Surface Science 576 (2005) L65L70

www.elsevier.com/locate/susc

Surface Science Letters

Reaction mechanisms of oxygen at SiO2/Si(1 0 0) interface

Toru Akiyama
a

a,b,*

, Hiroyuki Kageshima

NTT Basic Research Laboratories, NTT Corporation, 3-1 Morinosato-Wakamiya, Atsugi, Kanagawa 243-0198, Japan
b
Department of Physics Engineering, Mie University, 1515 Kamihama, Tsu, Mie 514-8507, Japan
Received 17 August 2004; accepted for publication 4 January 2005
Available online 11 January 2005

Abstract
First-principles total-energy calculations are performed to clarify the reaction mechanisms of O atoms and O2 molecules at SiO2/Si(1 0 0) interface. The calculated energies reveal that the incorporation of O2 molecules into the substrate
dominates the interfacial reaction of the oxidant. The low energy barrier for O2 incorporation (0.2 eV) corresponds to
the hybridization of oxygen-2p orbitals of O2 and the valence band states of the Si substrate, while that for O atom
incorporation corresponds to the OO bond dissociation and the formation of SiOSi bonds. The cooperative reaction
of each O atom in the O2 molecule with each Si atom at the interface leads to the low energy barrier.

2005 Elsevier B.V. All rights reserved.
Keywords: Density functional calculations; Oxidation; Silicon; Silicon oxides; Semiconductorinsulator interfaces

Silicon oxidation has received much attention

in these decades as fundamental phenomena in
materials. In addition, it is of great interest and
importance as a key process in the fabrication of
Si-based devices [1]. Due to recent demands for
further miniaturization of devices, the precise
control of SiO2 lm growth by Si oxidation is
required [2]. Although many studies on the
mechanisms of Si oxidation have been carried

Corresponding author. Address: Department of Physics

Engineering, Mie University, 1515 Kamihama, Tsu, Mie 5148507, Japan. Tel.: +81 59 232 1211x3978; fax: +81 59 231 9726.
E-mail address: akiyama@phen.mie-u.ac.jp (T. Akiyama).

out [316], its understanding on atomic scale still

remains controversial.
In ordinary dry oxidation (i.e., the oxidant is
gas-phase O2), it is widely believed that Si oxidation consists of a diusion process of oxidant in
SiO2 and its reaction process at the SiO2/Si interface: The diusion and the interfacial reaction
dominate the growth of thick and thin oxides,
respectively [4]. For both processes a number of
experimental studies have been intensively carried
out [310], while theoretical investigations on the
oxide formation have focused on diusion mechanisms in SiO2 [12] and oxygen absorption mechanisms on Si clean surfaces which can be regarded
as an initial stage of oxidation [13,14]. The physics

0039-6028/$ - see front matter
2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.susc.2005.01.001

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T. Akiyama, H. Kageshima / Surface Science 576 (2005) L65L70

ODB
OSi

0.0

eV)

, dSi) (

We here consider the oxidation by gas-phase O2 (dry

oxidation). Since the dissociation energy of gas-phase O2 (the
experimental value is 5.11 eV) is large enough, it is highly likely
that O2 molecules are dominantly incorporated into the oxide.
However, the possibility that O2 molecules dissociate near the
interface and each of them reacts with the Si substrate cannot
be completely eliminated.
2
The energy of O atom without bonds with host atoms is
higher than that of the most stable structure with peroxy
linkage conguration by 2.48 eV. This assures that the initial
state structure for the interfacial reaction of O atoms is the
structure with peroxy linkage.

OPL

y E(d

(a)

Energ

of the interfacial reaction such as reaction mechanisms of oxygen at the interface is still uncertain.
In this letter, we perform total-energy electronic
structure calculations to clarify the reaction mechanisms of oxygen at the SiO2/Si(1 0 0) interface
[17,18]. We here take account both of oxygen
atoms and molecules as reaction species. 1 From
calculated energies, we determine the form of oxygen dominating the interfacial reaction, and interpret the experimental data available.
First, we investigate the reaction mechanisms of
O atoms. From an extensive search for stable
geometries, we nd that a peroxy linkage conguration in the form of an SiOOSi bond is the
most stable atomic conguration in the SiO2 region. The energies with this conguration are
1.442.48 eV lower than those of the other congurations. 2 The exploration of the transition state
structures reveals that O atoms diuse by jumping
the positions of the peroxy linkage with an energy
barrier of
1.0 eV. This jumping process consists
of switching [12] and twisting of the SiOOSi
bond, indicating that O atoms near the interface
diuse by the exchange of moving atoms with host
O atoms.
Fig. 1(a) shows the energy surface for O atom
incorporation, starting from the initial OPL structure with the peroxy linkage [Fig. 1(b)]. The energy
variation for O atom incorporation is a complex
hypersurface in a multidimensional space [19,20].
In order to determine the reaction pathway in a
multidimensional space, we obtain the optimized
energies E(dO, dSi) by performing calculations in
which all the atoms except for the incorporated
O atom (O(I)) and the interfacial Si atom (Si(I))
are fully relaxed. Here, dO and dSi are the position

(b)

1.00
0.75
0.25
0.50
0.25
0.50
0.0
0.75 -0.25

OPL

O(II)

(c)

ODB

(d)

OSi

O(I)
Si (I)

Fig. 1. (a) Energy surface for O atom incorporation as a

function of dSi and dO, and geometries of (b) the initial state
OPL structure, (c) the transition state ODB structure, and (d) the
nal OSi structure. The dSi and dO denote the distances from
the initial position of the incorporated O atom (O(I)) and of
the interfacial Si atom (Si(I)), to their nal positions along the
vectors ~
RO and ~
RSi , respectively. Here, ~
RO and ~
RSi are
determined from the initial and nal position of O(I) and Si(I),
respectively. The ODB structure corresponds to (dO,
dSi) = (0.25, 0.49). For each grid-point of (dO, dSi), we obtain
E(dO, dSi) with the constraint that all the atoms except for O(I)
and Si(I) are fully relaxed. The dashed line on the energy surface
denotes the adiabatic path. The initial positions of Si(I) and O(I)
are also shown by dashed circles in (c) and (d). The O atom
bonded with O(I) in the OPL structure is labeled as O(II). The
host Si and O atoms are represented by white and gray circles,
respectively. Small white circles represent terminating H atoms.

of the incorporated O atom and that of the interfacial Si atom, respectively. In the energetically
lowest adiabatic path shown by the dashed line
in Fig. 1(a), Si(I) rst moves towards the SiO2 region. Through the transition state ODB structure
[Fig. 1(c)], O(I) intervenes in the nearby interfacial
SiSi bond, resulting in the formation of a new Si

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2.0

(b)
0.0

(a)
-2.0

Energy (eV)

OSi bond: The ODB structure becomes the nal

OSi structure [Fig. 1(d)] by this O atom insertion.
From the energies of the adiabatic path, we nd
that the energy barrier of the O atom incorporation is 0.9 eV.
Analyses of wave functions clarify that the energy barrier corresponds to the dissociation of
the OO bond and the formation of the SiOSi
bonds. The r-bonding orbital (with the 2pr character) between O(I) and another O atom [O(II) in
Fig. 1(b)] in the OPL structure is broken, and the
corresponding orbitals hybridize with the valence
band states of the Si substrate in the ODB structure. They nally result in the r-bonding states
(hybridization of O-2p orbitals and Si-sp3 states)
of SiO2 which constitute the covalent character
of SiOSi bonds. Simultaneously, the 2sr and
2sr* orbitals between O(I) and O(II) become two
distinct 2s-like states in the ODB structure, showing
that the dissociation of the OO bond occurs at
the ODB structure.
Next, we investigate the mechanisms of O2
incorporation into the substrate taking into account the spin degree of freedom. In the SiO2 region, the O2 molecule in a spin-triplet state is
stable at the opening space of SiO2 with the OO
bond almost parallel to the c axis. The length of
and the incorporation enthe OO bond is 1.29 A
ergy of gas-phase O2 is 2.15 eV, comparable to
those of the O2 in bulk SiO2 [12]. Therefore, it is
expected that the microscopic mechanisms of the
diusion of the O2 molecule from the bulk region
to this structure are similar to that of O2 in bulk
SiO2.
Fig. 2 shows the energy variation for the O2
incorporation into the Si substrate, starting from
the stable structure of O2 in the SiO2 region [Fig.
3(a)]. Through the transition state structure [Fig.
3(b)], the O2 moves to the substrate with the
rotation of the OO bond. This results in the formation of the metastable structure with a peroxylinkage-like SiOOSi conguration [Fig. 3(c)].
In the metastable structure, each of the interfacial
Si atoms simultaneously forms an SiO bond with
each of the O2 molecule: Si(I) and Si(II) are bonded
with O(I) and O(II), respectively. The calculated energy barrier of 0.2 eV for O2 incorporation corresponds to the transition between the initial and

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(c)

(d)

-4.0

(e)

-6.0
-8.0

(f)

-10.0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Reaction coordinate (A.)

Fig. 2. Energy variation for incorporation of the O2 molecule.
Each plot is obtained from the geometry optimization where all
atoms except for O atoms of the O2 are fully relaxed: The O
atoms of the O2 are relaxed so that the center of O2 is xed at
the articially controlled position along the reaction coordinate
[14,19]. The reaction coordinate is dened as the vector
determined from the initial and nal positions of the center of
the O2, where the nal structure is determined by the extensive
search for stable structures of the O2 in the substrate. The zero
of the energy is set to the energy of the O2 molecule in the SiO2
region. Geometries represented by open symbols are shown in
Fig. 3.

the metastable structures. The cooperative reaction of each O atom with each of the interfacial
Si atoms results in the appearance of the SiO
OSi conguration.
From the metastable structure, O(II) intervenes
in the nearby interfacial SiSi bond. Through another transition structure (not shown here) whose
energy is only 0.05 eV higher than that of the
metastable structure, a new SiOSi bond is
formed [Fig. 3(d)]. The dissociation of the O2 molecule occurs between this structure and the geometry shown in Fig. 3(e). After the dissociation, O(I)
intervenes in the nearby interfacial SiSi bond, and
another SiOSi bond is formed. This O insertion
results in the formation of the nal structure [Fig.
3(f)], which is similar to the structure with two O
atoms incorporated [15].
The distribution of valence electrons in the transition state structure [Fig. 4(a)] claries that the
atomic process corresponding to the energy barrier
is the bond formation between O(I) and Si(I). From
analyses of wave functions, we nd that the
hybridization between the O-2p orbitals and the

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T. Akiyama, H. Kageshima / Surface Science 576 (2005) L65L70

(a)

(b)
O(I)

Si (I)

(d)

(c)
O (II) O(I)

Si (I)

Si(II)

(f)

(e)

Fig. 3. Geometries of O2 molecule near the interface. O atoms

of O2 are labeled as O(I) and O(II), and Si atoms forming weak
SiO bonds are indicated by Si(I) and Si(II). The host Si and O
atoms are represented by white and gray circles, respectively.

(a)

(b)

1.0E-2

(c)

5.0E-4

O (II)
2.0E-3

O
O

O
(I)

O
Si

-2.0E-3

Si

Fig. 4. Contour plots of: (a) valence electron density; (b) the
squared wave function of one of the O-2pr-like hybridized
states on a plane including Si(I) and O(I), in the transition state
structure shown in Fig. 3(b); (c) the dierence between the
squared wave function of the O-2pr-like hybridized state in the
transition state structure and that of the 2pr orbital for gasphase O2, on a plane including O(I) and O(II), are also shown.
The dierence is obtained by subtracting the wave function of
the 2pr orbital from the wave function of the hybridized state.
The values shown in gures are the contour spacing in units of
e/(a.u.)3.

valence band states of Si substrate constitutes this

bond. Fig. 4(b) shows the distribution of the wave

function corresponding to one of the hybridized

states. This state possesses a 2pr-like character.
However, the wave function has amplitudes
around Si(I). The simple dierence between this
state and the 2pr orbitals of O2 [Fig. 4(c)] clearly
shows that the wave function is delocalized around
the OO bond. Therefore, this state also possesses
the SiO covalent character, indicating that the
transition state structure corresponds to the intersection between the energy surface of the O2 molecule in the SiO2 region and that of the SiOOSi
conguration at the interface.
The reaction mechanisms of the O2 molecule revealed for the rst time in the present calculations
are quite dierent from those of the O atom. It involves the formation of the SiOOSi conguration, in addition to the dissociation of the OO
bond and the formation of SOSi bonds. The energy barrier of O2 incorporation is determined by
the formation of the SiOOSi conguration.
On the other hand, the energy barrier for the O
atom is dominated by the dissociation of r-bonds
of the peroxy linkage and the formation of an Si
OSi bond. It should also be noted that the
appearance of SiOOSi is the consequence of
cooperative reaction of each O atom of the O2 with
each of the interfacial Si atoms. The dierence between the energy barrier of the O atom and that of
the O2 molecule is due to the dierence of the
microscopic process that determines the energy
barrier.
The calculated energies at the interface and the
barriers for incorporation clearly show that O2
molecules are the dominant reaction species during
Si thermal oxidation, consistent with experimental
data obtained from secondary ion mass spectrometry and medium energy ion scattering 3 [8,9]. The
energy of the initial structure shown in Fig. 3(a) is
lower than that of the OPL structure with an energy gain of 1.0 eV per O2 molecule. Assuming
that the concentration of oxygen in the oxide region is described by the Boltzmann distribution,
this energy dierence leads to the solubility of O2
molecules being at least 105 times that of O atoms

These experimental results imply that molecular-type

oxygen diuses toward the interface during oxidation.

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at 1000 C: The O2 molecules diusing in the oxide

react directly with the substrate without dissociation. In addition, the energy barrier for O2
(0.2 eV) is lower than that for O atoms (0.9 eV).
Thus, the energy barrier for O atom incorporation
by way of the dissociation of O2 molecule in the
SiO2 region of the interface (at least 1.9 eV) is larger than that for direct O2 incorporation. This assures that O2 molecules are the dominant reaction
species even if the dynamics of reaction species is
taken into account. Furthermore, the eect of tripletsinglet conversion for O2 molecules unchanges
the reaction species. We also estimate the probability of tripletsinglet conversion exchange P from
the energy slopes shown in Fig. 2 based on the
LandauZener theory [21]. Around 8001200 C,
the probability P is found to be
0.003. The tripletsinglet conversion narrows the channel of O2
incorporation [14], and results in the reduction of
the interfacial reaction rate. However, the oxide
growth rate by O2 incorporation approximately
expressed by the product of the solubility of O2
in SiO2 and the interfacial reaction rate [4] is still
higher than that of O atoms.
Finally, we comment on the experimentally reported activation energies. The calculated energy
barrier for the O2 molecule (0.2 eV) seems to agree
well with the activation energy of 0.3 eV for ultrathin oxide obtained from scanning reection electron microscopy combined with Auger electron
spectroscopy [6]. However, it is lower than the
activation energies for ultrathin oxide obtained
from reection dierence spectroscopy (1.2 eV)
[7] and for oxide layers with a thickness of 10
100 nm (1.762.00 eV) [4,5]. This implies that the
interfacial reaction process involves other mechanisms or eects in addition to the oxygen insertion
into the SiSi bonds at abrupt, at, and relaxed
interfaces claried in the present study. The eects
of interfacial roughness, accumulation of interfacial strain and its release mechanisms, or eects
of polymorphism of amorphous SiO2 could be crucial to the interfacial reaction. It is therefore of
importance to elucidate these mechanisms or effects in order to completely reveal the mechanisms
of Si thermal oxidation, but this is beyond the
scope of the present work. One of the essential
mechanisms of the interfacial reaction, which does

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not correspond to the previously consented severance of the interfacial SiSi bonds but to the formation of weak SiO bonds, is revealed in the
present study.
In summary, we have presented rst-principles
calculations that clarify the reaction mechanisms
of oxygen at the SiO2/Si interface. We have found
that O2 molecules around the interface are dominantly incorporated into the Si substrate. We have
also found that the corporative reaction with the
interfacial Si atoms enables O2 molecules dissociate with low energy barrier. The hybridization of
the O-2p orbitals of the oxidant and the valence
band states of the Si substrate is the principal factor of the reaction.
Note added. Very recently, a dynamical study
for reaction of O2 molecules at SiO2/Si interface
was carried out by the rst-principles molecular
dynamics [22].

Acknowledgement
We would like to thank Dr. M. Otani, Dr. M.
Uematsu, Prof. K. Shiraishi, and Prof. Y. Takahashi for their discussions and comments. Calculation codes used in this work are based on Tokyo
Ab-initio Program Package (TAPP) which has
been developed by us. Computations were partly
done at RCCS (National Institutes of Natural Sciences) and at ISSP (University of Tokyo).

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