Applied Surface Science 190 (2002) 166170

The influence of graded interfaces in the electronic

spectrum of nanometer silicon dots
J.S. de Sousaa, E.W.S. Caetanoa, J.R. Goncalvesa, G.A. Fariasa,
V.N. Freirea, E.F. da Silva Jr.b,*
a
Departamento de Fsica, Universidade Federal do Ceara, Caixa Postal 6030, Campus do Pici, 60455-760 Fortaleza, Ceara, Brazil
b
Departamento de Fsica, Universidade Federal de Pernambuco, Cidade Universitaria, 50670-901 Recife, Pernambuco, Brazil

Abstract

The effects imposed to the electron energy levels of Si/SiO2 quantum dots by the presence of smooth graded interfaces and
interfacial carriers trap is studied. For small diameter quantum dots, while the existence of graded interfaces strongly blue shifts
the carrier energy states (up to a few hundred meV), the effect of the interfacial carriers trap is to red shift the energies, but to a
lesser extend (under 50 meV). In addition, slight changes in the distance of the carriers trap in relation to the center of the dot
does not alter significantly the energy spectrum. # 2002 Elsevier Science B.V. All rights reserved.

PACS: 73.20.Dx; 73.20.At; 68.65.g; 73.20.Fz

Keywords: Si/SiO2 quantum dot; Graded interfaces; Electronic spectrum

1. Introduction matter of fact, Takahashi et al. [8] reported the exis-

The early proposal [1] and subsequent demonstra-
tions [26] of light emission from low-dimensional Si/
SiO2 systems, together with a very recent quantitative
estimate of efficient light amplification in silicon
nanocrystals [7] is driving considerable efforts toward
the understanding of the mechanisms involved. Quan-
tum confinement and interface states are the most
important candidates to explain luminescence of
low-dimensional silicon-based systems, but the con-
troversy is still unsolved. In both cases, determination
of the role of a graded Si/SiO2 interface is of funda-
mental importance since experimental data point to
the existence of graded interfaces 310 A wide. As a
*
Corresponding author. Tel.: 55-81-3271-8450;
fax: 55-81-3271-0359.
E-mail address: eron@npd.ufpe.br (E.F. da Silva Jr.).
tence non-abrupt SiO2/Si(0 0 1) interfaces with thick-
ness of the order of 10 A and concluded that the
interfacial layer was composed by a non-stochiometric
oxide SiOx. More recently, Oh et al. [9] studied the
chemical structure of SiO2/Si interfaces formed by
standard dry oxidation, and found experimental evi-
dence of transition layers containing suboxide states
(Si1, Si2, and Si3) gradedly distributed over three
interfacial layers. Accordingly, ab initio calculations
[10,11], the non-stoichiometric oxygen atoms may
reduce the silicon bandgap may at the graded interface
region, giving rise to the existence of interfacial traps
for carriers [12]. Sousa et al. [13,14] have demon-
strated that interface effects are very strong in 2D
SiO2/Si/SiO2 quantum wells, and can shift the exciton
related luminescence by more than a hundred meV for
wells less than 50 A wide. Particular aspects of growth
processes (like dot inhomogeneity induced by ionic

0169-4332/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 ( 0 1 ) 0 0 8 8 3 - 2
 J.S. de Sousa et al. / Applied Surface Science 190 (2002) 166170
implantation, for example) and post-growth annealing
of samples (which generates thickening of the inter-
faces) suggest that the existence of graded interfaces
must also be considered for a better description of the
electronic states in Si/SiO2 quantum dots.
In this work, we address the problem of how a graded
interface and interfacial carriers trap may change
the confinement properties of silicon quantum dots
(QDs) embedded in silicon dioxide. We obtain graded
interface related blue shifts on the carriers confine-
ment energies higher than 200 meV for dots with a
diameter smaller than 50 A. The interfacial carriers trap
also modify considerably the electronic states of the Si/
SiO2 QDs through a red shift. However, the interfacial
trap related changes on the carriers energy levels
depends on their spatial localization, and are much
smaller than the shifts related to graded interfaces.
2. Modeling a graded Si/SiO2 dot
We suppose the existence of non-stochiometric
SiOx layers composed of suboxide species in the
interfacial regions of the Si/SiO2 dots, in such a
way that the silicon molar fraction changes smoothly
throughout the interfaces. This assumption is based on
a Monte Carlo simulation performed by da Silva and
Stosic [15]. By disregarding high order contributions,
we consider the carriers confinement potential and
effective mass linearly proportional to the silicon/
oxygen content, which varies following an error func-
tion-like profile (Erf).
In the calculations, the effective mass approxima-
tion (EMT) was taken into account. One of the main
problems arises from the loss of the parabolicity for
higher silicon conduction bands of energy. However, it
only occurs for energy bands higher than 1 eV. For the
very high excited states inside the dot, the EMT is no
longer valid, because the dependence of the effective
mass on the energy becomes very complicated. For-
tunately, in general only the lowest confined states and
the radiative interface states are involved in the light
absorption and emission from silicon nanostructures
[7,16]. We assume that the QDs are oriented along the
Si[0 0 1] direction, normal to the bottom of a super-
cell. The electrons occupy the sixfold degenerate X
valleys. Also, the possibility of inter-valley splitting
and the individual electron spins are not considered.
167
The confined states within the QDs are obtained by
solving the following 3D eigenvalue equation corre-
sponding to the three twofold degenerate valley band
structure (i x; y; z in the equations below):
h2 1
r rci r Vrci r Ei rci r; (1)
2 Mi
  
1 2r  r0  D  a
Vr DEc 1  Erf
2 0:5a
e 2
; (2)
4perr  D0
where Mi is the electron effective mass tensor that
takes into account the different contributions from the
anisotropy of the silicon band structure; V(r) the
confinement potential, DEc the confinement barrier
height (3.2 eV), and e the position-dependent permis-
sivity coefficient (11.90e0 and 3.90e0 in the Si and
SiO2 regions, respectively); D the dot diameter, a the
interface width, r0 the center of the dot and D0 the
position of the interfacial carriers trap.
The graded interface trapped (binding) carrier
energy is calculated from EB En;l  En0 ;l0 , where
En,l and En0 ;l0 are the eigenvalues of Eq. (1) with
and without the interfacial trap contribution, respec-
tively [17]. Image charge corrections caused by dif-
ferences between the dielectric constants of Si and
SiO2, as well as strain induced effects are not con-
sidered in our model. In the later case, the overall
effect of the strain is to decrease the bottom of the
silicon conduction band by a hundred meV for a 1%
strain, without changing the carriers effective mass
[18]. Since the existence of graded interfaces reduce
the level of the strain, the shift of the confined carriers
energy states will be of only few meV, much smaller
than the graded interface related shifts. However,
despite our approximations it is still possible to qua-
litatively capture the physical effects of the presence
of an interfacial carriers trap on the energy spectrum.
The three-dimensional eigenvalue equation was
solved using finite difference methods.
3. Graded interface and interfacial carriers
trap effects
We investigate the dependence on dot diameter of
the five initial confined states for abrupt Si/SiO2 dots.
168 J.S. de Sousa et al. / Applied Surface Science 190 (2002) 166170

Fig. 1. The dependence on dot diameter of the five lowest electron confined states in Si/SiO2 dots for the abrupt interface case. The upper inset
depicts the five lowest electron confined states in graded Si/SiO2 dots with interface 10 A wide. The wave functions for the five lowest states
are shown in the lower inset, ordered from left to right.

The electronic states are highly sensible to dot dia-
meter, as show in Fig. 1. The third (dash-dotted line)
and fourth (dash-dot-dotted line) excited states are
degenerated, but due to the coarseness of the grid, it
appears as being nearly degenerated, as can also be
observed by looking at the tri-dimensional wave
functions in the bottom inset of Fig. 1. The depen-
dence of the confined electron energy on the dot
diameter when a 10 A wide graded interface is con-
sidered is depicted in the upper inset of Fig. 1. A
remarkable blue shift related to the existence of the
non-abrupt interface is clear. For the 50 A diameter
dot, the ground state blue shift is of the order of
150 meV, while for a 100 A diameter dot diameter the
blue shift is reduced to about 15 meV. We also find
that the graded interface does not change either the
shape or degeneracy of the wave functions since the
symmetry is unchanged.
In order to investigate the influence of the inter-
facial carriers trap on the energy spectrum, we con-
sider two different positions for the trap, one located
at the external layers of the non-abrupt interface
(position A), and the other located at the internal
layers of the non-abrupt interface (position B). The
effect of the interfacial carriers trap on the electron
ground state energy in non-abrupt Si/SiO2 QDs with
a 10 A wide interface is depicted in Fig. 2. The solid
line indicates the case without interfacial carriers
trap, while that of interfacial carriers trap located
at A and B are indicated by dashed and dotted
lines, respectively. The overall effect is to lower
the energy levels, which for the ground state means
a red shift of the order of 55 and 27 meV for dot
diameters of 50 and 100 A, respectively. These
values decreases when the interface is thinner. We
observe that different positions of the interfacial
carriers trap in the non-abrupt interface region does
not alter the spectrum significantly, which is not the
case if the interfacial carriers trap is located deepest
in the dot. In the inset of Fig. 2, we note that the
binding energy of the interfacial carriers trap located
at A and B changes approximately from 53 to
27 meV when the Si/SiO2 dot diameter varies from
50 to 100 A.
 J.S. de Sousa et al. / Applied Surface Science 190 (2002) 166170 169

Fig. 2. The electron ground state energy dependence on dot diameter of Si/SiO2 dots with a graded interface 10 A wide, without interfacial
carriers trap (solid line), and with interfacial carriers trap in the positions A (dashed line) and B (dotted line). The inset shows the binding
energy (left scale) of the interfacial carriers trap at the positions A (dashed line) and B (dotted line), and the distance between the interfacial
carriers trap located at A (dashed line) and B (dotted line) regarding the center of the dot.

Although obtained for an interfacial carriers trap,
our results strongly suggest that even if the existence
of deep levels at the interfaces are the main contribu-
tion to the luminescence characteristics of low-dimen-
sional Si/SiO2 devices, interface effects must be
considered since they can change considerably their
binding energy. As a matter of fact, our results allow to
conclude that to provide an estimate better than a
hundred meV of the luminescence peaks in these
systems, not only the deep levels at the interfaces
must be characterized but also the width and profile of
the interfacial region.
confined electron energy levels, and the overall effect
of the interfacial carriers trap is to red shift them. We
conclude that accurate information concerning graded
interfaces in Si/SiO2 QDs is of fundamental impor-
tance in order to attain a better understanding of the
light emission properties of their samples, suggesting
strongly that characterization of QDs interfaces are
highly necessary. Finally, despite the assumptions
made here, we believe that the approach used can
be generalized to simulate more realistic structures.
Acknowledgements

4. Concluding remarks J.S. de Sousa acknowledges the support of a grad-

In this work, we have investigated the role of graded
interfaces and an interfacial carriers trap on the con-
fined electron energy spectrum of Si/SiO2 QDs. The
calculations were performed within the effective
mass approximation, and a finite difference method
was used to solve the 3D eigenvalue equation. We
found that the graded interface strongly blue shifts the
uate fellowship from the Brazilian Ministry of Educa-
tion at the Physics Department of the Universidade
Federal do Ceara. GAF, VNF and EFS Jr. would like to
acknowledge the financial support received from the
Science Funding Agency of the Ceara (FUNCAP), the
Brazilian National Research Council (CNPq), and
the Ministry of Planning (FINEP) through CTPETRO
under contract No. 65.00.02.80.00.
170 J.S. de Sousa et al. / Applied Surface Science 190 (2002) 166170
References
[1] R. Tsu, Nature 364 (1993) 19.
[2] Y. Takahashi, T. Furuta, Y. Ono, T. Ishiyama, M. Tabe, Jpn. J.
Appl. Phys. 34 (1995) 950.
[3] Z.H. Lu, D.J. Lockwood, J.-M. Baribeau, Nature 378 (1995)
258.
[4] Y. Kanemitsu, Phys. Rev. B 53 (1996) 13515.
[5] P.N. Saeta, A.C. Galagher, Phys. Rev. B 55 (1997) 4563.
[6] D.P. Yu et al., Phys. Rev. B 59 (1999) R2498.
[7] L. Pavesi, L. Dal Negro, C. Mazzoneli, G. Franzo, F. Priolo,
Nature 408 (2000) 440.
[8] I. Takahashi, S. Okita, N. Awaji, Y. Sugita, S. Komiya,
Physica B 245 (1998) 306.
[9] J.H. Oh, H.W. Yeom, Y. Hagimoto, K. Ono, M. Oshima, N.
Hirashita, M. Nywa, A. Toriumi, A. Kakizaki, Phys. Rev. B
63 (2001) 205310 and references therein.
[10] P. Deak, M. Rosenbauer, M. Stutzmann, J. Weber, M.S.
Brandt, Phys. Rev. Lett. 69 (1992) 2531.
[11] K. Takeda, K. Shiraishi, Solid State Commun. 85 (1993)
301.
[12] Y. Kanemitsu, T. Ogawa, K. Shiraishi, K. Takeda, Phys. Rev.
B 48 (1993) 4883.
[13] J.S. de Sousa, G.A. Farias, V.N. Freire, E.F. da Silva Jr., J.
Appl. Phys. 84 (1998) 5369.
[14] J.S. de Sousa, H. Wang, G.A. Farias, V.N. Freire, E.F. da
Silva Jr., Proceedings of the Seventh International Conference
on the Formation of Semiconductors Interfaces, June 2125,
1999, Goteborg, Sweden, Appl. Surf. Sci. 166 (2000) 469.
[15] E.F. da Silva Jr., B.D. Stosic, Semicond. Sci. Technol. 12
(1997) 1038.
[16] M.V. Wolkin, J. Jorne, P.M. Fauchet, G. Allan, C. Delerue,
Phys. Rev. Lett. 82 (1999) 197.
[17] A. Montes, C.A. Duque, N. Porras-Montenegro, Phys. Stat.
Sol. (b) 210 (1998) 731.
[18] S. Horiguchi, M. Nagase, K. Shiraishi, H. Kageshima, Y.
Takahashi, K. Murase, Jpn. J. Appl. Phys. 40 (2001) L29 and
references therein.