Chemical Physics Letters 423 (2006) 225–228

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Electronic transport in Si–SiO2 nanocomposite films

a,*
M.L. Ciurea , V.S. Teodorescu a, V. Iancu b, I. Balberg c

a
National Institute of Materials Physics, P.O. Box MG-7, Bucharest-Magurele 77125, Romania
b
Department of Physics, University ‘Politehnica’ of Bucharest, Bucharest 060042, Romania
c
The Racah Institute of Physics, Hebrew University, Jerusalem 91904, Israel

Received 13 March 2006

Available online 5 April 2006

Abstract

We report experimental investigations and modeling of the electronic transport in Si–SiO2 nanocomposite films. The current–voltage
characteristics measured at room temperature are interpreted as due to high field-assisted tunneling. The activation energies from the
current–temperature curves are given by the energy separations between quantum confinement electronic states, determined from a quan-
tum well model. Consequently, the calculated mean diameter of a nanodot (5.2 nm) is in good agreement with the microstructure data
(5 nm). Also, the potential barrier between nanocrystalline Si and amorphous SiO2, previously obtained for nanocrystalline oxidized por-
ous Si (2.2 eV), is confirmed.
 2006 Elsevier B.V. All rights reserved.

Semiconducting nanomaterials and nanostructures have
an increasing number of applications in biomedical devices,
sensors, optoelectronics, and ultra-large scale integrated
electronics. The understanding of the specific processes that
take place at this scale represents a major challenge. In
addition, the behavior of the indirect gap semiconductors
raises several problems [1–5]. Thus, several conduction
mechanisms were proposed to describe the various aspects
of the electronic transport in nanocrystalline silicon (nc-Si)
and silicon-based nanostructures. The Ohmic conduction
and surface states contributions were discussed for silicon
nanowires [6]. Fowler–Nordheim tunneling was used to
describe carrier injection from the substrate of a nanocrys-
talline floating-gate MOS transistor [7], and the Schottky
tunneling was investigated for ultra-small diodes [8]. Other
proposed mechanisms are the Poole–Frenkel tunneling in
nanocrystalline porous silicon (nc-PS) [9] and nc-Si/CaF2
multilayer structures [10], and fractal percolation for nc-
PS [11].
The purpose of the present work is to investigate the
electronic transport mechanism in Si–SiO2 nanocomposite
*
Corresponding author. Fax: +40 21 493 0267.
E-mail address: ciurea@infim.ro (M.L. Ciurea).
films, taking into account the potential barrier between nc-
Si and amorphous silicon dioxide (a-SiO2).
The Si–SiO2 films were prepared by co-sputtering of Si
and SiO2 on an elongated quartz substrate, followed by
the annealing in N2 flow at 1100 C to form Si crystallites
[12,13]. This method offers the advantage of an almost lin-
ear variation of the volume content of the nc-Si phase (x)
from one end of the substrate (x  0%) to the other one
(x  100%). The films thickness was in the 5–9 lm range.
For the transport measurements, 50 coplanar Al electrodes
were deposited at 1 mm distance from each other. In this
Letter, we present investigations performed on samples in
the x = 65–75% range.
The films microstructure was investigated with a JEOL
200CX microscope for transmission electron microscopy
(TEM) and a TOPCON 002B instrument for the high res-
olution measurements (HRTEM). The current–voltage (I–
V) and current–temperature (I–T) characteristics were
taken using a Keithley 642 electrometer and an Agilent
E3631A d.c. power supply.
The microstructure measurements show the segregation
of the nc-Si and a-SiO2 phases at nanometric scale. This
segregation decreases with the increase of the nc-Si concen-
tration. Fig. 1 presents a typical non-uniform distribution
of nc-Si in a-SiO2 matrix at x  66%. Differently oriented

0009-2614/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2006.03.070
226 M.L. Ciurea et al. / Chemical Physics Letters 423 (2006) 225–228
Fig. 1. HRTEM image from x  66% region.
silicon crystallites of practically the same size (around
5 nm) and quasi-spherical shape form a network with chain
morphology, while the width of the amorphous regions
does not exceed 5 nm. The apparent nc-Si phase concentra-
tion is smaller than the real one, as not all the crystallites
are properly oriented to exhibit (1 1 1) lattice fringes con-
trast in the HRTEM image.
A typical I–V characteristic, taken at room temperature
(RT) at x  66% is shown in Fig. 2. The curve is superlin-
ear and practically symmetric. Three I–T curves, measured
on the same sample, are presented in Fig. 3. At low bias (4
and 5 V) one finds three activation energies (E1 = 0.22 ±
0.02 eV, E2 = 0.32 ± 0.02 eV, and E3 = 0.44 ± 0.02 eV),
while at high bias (25 V) only the values (0.33 ± 0.02 eV
and 0.44 ± 0.02 eV, practically equal with E2 and E3,
respectively) can be observed. The activation energies were
determined under two restrictions: (i) the linear correlation
coefficient must be greater than 0.9995 and (ii) no experi-
Fig. 2. I–V characteristic for x  66% region. The solid line represents the
theoretical fit.
Fig. 3. I–T characteristics for x  66% region, measured at 4, 5 and 25 V.
mental point is farther from the fitting line than its exper-
imental error.
The electronic transport presents two aspects, the trans-
port inside and between the nanodots. Inside the nanodots,
the Coulomb blockade (CB) effect appears. For the mean
nanodot diameter of 5 nm, the CB energy is ECB = e2/
(2pe0erd) = 46 meV. At RT this means 1.8 kBT, so that no
shape modification of the I–V curves could be observed
between liquid nitrogen temperature (LNT) and RT. Inside
the nanodots the carriers will perform ballistic movements,
due to the absence of impurities and/or point defects [14].
The transport between the nanodots is mainly performed
by tunneling under high field (eU  kBT) through a perco-
lation network (see [15]). From Fig. 1 it results that the car-
riers move preferentially along nc-Si chains and tunnel
through a number of barriers. Then, the high field-assisted
tunneling (HFAT) current is well described by the relation
[16]
 pffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
I ¼ a½u exp dv u  ðu þ qU b Þ expðdv u þ qU b Þ;
ð1Þ
where u and d are the mean height and width of the poten-
tial barrier between nanodots, jqj = e (the elementary
charge) and v = (8m*/h2)1/2 (m* being the effective carrier
mass), while a is a constant proportional to the number
of equivalent paths and the ionic transport through
a-SiO2 was neglected. If one considers the tunneled barriers
as roughly equal, then Ub = U/N, where U is the applied
bias and N the mean number of barriers. For superlinear
curves, the relation (1) can be rewritten in the form
h pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i
I ¼ I 0 signðU Þ ð1  jU j=U 0 Þ expða 1  jU j=U 0 Þ  expðaÞ ;
ð2Þ
1/2
with I0 = jaju, U0 = Nu/e, a = dvu and q = e. From
the experimental results one cannot determine all the four
theoretical parameters (a, N, d and u), but only the fit
parameters I0, U0 and a.
 M.L. Ciurea et al. / Chemical Physics Letters 423 (2006) 225–228
The solid line in Fig. 2 represents the fit of the experi-
mental characteristic to Eq. (2). The fit parameters are
I0 = (3.383 ± 0.003) A, U0 = (191.2 ± 0.2) V and a =
14.74 ± 0.01, with a correlation coefficient q = 0.9996.
For a potential barrier height u = (2.2 ± 0.2) eV (previ-
ously obtained for oxidized nc-PS) [17], one finds
N = 87 ± 8 and d = (1.0 ± 0.1) nm. Then, the CB effect
should appear for jUj6UCB = N(ECB-kBT)/e. The CB
threshold, UCB, is equal to 1.75 V at RT and 3.45 V at
LNT, respectively. At the same time, eUmax/Nu  1/6, jus-
tifying the choice of the HFAT mechanism (corresponding
to a trapezoidal-like barrier) instead of the other tunneling
mechanisms (corresponding to triangular-like ones). As the
carrier path is along the chains and the width of a barrier
between neighboring crystallites in a chain is an inter-
atomic distance (twinned crystallites), the mean width of
a barrier is much smaller than the distance between the
chains. The number of tunneled barriers does not give
the total electron path through the sample (see Fig. 1). This
means that the rest of the path is covered through less resis-
tive mechanisms (e.g. the resistance of a full crystallite
chain is much smaller than the equivalent resistance of a
single mean width barrier and the ionic transport short cir-
cuits most of the barriers), which do not influence the I–V
characteristic in a significant manner. Similar investiga-
tions made on different samples in the x = 65–75% region
showed that d varies with less than 10% and N with more
than 50%, in a fluctuating manner (due to the randomness
of the nc-Si space distribution).
The nanodot surface acts as the wall of a quantum well
that generates the quantum confinement (QC) energy lev-
els. These levels are located in the band gap because the
fundamental QC level coincides with the highest occupied
level at absolute zero (top of the valence band). Different
types of potentials (rectangular, parabolic, Woods-Saxon
etc.) were used to describe the QC [17–19]. If the nanodot
is small enough, a spherical shape and an infinite rectangu-
lar quantum well adequately describe the QC (less than 5%
differences for the first 3–4 levels, in comparison with a 2–
5 eV deep rectangular quantum well, for sizes between 1
and 10 nm) [17]. Then, the QC energy levels are given by
the expression
2h2  
el;p ¼  2 x2l;pþ1  x20;1 . ð3Þ
md
Here d is the nanodot diameter and xl,p the p-th zero of the
spherical Bessel function jl(x) for the angular quantum
number l (by convention, e0,0 ” 0).
The expression (3) is correct only in the effective mass
approximation (EMA) limits. The LCAO method [20]
proved that the diameter dependence of the band gap has
the form Eg  da, with a = 1.39 for spherical nanodots,
instead of a = 2 as obtained from EMA. Exciton measure-
ments [5] suggest an even lower exponent, a = 0.6–0.8.
However, recent investigations [21] proved that EMA can
be applied if one introduces a size dependence of the effec-
tive mass. Therefore the nanodot diameter can be esti-
227
mated from Eq. (3). On the other hand, Eq. (3) can be
applied to any kind of nanomaterials.
The energy differences between consecutive levels for
d  5 nm are an order of magnitude greater than both
ECB and kBT, even at RT. Consequently, at a given T,
the carrier concentration will be given by the Boltzmann
law, n  exp(Ea/kBT), where the activation energy Ea is
the absolute value of the energy difference between the last
occupied level and the following one. The drift velocity is
constant (ballistic transport inside the nanodots), so that
the I–T curves present an Arrhenius-like behavior. When
a level is practically filled, a following one starts to be
excited and, at this ‘jump’ temperature, the activation
energy is modified. Therefore, the ratio of the two consec-
utive activation energies is
2 2
E00a el00 ;p00  el0 ;p0 xl00 ;p00 þ1  xl0 ;p0 þ1
RE  ¼ ¼ . ð4Þ
E0a el0 ;p0  el;p x2l0 ;p0 þ1  x2l;pþ1
This ratio depends on the excitation conditions. For ther-
mal excitation (eU  kBT), the first three levels correspond
to l = 0, 1, 2 and p = 0, so that RE = 1.26. If the excitation
is made under a high field, the first three levels correspond
to l = 0 (angular momentum conservation) and p = 0, 1, 2,
with RE = 1.67. If the field is applied at a temperature
where the (1, 0) level is thermally excited, RE = 1.50, and
so on.
As mentioned before, three activation energies are
observed in the I–T characteristics measured at 4 and
5 V. Their ratios are RE ” E2/E1 = 1.45 and R0E 
E3 =E2 ¼ 1:37. For E1 = e1,1  e1,0, E2 = e1,2  e1,1 and
E3 = e1,3  e1,2, the differences between the theoretical
and the experimental ratios are of the order of 3%. From
Eq. (3) we derive d = 5.2 ± 0.4 nm, in agreement with the
microstructure results. At 25 V, only the last two activation
energies (E2 and E3) appear. The disappearance of E1
means that this bias is high enough to excite the (1, 1) level
from the (1, 0) one, which should be expected at this tem-
perature range. The energy shift induced by the voltage
increase from 5 to 25 V can be evaluated on the basis of
the I–V fit. For N = 87, a bias variation of 20 V gives an
average bias per barrier of (0.23 ± 0.02) V, almost equal
to E1/e. This does not only suggest that the nc-Si/a-SiO2
barrier height is practically the same for oxidized nc-PS
and Si–SiO2 nanocomposite films, but also proves the
self-consistency of the different results presented above.
On different samples, where the average bias per barrier
is significantly smaller than E1/e, the first activation energy
value appears at all applied biases.
In conclusion, the analysis of the electronic transport
proves that: (i) the I–T characteristics depend on the
transitions between the electronic states and (ii) between
nanodots the dominant mechanism observed in the I–V
characteristics is the HFAT. The electron energies and
the mean nanodot diameter of 5.2 nm, evaluated by
means of a simple quantum well model, are in good
agreement with the activation energies found in the I–T
228 M.L. Ciurea et al. / Chemical Physics Letters 423 (2006) 225–228
characteristics and the microstructure data. The potential
barrier between nc-Si and a-SiO2, previously obtained for
oxidized nc-PS, is also confirmed.
Acknowledgements
This work was supported in part by CERES Contract
No. 9/2001 (Romanian National RD Plan), in part by Is-
rael Science Foundation (ISF) and in part by Intel
Corporation.
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