Thin Solid Films 518 (2010) 5378–5381

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Raman study of stress effect on Ge nanocrystals embedded in Al2O3

S.R.C. Pinto a, A.G. Rolo a, A. Chahboun a,b,⁎, R.J. Kashtiban c, U. Bangert c, M.J.M. Gomes a
a
Physics Department, University of Minho, 4710-057 Braga, Portugal
b
LPS, Physics Department, Faculty of Sciences, BP 1796, FES, Morocco
c
Nanostructured Materials Research Group, School of Materials, The University of Manchester, PO 88, Manchester, M17HS, UK

a r t i c l e i n f o a b s t r a c t

Article history: Ge nanocrystals (NCs) embedded in Al2O3 were grown by RF-sputtering. X-ray diffraction, high resolution
Received 11 October 2009 transmission electron microscopy, and Raman spectroscopy techniques were used to characterize the
Received in revised form 6 March 2010 stresses on the NCs. While small NCs (b 10 nm) have been observed to be spherical and fully relaxed in the
Accepted 11 March 2010
matrix, the larger ones (N 17 nm) demonstrated a compressive stress effect. This could be linked to the
Available online 19 March 2010
crystal structure of the adjacent Al2O3 matrix.
Keywords:
© 2010 Elsevier B.V. All rights reserved.
Germanium
Aluminium oxide
Nanocrystals
Stress
Raman spectroscopy
Transmission electron microscopy

1. Introduction There is a considerable body of literature relating to the stress

Ge nanocrystals (NCs) embedded in dielectric matrices have
attracted considerable attention because of their potential applica-
tions in non-volatile memory and integrated optoelectronics [1]. Most
of the previous work has focused on Ge NCs embedded in SiO2 matrix
[2]. Since Al2O3 presents a high dielectric constant comparative to
SiO2, possesses good mechanical properties and endures high
temperature, this makes it a good candidate for replacing silica in
flash memory systems and thereby can improve their performance
[3]. However, few studies have been reported on Ge NCs embedded in
Al2O3 matrices [4–9]. Interfacial strain was usually observed in NCs/
matrix systems, such as with Ge NCs [10,11]. Considering the large
interface-to-volume ratio in NCs/matrix systems the characters of the
stress and strain fields play an important role in deciding the physical
and thermodynamic properties of NCs. Moreover, strain in Ge NCs is
known to modify significantly the electrical properties of these NCs
[12].
Various techniques are used to estimate the stress in embedded
NCs. Among them, X-ray diffraction (XRD) and high resolution
transmission electron microscopy (HRTEM) provide measurement
of the lattice parameter, thereby giving the most fundamental
measurements of the stress [13]. However, one of the most powerful
methods to access information on strain in embedded nanostructures
is Raman scattering spectroscopy [10].
⁎ Corresponding author.
E-mail address: chahboun@msn.com (A. Chahboun).
effect on Ge NCs embedded in SiO2 [14–17]. However, little work [5]
has been dedicated to examination of the stress effect in the Ge/Al2O3
system. In this report, we studied the stress effect on Ge NCs
embedded in Al2O3 by XRD, HRTEM, and Raman spectroscopy. We
observed that the stress is intimately linked to the sizes of the NCs.
2. Experimental details
In this work, Ge NCs embedded in Al2O3 were grown in a
commercial RF magnetron Alcatel SCM 650 apparatus using a
conventional co-sputtering method. Two materials, Al2O3 (99.99%)
and polycrystalline Ge (99.99%), were simultaneously used as target
to produce the doped films. Low electrical resistivity (3–6 Ωcm) n-
type Si(111) 2-inch wafers were used as substrates. Prior to
sputtering, a pressure of at least 1 × 10−6 mbar was reached inside
the chamber and in situ argon plasma treatment of target and
substrates was performed in order to clean the surfaces and remove
any impurities. More details of the sample preparation methods can
be found in previous work [9,17]. In order to improve the crystallinity
of the Ge phase and to achieve control over the NCs sizes, the as-
grown samples were annealed at 800 °C and 900 °C, for 1 h, under an
air pressure at 10−1 to 10−2 Pa. The sizes and size distribution of Ge
NCs were determined by XRD, HRTEM, and Raman spectroscopy using
a theoretical analysis based on the phonon confinement model [18].
The details of growth conditions and NC's size estimated from XRD,
Raman, and HRTEM are illustrated in Table 1.
In order to identify the chemical elements present in the films and
any variation of their atomic percentage with depth, the Rutherford

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doi:10.1016/j.tsf.2010.03.035
 S.R.C. Pinto et al. / Thin Solid Films 518 (2010) 5378–5381 5379

Table 1
Details of growth conditions and NC's size estimated from XRD, Raman, and HRTEM.

Sample Deposition parameters Annealing conditions Nanocrystals Size (nm)

RF Power Time Árgon Pressure Temp. Temperature Pressure

Name (W) (min) (Pa) (°C) (°C) (Pa) XRD Raman HRTEM

A4 50 240 0.3 500 800 4.6 × 10−1 4.2 4.0 4.8

A6 50 255 0.5 500 800 4.6 × 10−1 6.0 5.5 5.3
A7 80 270 0.4 500 800 4.6 × 10−1 7.1 7.0 8.0
A10 80 270 0.4 500 800 3.0 × 10−1 10.4 10.0 –
B17 50 240 0.8 500 900 8.0 × 10−4 17.0 17.0 18
B20 50 255 0.5 500 800 1.5 × 10−3 20.0 20.0 –

Back Scattering (RBS) characterization technique using a 2.0 MeV 4He+
beam was employed.
Investigations of crystallographic structure were performed with
XRD, in conventional θ−2θ geometry (Philips PW1710) using Cu Kα
radiation. The identification of the crystalline phases was made using
the JCPDS (Joint Committee of Powder Diffraction) database. The
structure of the samples was examined using a Tecnai F30 FEG
transmission electron microscope. The HRTEM cross-sectional speci-
mens were prepared by manual polishing followed by ion beam
milling. Raman scattering spectra were obtained using a Jobin-Yvon
T64000 system with an Olympus BH2-UMA microanalysis system and
a CCD detector, in a backscattering geometry. Raman spectroscopy
was performed at room temperature using the 514.5 nm and
488.0 nm lines of an argon laser at a power of 50 μW and an area of
the sample ∼1 μm2.
3. Results and discussion
RBS results (not shown here) demonstrated that the studied
samples have homogeneous composition profiles, with Ge content
ranging from 16 to 20 at.%. The other elements present (O and Al) also
are distributed rather uniformly through the thicknesses of the films
[17].
For this study, we have considered two set of samples that we
named Ai and Bj, with small NC's diameter (i b 10 nm) and larger NC's
diameter (j N 17 nm), respectively. The index is the mean size of NCs
observed in a given sample. This choice comes from the fact that these
two sets of samples showed two different behaviours, as we will see
below.
Typical XRD diffractograms from samples Ai and Bj are shown in
Fig. 1. They clearly reveals (111), (220), (311) and (400) reflections
corresponding to peaks from the diamond structure of Ge. Annealing
was observed to lead to sharper peaks and a better crystallinity of Ge
Fig. 1. Typical XRD diffractograms for Ai and Bj samples. Here are shown the graphs for
A7 and B17. Dashed lines denote the positions of diffraction peaks in bulk Ge.
NCs. While Ai show broad peaks, Bj show slightly shifted sharp peaks
indicative of a more crystalline phase. The observed shift possibly
could be explained by the stress exerted by the matrix on the NCs.
NC's average sizes were deduced from X-ray spectra using the Debye-
Scherrer equation [19]. Using Lorentzian functions to fit each XRD
peak of the samples, we obtained mean diameter values of the NCs.
The NC's sizes obtained for the samples A and B, were 4 nm (A4), 6 nm
(A6), 7 nm (A7), 10 nm (A10), 17 nm (B17), and 20 nm (B20),
respectively. Analyzing carefully the XRD diffractograms of the Bj
sample, it is clear that the peaks are shifted for larger angles (that
means a smaller lattice parameter) in relation to the diamond
structure of Ge crystallites, which is evidence of stress in the structure.
In fact, the estimated stress was 0.3% and 0.8% for the (220) planes in
the plane for samples B20 and B17, respectively.
HRTEM measurements allowed the determination of statistical
average size of the NCs by measuring lattice plane spacings in the NCs
using the fast Fourier transforms (FFTs) of the HRTEM images. Fig. 2a
shows a typical HRTEM image of Ai samples with a spherical NC. The
HRTEM study of this sample (A6) confirmed that the Ge NCs have good
homogeneity and spherical shapes [20]. Extensive twinning, observed
in most of the NCs, indicates that stress relaxation has taken place and
we might therefore expect the NCs to be unstrained. A statistical
average diameter of 5.3 nm was obtained from the HRTEM images
with a standard deviation of 1.3 nm. Fig. 2b shows a typical HRTEM
image of sample Bj. The NCs are quasi elliptical with minor and major
diameters about 10 nm and 18 nm, respectively (sample B17). Lattice
plane spacings of the Ge NCs in Bj samples were measured using FFT
analysis of the HRTEM images. Error margins were obtained from
measurements of the Si substrate lattice spacing using HRTEM images
with the samples aligned with the electron beam along the (110) zone
axis of the silicon substrate. The observed changes in the lattice
distances of NCs were within the error values, and hence the strains
would be below 1%. In fact, in earlier theoretical calculations by Cheria
et al. [21] it was shown that the change in the lattice constant is about
0.4% and approaches a bulk-like value for very small clusters.
Raman spectroscopy provides the sensitivity and the resolution
required to determine the stress on NC's. Confinement of optical
phonons in semiconductor NC's leads to relaxation of q ≅ 0 selection
rules for Raman scattering. As a result, optical phonons with q ≠ 0
are excited and Raman spectra from NCs are asymmetrically
broadened and red shifted relative to the bulk [13,14].
The main observed feature in the Raman data is the red shift for Ai
and the blue shift for the Bj samples of the Raman peak in comparison
to bulk Ge (300.5 cm−1). Fig. 3 shows the Raman spectra for samples
A7 and B17. It is possible to observe that modifications of the spectral
shape of the LO phonon mode occur for the Ai samples. As the average
size decreases the Raman peak broadens and shifts slightly to smaller
frequencies. The red shift and the broadening of the Raman peak have
been observed in many systems and have been explained by the
quantum confinement effect on phonons in a finite volume of the NCs
[13,14,18,22].
The average sizes of the NCs from samples Ai were estimated from
the Raman spectra using the Fauchet Campbell model [18], a
5380 S.R.C. Pinto et al. / Thin Solid Films 518 (2010) 5378–5381

Fig. 2. HRTEM micrographs of A6 and B17 samples. While Ai presents quasi-spherical fully relaxed NCs, B17 shows elliptical shapes. The lattice planes are clearly seen in the pictures.

confinement model for spherical and fully relaxed NCs. This model
takes in consideration that the intensity of diffusion is the sum of
intensities for each frequency and it is given by:
∞ demonstrating the quality of the samples produced.
IðωÞ = ∫ PðLÞdL IL ðωÞ
0 As it was seen in Fig. 4, for the larger size of NCs (Bj), the LO Raman
where IL(ω)is the Raman spectrum without size distribution function
and P(L) is a size distribution function with mean value d and standard
deviation σ. P(L) was assumed to be a Gaussian function, and the
instrumental transfer function was considered as triangular function
with full width half maximum (FWHM) Γs = 1 cm−1. The optical
phonon dispersion for Ge was taken as ωμ(q) = C1 + C2 cos (qa/2)
where C1 = 288.3 cm−1 and C2 = 12.01 cm−1 [23].
Fig. 4 shows the simulation of the experimental LO Raman peak for
sample A7, using the model explained above. The parameters used in
the fit were 7 nm for the crystallite diameter and 1 nm for the size
distribution. As can be seen in the Fig. 4, the experimental values are
perfectly fitted by the calculated spectrum. The value of the crystallite
diameter used in the calculated curve agrees well with that deduced
from XRD (7.14 nm) and HRTEM (8 ± 3 nm). The Raman peaks of all
Ai samples were perfectly fitted with the model described above using
i as a diameter and a small dispersion for NCs (b1 nm). Thus, it is
possible to state that for this range of NCs diameters (b10 nm) the NCs
are fully relaxed in the Al2O3 matrix. Fig. 5 gives a summary of peak
positions for the studied samples. The continuous line presents the
calculated position using the theoretical model for homogenous NC's
size. The dashed continuous line indicates the Ge bulk position. The
calculated line does not follow perfectly the experimental points of Ai
due to the size dispersion. However, as it was mentioned above, all Ai
peaks were fitted well using size dispersion less than 1 nm,
ð1Þ
peak is blue shifted. One possible explanation for this is the
compressive stress exerted on Ge NCs due to the Al2O3 matrix. This
effect in Ge NCs due the SiO2 matrix has already been studied by other
groups [14–17], but for NCs in an Al2O3 matrix this effect has not fully
been studied.
The evolution mechanism of the interface strain with pressure
could roughly be estimated with the following simple elastic model:
ωðpÞ = ω0 + α⋅P ð2Þ
where ω(p) and ω0 are the experimental and theoretical frequency
respectively, α is the pressure coefficient (αbulk = 0.39 10−8 cm−1 Pa−1
[24]) and P is the effective pressure.
The solid curve in Fig. 6 shows the Raman spectrum of B17 fitted
with the Fauchet Campbell model after introducing the stress exerted
on the NCs. The parameters used in the fit were 17 nm for the
diameter, deduced from XRD. The pressure value of 3.17 108 Pa was
estimated from the relationship (2) taking into account the LO peak
shift relative to that of free-standing Ge crystals. It is obvious that the
experimental spectrum is not perfectly fitted especially for higher

Fig. 4. Experimental (squares) and calculated [18] (continuous line) Raman peaks for
Fig. 3. Typical Raman spectra for Ai and Bj samples. The LO peak shows a red shift for Ai A7. The parameters used in the fit were 7 nm for the crystallite diameter and 1 nm for
and a blue shift for Bj, relative to the peak for bulk Ge (dashed line). the dispersion.
 S.R.C. Pinto et al. / Thin Solid Films 518 (2010) 5378–5381
Fig. 5. Summary of the evolution of the experimental Raman peak frequency against the
NC's size. The continuous line is the calculated frequency versus NC size using the
theoretical model [18].
Fig. 6. Simulation of the LO Raman peak for the B17 sample, using the model [18] and
introducing the pressure.
frequencies. This could be explained by the fact that the theoretical
model considers spherical NCs, whereas it is seen in HRTEM images
that the NCs for Bj samples are more likely to be elliptical. As expected,
Raman data show that the LO peak is more blue shifted for the sample
with larger NCs (B20). This is in disagreement with strain measured
from XRD. The observed incoherency may come from the fact that
Raman gives us an average measurement on all crystallographic
orientations, while the measurement from XRD was carried out only
from (220) reflection.
The local stress observed for large NCs could result during cooling
and heating, due to differences between the thermal expansion
coefficients of the NCs and the matrix. In fact, Ge nucleates and grows
in the liquid phase, and due to the 6% volume expansion of Ge upon
solidification, the matrix exerts a compressive stress on the solid NCs.
Moreover, there is a size threshold (between 10 and 17 nm) for the
stress effect that could be linked to the inner structure of Al2O3.
The compressive stress in Ge NCs due the SiO2 matrix was already
studied by other groups [25] and linked to the size effect. However,
the stress on Ge NCs embedded in Al2O3 matrix has not yet been fully
investigated. Indeed, the red shift caused by phonon confinement
could be compensated by the blue shifts which are caused by the
compressive stress on the Ge NCs in Al2O3 matrix. The stress may also
affect the linewidth of the Raman peak. However, discussion of the
5381
effect of the stress on the linewidth is extremely difficult, because
detailed information about the stress is not available. More investi-
gation is needed in order to clarify the effect of the stress in
microcrystalline phase on both the linewidth and peak positions in
Raman spectroscopy, in order to tune the stress effect with the aims of
optimizing and predicting the performance of NCs.
4. Conclusions
Ge NCs embedded in Al2O3 matrix were produced by RF
magnetron sputtering. By using X-ray diffraction, Raman spectrosco-
py and HRTEM it was possible to estimate the sizes of Ge NCs. For the
smallest Ge NCs, Raman spectra are red shifted and the spectra are
well fitted with the quantum confinement model, using the average
size estimated from XRD and HRTEM. However, for larger NCs there is
a blue shift of the Raman peaks relatively to the Ge bulk. Introduction
of the pressure into the confinement model allows a good fitting of
spectra. This a demonstration that these NCs are under compressive
stress in the matrix. More quantitative studies are needed to estimate
the threshold size of NCs to pass from the fully relaxed to the strained
regime, and quantify the effect of the stress on the optical and
electrical properties of the embedded NCs.
Acknowledgments
This work has been partially funded through the projects PTDC/
FIS/70194/2006, financed by Portuguese Foundation for Science and
Technology and the Bilateral Cooperation Programme BC/CRUP-B 26/
08, financed by British Council and Council of Portuguese’ Rectors.
SRCP would like to thank FCT for the grant FRH/BD/29657/2006. We
would like to knowledge Emeritus Professor David Barber for his
discussion about our HRTEM data and for his careful reading of the
manuscript.
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