Model for defect generation at the (1 0 0)Si/SiO

2
interface
during electron injection in MOS structures
M. Houssa
a,*
, J.L. Autran
a
, M.M. Heyns
b
, A. Stesmans
c
a
Laboratoire Materiaux et Microelectronique de Provence, Universite de Provence,
UMR CNRS 6137, 49 rue Joliot-Curie, 13384 Marseille Cedex 13, France
b
IMEC, 75 Kapeldreef, B-3001 Leuven, Belgium
c
Department of Physics, University of Leuven, Celestijnenlaan 200 D, B-3001 Leuven, Belgium
Abstract
The generation of interface defects during the injection of electrons in metal-oxidesemiconductor (MOS) structures with thin
SiO
2
gate layers and SiO
2
/ZrO
2
gate stacks is investigated. A model is proposed to explain the kinetics of interface defect
generation, based on the depassivation of trivalent silicon dangling bonds (Si
3
BSiH !Si
3
BSi

) at the (1 0 0)Si/SiO
2
interface by
the injected electrons. A gaussian spread for the activation energy E
d
related to the dissociation of the SiH bond is included in
this model. Comparison with experimental results reveals that the mean value of the activation energy E
di
decreases linearly with
the electric eld E
ox
across the SiO
2
layer. This behaviour is attributed to the alignment of the SiH dipole moment with respect
to E
ox
, which favours the dissociation of the SiH bond.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Metal-oxidesemiconductor (MOS) structures; Defect generation; Interface dipole moment
1. Introduction
The generation of defects at the (1 0 0)Si/SiO
2
interface is one of the major reliability issues in
metal-oxidesemiconductor (MOS) devices. It is
indeed well known that the generation of defects at
this interface is responsible for the degradation of the
electrical properties of these devices, like the decrease
of the threshold voltage V
th
, the drain current I
D
, and
the transconductance g [14].
In this paper, we describe a model based on the
depassivation of Si
3
BSiH centers at the (1 0 0)Si/SiO
2
interface during electron injection through MOS
devices, resulting in the generation of Si
3
BSi

centers
(so called P
bo
centers). This model takes into account a
gaussian distribution of activation energies for the
generation of the P
bo
centers [5], as well as the eld
dependence of the mean activation energy E
di
. This
eld dependence of E
di
is related to the alignment of
the SiH dipole with respect to the applied electric
eld during the electrical stress.
This model allows to reproduce various experimen-
tal results in MOS devices with thin SiO
2
gate layers
and SiO
2
/ZrO
2
gate stacks, with realistic values for the
physical parameters pertaining to this model.
2. Results and discussion
When electrons are injected through MOS devices,
they can produce the depassivation of Si
3
BSiH centers
by breaking SiH bonds at the (1 0 0)Si/SiO
2
interface,
Applied Surface Science 212213 (2003) 749752
*
Corresponding author. Tel.: 33-4-96-13-97-18;
fax: 33-4-96-13-97-09.
E-mail address: houssa@up.univ-mrs.fr (M. Houssa).
0169-4332/03/$ see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00042-4
leading to the generation of electrically active P
bo
centers [2,3].
The kinetics of P
bo
center generation is calculated
using the following electro-chemical reaction:
Si
3
BSiH e

!Si
3
BSi

H e

; (1)
leading to the following rst-order differential equa-
tions:
dSi
3
BSi

dt
k
d
Si
3
BSiHe

;
de

dt

J
inj
q
; (2)
where J
inj
is the injected current density and k
d
the
dissociation rate constant, assumed to be given by the
Arrhenius equation:
k
d
k
0
exp
E
d
k
B
T
_ _
; (3)
where k
0
and E
d
are related to the attempt frequency
and the activation energy for the dissociation of the
Si
3
BSiH center, respectively.
It has been recently demonstrated through extensive
ESR work [5] that the activation energy E
d
is not a
single value, but that there exists a (gaussian) spread
characterized by the standard deviation s
E
d
. The phy-
sical origin of this spread most probably arises from
slight variation in the local strain at the Si/SiO
2
interface that leads to slight variation of P
bo
defects
morphology [5]. Taking into account this gaussian
spread of activation energies E
d
, the following equa-
tion is found for the kinetics of generation of interface
defects:
Si
3
BS
i

N
0
1
1

2p
p
s
E
d
_
1
0
exp
E
d
E
di

2
2s
2
E
d
_ _
exp
J
inj
2q
t
2
k
0
exp
E
d
k
B
T
_ _ _ _
dE
d
(4)
where N
0
is the initial density of Si
3
BSiH centers and
E
di
the mean activation energy.
The kinetics of P
bo
generation, calculated from
Eq. (4), is presented in Fig. 1 for different values of
s
E
d
. For s
E
d
6 0, i.e. when a gaussian spread of
activation energies is accounted for, the curvature of
the theoretical curve is changing. It will be shown
belowthat the distribution of activation energies has to
be included in order to reproduce the shape of experi-
mental curves. Besides, as s
E
d
is increased, P
bo
centers
are generated more rapidly, which arises from the
fast dissociation of the centers with low activation
energies.
The generation of interface defects in a MOS
transistor with a 7 nm SiO
2
gate layer during injection
of electrons from the poly-Si gate (using a constant
current density xed at 100 mA/cm
2
) is shown in
Fig. 2 [6]. From these data, it is clear that the dis-
tribution of activation energies has to be included in
the model in order to obtain the correct curvature. The
solid line in Fig. 2 is a t obtained from Eq. (4), xing
Fig. 1. Time-dependence of the normalized concentration of P
bo
centers calculated from Eq. (4), for different values of the spread
s
Ed
of activation energies.
Fig. 2. Interface state density N
it
as a function of the injected
charge Q
inj
in a MOS transistor with a 7 nm SiO
2
gate layer
(electron injection from the gate, using a constant gate current
density xed at 100 mA/cm
2
). The solid line is a t obtained from
Eq. (4).
750 M. Houssa et al. / Applied Surface Science 212213 (2003) 749752
the following values of the parameters: k
0
2:5
10
23
cm
2
/s, s
E
d
0:16 eV, E
di
2:8 eV and N
0

1:5 10
12
/cm
2
. It should be pointed out that these
parameters are very close to those derived from ESR
experiments performed after vacuum annealing of
Si/SiO
2
interfaces (s
E
d
0:1 eV, E
di
2:83 eV and
N
0
1:2 10
12
/cm
2
) [5]. The agreement between the
experimental data and numerical simulations is quite
good.
The generation of interface defects in a p-Si/SiO
2
/
ZrO
2
/TiN capacitor during constant gate voltage
stress V
s
(injection of electrons from the TiN gate)
is shown in Fig. 3 for different values of V
s
[7]. One
observes that the interface defect density increases
with |V
s
|, i.e. with the energy of the injected electrons
q|V
s
| (assuming that electrons travel ballistically
through the gate stack). Solid lines are ts to the data
using the P
bo
generation model. An excellent agree-
ment between the experimental results and theoretical
curves could again be obtained, with the following
values of the physical parameters (xed for the differ-
ent V
s
values): k
0
2:5 10
23
cm
2
/s, s
E
d
0:15 eV,
and N
0
3:15 10
12
/cm
2
. Besides, we had to assume
that themeanvalueof theactivationenergy, E
di
, depends
on the stress voltage V
s
.
The values of E
di
derived from the ts shown in
Fig. 3 are presented in Fig. 4 as a function of the
electric eld across the interfacial SiO
2
layer, and
corresponding to different values of V
s
. It is found
that E
di
decreases linearly with E
ox
.
This linear decrease of E
di
with E
ox
can be
explained as follows. Due to the different electrone-
gativity between Si (1.8) and H (2.1), the SiH bond
presents a permanent dipole moment oriented towards
the Si atom. When a negative bias is applied to the
gate, an electric eld is developed across the SiO
2
layer, and the dipole moment of the SiHbond tends to
align parallel with the electric eld, i.e. the SiH bond
tends to ip towards the Si substrate (see Fig. 5). Since
the SiH dissociation pathway is believed to occur via
the ipping of H towards a SiSi bond next to the
dangling bond [8,9], the alignment of the SiH dipole
with respect to the electric eld may favour the
dissociation of the H atom, and leads to the reduction
of the mean activation energy, given by:
E
di
E
di
0 p cosyE
loc
; (5)
where p is the SiH permanent dipole moment, y the
angle between the SiH bond and the electric eld
Fig. 3. Variation in the density of interface defects N
it
during
constant gate voltage stress V
s
of p-Si/SiO
2
/ZrO
2
/TiN capacitors,
for different values of V
s
. Solid lines are ts to the data using
Eq. (4).
Fig. 4. Mean activation energy E
di
for SiH bond dissociation as a
function of the electric eld across the interfacial SiO
2
layer, E
ox
.
The solid line is a linear t using Eqs. (5) and (6).
Fig. 5. Schematic illustration of a Si
3
BSiH center at the (1 0 0)Si/
SiO
2
interface in presence of an electric eld E
loc
applied parallel
to the interface: (*) silicon; (*) hydrogen.
M. Houssa et al. / Applied Surface Science 212213 (2003) 749752 751
(y 45

for the electric eld applied normal to the

(1 0 0)Si surface) and E
loc
the local electric eld,
which is related to the eld across the oxide by the
Lorentz expression [10]:
E
loc
1
w
3
_ _
E
ox
; (6)
where w is the electric susceptibility of the gate oxide
(w 2:9 for SiO
2
).
The solid line in Fig. 4 is a t to the data using
Eqs. (5) and (6). From this linear t, E
di
(0) is found to
be equal to 2.98 eV, i.e. almost the SiHbinding energy
(3 eV) [11], and the dipole moment of the SiHbond at
the interface is found to be 1:3 10
29
C m. This
dipole moment is the product of the SiH bond length
d
SiH
and the effective charge of the dipole d
q
, where q
is the electron charge, i.e.
p d
SiH
d
q
: (7)
Fixing the SiH bond length at 1.48 A

[8], one then

nds d % 0:5. This value is about two times larger than
the value calculated by Biswas and Li in bulk hydro-
genated amorphous silicon, i.e. d % 0:20.3 [12]. It
should be pointed out that the SiO
2
layer is in fact
a nitride oxide, with about 10 at.% nitrogen at the
interface. This probably results in a larger electric
susceptibility of the material at the interface (the
electric susceptibility of Si
3
N
4
is about 4) that would
lead to a smaller derived value of d when combining
Eqs. (5)(7).
3. Conclusions
In conclusion, we have investigated the genera-
tion of defects at the (1 0 0)Si/SiO
2
interface during
electron injection in MOS devices. An electro-chemi-
cal model for the generation of P
bo
centers during the
electrical stress has been developed, including a gaus-
sian spread of activation energies of these defects. A
good agreement between various experimental results
and numerical simulations has been obtained, with
realistic values of the physical parameters. In order to
reproduce experimental data obtained at different
stress voltages, the electric eld dependence of the
mean activation energy E
di
had to be included in the
model. The physical origin of the eld dependence of
E
di
can be related to the alignment of the SiH dipole
with respect to the electric eld, leading to the ipping
of the SiH bond which favours its dissociation and
hence the generation of the P
bo
centers.
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752 M. Houssa et al. / Applied Surface Science 212213 (2003) 749752