studies of silica structure have shown the presence of pores, about 10
A in diameter, in very thin oxides grown in dry oxygen. These allow the oxidant to remain in direct contact with the silicon in the early phases of growth.
Such pores have not been observed in wet oxides, presumably because their

Heavily doped silicon oxidizes at a faster rate than lightly doped material. However, detailed studies of boron- and phosphorus-doped material have shown considerable differences in oxide growth behavior. Thus, during oxidation, boron
is preferentially incorporated into the silicon dioxide because of its relatively
small segregation coefficient* (= 0.15 to 0.3). This results in a weakening of
the bond structure of the silica film, and an increase in the diffusivity of the
oxidizing species through it. Consequently, there is an increase in the parabolic
rate constant with boron doping concentration, but little change in the linear
rate constant [14].
Phosphorus, on the other hand, has a large segregation coefficient (=lo), is
only slightly incorporated into the growing oxide, and piles up at the Si-Si02
interface. This causes an increase in the reaction rate, with a corresponding
increase in the linear rate constant. On the other hand, the lack of phosphorus

*This is because the solid solubility of water in silica is three orders of magnitude larger than that
of oxygen.

*Defined as the ratio of the equilibrium concentration of the impurity in silicon to its equilibrium
concentration in the oxide. See Section 4.8.1.