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Porous SiGe Nanostructures Formed by Electrochemical Etching of Thin Poly-SiGe

Films

Article  in  Journal of The Electrochemical Society · May 2004

DOI: 10.1149/1.1695531

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C326 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲
0013-4651/2004/151共5兲/C326/7/$7.00 © The Electrochemical Society, Inc.

Porous SiGe Nanostructures Formed by Electrochemical

Etching of Thin Poly-SiGe Films
T. Del Caño,a L. F. Sanz,a P. Martı́n,a M. Avella,a J. Jiménez,a A. Rodrı́guez,b
J. Sangrador,b T. Rodrı́guez,b,z V. Torres-Costa,c R. J. Martı́n-Palma,c
and J. M. Martı́nez-Duartc
a
Departamento de Fı́sica de la Materia Condensada, Universidad de Valladolid, 47011 Valladolid, Spain
b
Departamento de Tecnologı́a Electrónica, E.T.S.I. de Telecomunicación, Universidad Politécnica de Madrid,
28040 Madrid, Spain
c
Departamento de Fı́sica Aplicada, Universidad Autónoma de Madrid, 28049 Madrid, Spain

We have studied the effect of the current density 共J兲 and etching time in the formation of porous poly-SiGe 共pp-SiGe兲 layers, with
Ge fractions in the 0 to 0.55 range, by electrochemical etching. The starting material was unintentionally doped polycrystalline
SiGe thin films, deposited in amorphous state by low-pressure chemical vapor deposition and subsequently crystallized. pp-Si
structures were found to be homogeneous at large scale and show nanocrystalline of around 5 nm for low J values. The pp-SiGe
structures show nonuniformities in their structure; the nanocrystal size is around 10 nm for low J and decreases for high J values
and increasing etching times, reaching values of 2-4 nm. The composition of the pp-SiGe films, for low to moderate J values,
shows a slight Ge enrichment. For high J values, in samples with x ⫽ 0.38, all the Si was etched and the composition of the
porous layer is pure Ge. This effect is not so strong for samples with high Ge fractions (x ⫽ 0.55). The dominant radiative
recombination mechanism is not excitonic; we associate it with recombination via defects in the crystalline structure of the porous
film or states at the interface nanocrystals/native SiO2 .
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1695531兴 All rights reserved.

Manuscript submitted October 31, 2003; revised manuscript received November 27, 2003. Available electronically April 7, 2004.

SiGe presents several advantages respect to Si, e.g., higher mo-
bility, faster response, and shorter exciton lifetime with the corre-
sponding increase of the radiative recombination efficiency. In ad-
dition to the confinement effects due to the nanocrystals size,
tunable emission could also be expected from porous SiGe within a
large range of Ge atomic fractions, because the band gap of SiGe
changes by 0.22 eV between x ⫽ 0 and 0.8, and then drops abruptly
to the band gap of crystalline Ge. Porous SiGe with Ge fractions up
to 0.41 共although most of the studies are done for Ge fractions up to
0.2兲, have been reported to be formed by different processes 共elec-
trochemical and stain etching兲 on different types of starting materi-
als, like multicrystalline bulk SiGe alloys,1 SiGe layers grown by
molecular beam epitaxy 共MBE兲2,3 or strain relaxed SiGe films de-
posited in an standard Si-epitaxy horizontal tube reactor.4 In all
cases the SiGe layer was doped with boron in the 1017 to
⬎1019 cm⫺3 range. The intensity of visible photoluminescence 共PL兲
of porous SiGe formed by anodization of SiGe layers grown by
solid state MBE 共SSMBE兲 and strain relaxed SiGe has been found
to be nearly as intense as that of porous Si per unit volume of
nanostructure.5,6 Also, PL intensity in porous SiGe has been reported
to significantly decrease with increasing Ge fraction for porous
samples formed by electrochemical or stain etching of epitaxial
SiGe layers.2,4 The method proposed in this work, low-pressure
chemical vapor deposition 共LPCVD兲, can be used to deposit amor-
phous or polycrystalline thin SiGe films on large areas of different
substrates like silicon, silicon oxide, metal or glass; therefore porous
poly-SiGe films can be formed on them using a simple and low-cost
procedure compatible with well established semiconductor device
manufacturing technologies. In addition, it has been reported that
porous poly-Si films have a smoother surface and a more uniform
microstructure than porous Si, properties which are advantageous
for diverse applications of this material.7,8 These expectations make
the fabrication of porous poly-SiGe for applications in integrated
optoelectronics a very attractive research field, that has not received
up to now a so great deal of attention as porous Si.
The origin of visible luminescence emitted by porous SiGe re-
mains a matter of controversy. Previous work on porous SiGe using
different kinds of starting material and preparation conditions report
on the existence of a luminescence peak in the 1.65-2.1 eV energy
z
E-mail: tomas@etsit.upm.es
interval. Shi et al.9 reported two luminescence peaks, at 198 K, one
of them located at 1.72 eV associated with porous Si, and the other
one at 1.96 eV and associated with porous SiGe, those peaks look to
converge in one peak at 1.86 eV at room temperature. Radiative
recombination of quantum-confined excitons, recombination via de-
fects or dislocations in the crystal structure of the porous layer, and
also small units containing only a few Si atoms that are responsible
for the light emission have been proposed as tentative source mecha-
nisms for the luminescence emission of porous Si.2-6,10 The PL spec-
tral parameters were found in another work to be independent of the
alloy composition, current density and etching time, which allowed
the authors to exclude excitonic recombination as the origin of the
luminescence.11 In porous Si, the band at 1.70-1.75 eV is attributed
to oxide-related radiative defects at the Si/SiOx interface.12 Also,
defects in the silicon oxide or at the Si/SiO2 interface have been
pointed out as the origin of the luminescence in the red spectral
range 共1.6-2.0 eV兲 of Si nanocrystallites embedded in SiO2 formed
by thermal oxidation of a polycrystalline silicon layer.13 As anodized
porous Ge shows a peak at 1.17 eV and after thermal oxidation of
the sample the peak shifts to 2.15 eV; this band is associated with
radiative recombination through localized states at or near the
Ge-GeO2 interface.14 Also, the PL peaks at 2.1 eV found in the
Ge-SiOx and Si-SiOx systems have been associated with oxide re-
lated defects in silicon dioxide, such as the so-called E⬘ center.6
In this paper, we present a study of porous SiGe structures, start-
ing from unintentionally doped polycrystalline thin films obtained
by solid phase crystallization of amorphous SiGe films deposited by
LPCVD, formed by electrochemical etching. The Ge fractions in-
vestigated range from x ⫽ 0 to x ⫽ 0.55. The morphology of the
samples has been analyzed by atomic force microscopy 共AFM兲, the
composition of the porous layers and the nanocrystal size by mi-
croraman spectroscopy, and the luminescence emission and its uni-
formity by microphotoluminescence spectroscopy.
Experimental
The original unintentionally doped SiGe layers, 240 nm thick,
were deposited in amorphous state by LPCVD at 450°C and subse-
quently annealed in vacuum at 625°C until their complete crystalli-
zation. More experimental details on the deposition process are
available elsewhere.15 The Ge fractions of the polycrystalline layers
were determined by X-ray diffraction 共XRD兲, they were in the range
of x ⫽ 0-0.55. The sheet resistance of the polycrystalline layers,
 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲 C327

lightly p-type, ranges from 1010 ⍀/ for pure Si to 3.5 • 102 ⍀/䊐
for SiGe with x ⫽ 0.55. The lateral grain diameter is around 1000
nm for x ⫽ 0 and below 300 nm for SiGe with x ⫽ 0.55, as deter-
mined from transmission electron microscopy 共TEM兲 measure-
ments. The grains exhibit 共111兲 preferred orientation for x ⫽ 0
which progressively disappears as the Ge fraction increases, in such
a way that the films with x ⬎ 0.3 are almost randomly oriented
polycrystals. A detailed study of the film properties can be found
elsewhere.16 The porous SiGe nanocrystals were formed by electro-
chemical etching of the poly-SiGe films. The wafers were coated
with an aluminum layer on their back side. To form a low resistance
ohmic contact, they were annealed at 450°C for 30 min in forming
gas. The wafers were cut into 1 ⫻ 1 cm2 pieces which were
mounted into a sample holder with an exposed area to the electro-
chemical etching solution of 0.64 cm2 . The electrolyte consisted of
a 2:1 HF 共48 wt %兲: ethanol 共98 wt %兲 mixture. The samples were
electrochemically etched under illumination from a 100 W halogen
lamp using current densities in the 10-80 mA/cm2 range. Etching
times of several minutes, similar to those reported in the literature
共usually in ranging from 3 to 60 min兲 produce the peeling and even
the complete etching of the our polycrystalline thin films. To avoid
this, we have kept the total transferred charge below 800 mA
• s/cm2 for all the anodization processes. Thus, the etching times
ranged from 6 to 25 s. Finally, the samples were rinsed in ethanol
and stored in vacuum to minimize the oxidation of the layers due to
prolonged air exposure. No subsequent treatments of any kind were
carried out in the as-anodized samples. The samples were analyzed
by the different techniques trying to minimize the time elapsed after
they were extracted from their vacuum storage, to reduce the effects
of ambient oxidation on the porous structures.
Atomic force microscopy 共AFM兲 measurements were carried out
to determine the sample structure and roughness using a Topometrix Figure 1. 3D 1 ␮m2 scanned area AFM images of porous samples obtained
TFM 2010 Discoverer instrument. The microscope was operated in from polycrystalline layers of 共a兲 x ⫽ 0 and 共b兲 x ⫽ 0.38 by anodization at
contact mode using a Si3 N4 tip and interaction forces ca. 0.02 nN. 10 mA/cm2 for 20 s. The scanned area is the same in both cases, thus allow-
Photoluminescence was measured in the scanning mode at room ing direct comparison between the structures.
temperature, under the excitation of the 488 nm line of an Ar⫹ laser.
The laser beam was focused onto the sample surface using a micro-
scope objective. The emitted light was also collected by the objec-
tive lens and driven to the monochromator, where it was analyzed 共RMS兲 of up to 5 nm is found, and the vertical nanometric columns
and detected by a photomultiplier tube cooled by a Peltier stage. The seem to be not as well defined as they were for porous poly-Si. The
sample was mounted on a motorized X-Y stage. To obtain two di- etching rate appears to be nonuniform in the whole area, and some
mensional monochromatic maps, a narrow spectral window was se- depressions and voids are formed. The size of these structural fea-
lected in the monochromator and the sample was moved using the tures is in agreement with the grain size of the starting poly-SiGe
X-Y stage. Local spectra were also obtained at selected points of the films, which is around 300 nm for this composition, pointing to a
samples. The beam diameter on the sample surface is around 1 ␮m. preferential etching at the grain boundaries. These results evidence
Microraman spectroscopy measurements were carried out with a that the final structure depends on the crystallographic quality of the
DILOR X-Y Raman spectrometer, exciting with the 514.5 nm line starting layers. Similar result has been reported for porous poly-Si.13
of an Ar⫹ laser. The beam size at the focus was slightly smaller than As-anodized samples with x ⫽ 0.55 show a cracked quasi-
1 ␮m in diam. The detection was done with a liquid nitrogen refrig- continuous layer on their top that do not allow to reveal the porous
erated CCD multichannel detector. The Raman spectra were re- structure by AFM 共not shown兲. Wong et al. reported that a crystal-
corded in selected areas revealed by the PL maps in view to corre- line silica layer is grown on the top of the as-anodized porous
late luminescence and structure. poly-Si.8
Composition and nanocrystal size.—Micro-Raman measure-
Results and Discussion ments were carried out to establish a relation between the structure
Morphology.—After the electrochemical etching, the porous lay- and the electrochemical etching parameters. The Raman spectrum
ers presented a dark aspect to the naked eye, revealing the existence provides information about several aspects relevant to the porous
of a rough surface. The morphology of the porous layers was char- structures. In particular, composition, and crystal size can be
acterized by AFM. Square areas with 1 ␮m side were scanned. For studied.18 The results reported by other authors about the effect of
samples with x ⫽ 0 and low anodization current density and time the forming process on the composition of the porous alloy layers
(10 mA/cm2 and 20 s兲 the surface was very homogeneous. The 3-D appear disperse, it has been reported that: the Ge fraction in the
AFM image of the scanned area shown in Fig. 1a reveals the for- alloy 共initially x ⫽ 0.5) decreases after the anodization at
mation of island-like structures around 55 nm wide and 6 nm high, 20 mA/cm2 for 10 min 共suggesting preferential etching of Ge兲,19 it is
which corresponds to the expected morphology of porous Si. More- maintained after anodization of epitaxial SiGe layers with Ge frac-
over, the morphology analysis leads to surface roughness values tions up to x ⫽ 0.2,5 and finally, that it increases after stain etching
共RMS兲 of 1.7 nm, in good agreement with previously reported data of the SiGe alloys with initial Ge fraction of x ⫽ 0.25.20
for porous silicon.17 Drastic morphological changes are observed in Raman spectra of a sample with x ⫽ 0 before and after etching
the samples based on the SiGe layers. For samples of x ⫽ 0.38 with a current density of 10 mA/cm2 for 20 s are shown in Fig. 2.
anodized with 10 mA/cm2 for 20 s 共see Fig. 1b兲, surface roughness For this low value of the current density, the porous poly-Si presents
C328 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲
Figure 2. Raman spectra of a Si sample before 共a兲 and after 共b兲 etching the
original polycrystalline layer at 10 mA/cm2 for 20 s to form the porous
poly-Si sample. The distance between ticks in the vertical axis represents 500
counts.
phonon confinement as observed by the down frequency shift of
around 2 cm⫺1 and the asymmetric broadening of the TO Si-Si Ra-
man band. The estimated size of the Si nanocrystals, after subtract-
ing the contribution of the substrate, is close to 5 nm. In porous
SiGe samples prepared by etching layers of x ⫽ 0.38 with
10 mA/cm2 for 20 s, one cannot appreciate a significant phonon
confinement effect since the Raman bands are neither down shifted
nor broadened after the anodization, see Fig. 3. This means that
crystal sizes below 10 nm are not dominant. This is consistent with
the AFM data, that reveal smaller structures for Si than for SiGe, as
shown in Fig. 1. At this low anodization current density
(10 mA/cm2 ), one cannot appreciate Ge enrichment and basically
the Raman spectra indicate that the composition of the layer is con-
served after the anodization process.
Figure 4a shows two examples of Raman spectra obtained in a
sample with x ⫽ 0.38 anodized using a current density of
Figure 3. Raman spectra of a SiGe sample with x ⫽ 0.38 before 共a兲 and
after 共b兲 etching the original polycrystalline layer at 10 mA/cm2 for 20 s to
form the porous poly-SiGe sample. The distance between ticks in the vertical
axis represents 100 counts. The spectra have been shifted for a sake of
clarity.
Figure 4. 共a兲 Raman spectra obtained at two different points of a porous
poly-SiGe sample obtained from a SiGe layer of x ⫽ 0.38 using a high
anodization current density (80 mA/cm2 ) for 9 s. The distance between ticks
in the vertical axis represents 100 counts. The spectra have not been shifted.
Note the full enrichment of Ge and the two components of the Ge-Ge band.
共b兲 Plot of the Ge-Ge peak frequency as a function of the peak fwhm. The
data are obtained from several spectra taken at different points of the sample.
80 mA/cm2 for 9 s. These spectra evidence a complete enrichment
of Ge, since the Si-Ge and Si-Si related bands are no more observed,
during the anodization. The Ge-Ge band consists of a peak around
296 cm⫺1 and a broad shoulder in the low wavenumber side. The
first peak corresponds to Ge nanocrystals less than 5 nm in diameter,
while the broad band seems to correspond to either a Ge amorphous-
like phase or very small Ge nanocrystals. Figure 4b shows the peak
frequency (⬇296 cm⫺1 for nanocrystalline Ge兲 vs. the full-width at
half-maximum 共fwhm兲 plot obtained from a set of Raman spectra,
similar to those shown in Fig. 5a, recorded at different regions of
this sample. There is a linear correlation between both parameters
that demonstrates that the estimated crystal sizes are distributed in
the interval between 4 and 7 nm. Note that the presence of the broad
band in the low energy side accounts for the presence of even
smaller crystal sizes.
The Raman spectra corresponding to porous samples obtained
from a polycrystalline layer with x ⫽ 0.55 by anodization at
20 mA/cm2 共which can be considered a low value in the interval
considered here兲 for 25 s and at 80 mA/cm2 for 9 s are shown in Fig.
5, together with the reference spectrum acquired before the sample
was etched. A down frequency shift and an asymmetric broadening
 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲
Figure 5. Raman spectra of SiGe samples with x ⫽ 0.55 共a兲 before and 共b兲
after anodization at 20 mA/cm2 for 25 s or 共c兲 at 80 mA/cm2 for 9 s. The
distance between ticks in the vertical axis represents 100 counts. The spectra
have been shifted for a sake of clarity. Note the progressive down frequency
shift and the asymmetric broadening of the bands as the etching current
density increases.
of the Raman bands, indicating phonon confinement effects, is also
observed. These effects are stronger as the current density increases.
No amorphous-like contribution are observed. Some Ge enrichment
of the crystals keeping the alloy nature of the layer and phonon
confinement is detected. This suggests that the lower reactivity of
Ge reinforces the Si-Ge bonds, more abundant at this composition,
partially inhibiting the etching of the silicon atoms. No bands related
to trigonal GeO2 were found in any of the samples studied.21 The
increase of the anodization time also results in a broadening and
down frequency shifting of the Raman bands. See Fig. 6 for the
influence of the etching time at 80 mA/cm2 in the Raman spectrum
of a sample with x ⫽ 0.55, which reveals the presence of smaller
Figure 6. Raman spectra of porous poly-SiGe samples obtained from a
polycrystalline layer with x ⫽ 0.55 by anodization at 80 mA/cm2 for two
different times, 共a兲 6 and 共b兲 9 s. The distance between ticks in the vertical
axis represents 100 counts. The spectra have been shifted for a sake of
clarity. Note the progressive down frequency shift and the asymmetric broad-
ening of the bands as the etching time increases.
C329
Figure 7. PL spectra of porous samples obtained from polycrystalline layers
with x ⫽ 0, 0.38, and 0.55. The samples were anodized at 10 mA/cm2 for 20
s in all cases. The spectra have been shifted for clarity. The positions of the
two bands have been marked 共see text兲.
size crystallites for increasing anodization time. Therefore, the size
of the nanocrystals can be reduced either by increasing the current
density or the time of the electrochemical etching.
Photoluminescence emission.—Typical photoluminescence spec-
tra of samples with different compositions anodized at 10 mA/cm2
during 20 s are shown in Fig. 7. The spectrum consists of a broad
band that can be fitted by at least two Gaussian subbands, labeled
B-1 and B-2, respectively. Band B-1 is centred around 635-640 nm
共1.95 eV兲 and its fwhm is between 230 and 260 meV. The center of
band B-2 is located around 708 nm 共1.75 eV兲 and its fwhm ranges
from 160 to 200 meV. There is not a consistent relation between the
spectral parameters 共intensity, peak wavelength and linewidth兲 and
the composition of the layers. The energies of these bands lie in the
range of energies reported by other authors for porous SiGe formed
on epitaxial layers.2,5,6 It should be noted that the porous poly-SiGe
samples practically show the same spectrum than the Si ones,
and that for the large range of compositions inspected
(0 ⬍ x ⬍ 0.55), no consistent peak shift was observed although
the band gap of monocrystalline SiGe with a Ge fraction of
x ⫽ 0.55 is 0.2 eV narrower than the one of pure Si.
The luminescence emission for samples anodized at high current
density showed the same spectral shape as the one obtained for
lower anodization current, with some intensity variations, see Fig. 8.
The high energy peak, B1, seems to be reinforced. However, a clear
shift of the peak energy to the blue is not observed; therefore the
crystal size reduction, for high current densities, is not accompanied
by a concomitant shift of the emission spectrum toward higher en-
C330 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲
Figure 8. PL spectra of porous samples obtained from polycrystalline layers
with x ⫽ 0.38 and 0.55 for two different anodization conditions (80 mA/cm2
for 9 s and 10 mA/cm2 for 20 s兲. The two sets of spectra have been shifted
for clarity.
ergies, as it would be expected if excitonic recombination is the
main luminescence mechanism.
The spatial uniformity of the luminescence emission over the
sample area was also analyzed. Monochromatic PL maps acquired at
1.87 eV for samples electrochemically anodized with a current den-
sity of 10 mA/cm2 during 20 s are shown in Fig. 9. The emission in
the sample with x ⫽ 0 is rather homogeneous through the whole
area, a detail is displayed in Fig. 9a. Porous poly-SiGe samples
show a more inhomogeneous luminescence intensity distribution at
the mm scale. See for example the PL distribution for a porous
sample formed using a layer with x ⫽ 0.55 (10 mA/cm2 , 20 s兲
shown in Fig. 9b, which shows a strong emission in the center and
weak luminescence in the meniscus region, probably due to a lower
current density in this region during anodization. Luminescence
nonuniformity at large scale was a common feature to all the porous
poly-SiGe layers studied, illustrating the difficulties of the anodiza-
tion process in these layers compared to Si. However, ignoring the
small center and the meniscus regions, luminescence intensity is
rather homogeneous in the other parts of the samples. The inhomo-
geneity was already observed by micro-Raman measurements, see
Fig. 4a. The regions of the sample with a high luminescence inten-
sity show phonon confinement effects. Figure 10 shows two Raman
spectra 共Ge-Ge band兲 corresponding to different regions of a porous
sample (x ⫽ 0.55, 20 mA/cm2 , 25 s兲 with different luminescence
emission intensities. There is a clear asymmetric broadening and
downshift of the Raman bands of the spectra acquired in the regions
of high PL intensity. This result suggests that the existence of small
nanocrystals has a beneficial effect on the intensity of the lumines-
cence emission.
The origin of visible PL emission in these porous poly-SiGe
samples can be analyzed based on the different results presented up
to now. The Raman spectra show that there are phonon confinement
effects in the samples, depending on the anodization conditions.
Nanocrystals from a few nm 共2-3 nm兲 to 10 nm 共limit of the Raman
sensitivity兲 are estimated 共see Fig. 2, 4a, 5, and 10兲. The indepen-
dence of the PL spectra on the composition of the porous poly-SiGe
films and on the size of the nanocrystals exclude exciton recombi-
nation inside the nanocrystals as the source mechanism for lumines-
cence. Although the expected shift due to the composition could be
compensated by the reduction in the crystallite size, such an exact
matching of the two effects over the analyzed composition range
appears unlike. Furthermore, we did not found any PL peaks related
with porous Ge, either the peak at 1.17 eV reported in as-anodized
Ge or the 2.1 eV peak presented in oxidized porous Ge, associated
with localized states at or near the Ge-GeO2 interface,21-23 even in
the porous layers formed by anodization of low Ge fraction samples
at high current density, which are formed mostly by Ge nanocrys-
tals. Also, no band related with GeO2 was detected in the Raman
spectra of the samples; therefore pure Ge nanocrystals and Ge-GeO2
interfaces can also be excluded as the origin of the PL. Finally, the
luminescence cannot be associated with either the band tail states of
the amorphous phase since the amorphous phase was not detected in
some of the Raman spectra.6,24
The remainder recombination mechanisms can be recombination
at defects in the crystalline structure of the porous film, which has
been reported even for porous layer formed from monocrystalline
SiGe, and recombination at electronic states located at the interface
between nanocrystals and the surrounding native SiO2 grown due to
the exposure of the samples to the atmosphere. The first of these
mechanisms could play a more important role in our porous layers
than in the work of Schoisswohl et al., due to the higher density of
defects expected in our porous layers, because the original films
were polycrystalline instead the crystalline layers.5 Also, the Gauss-
ian shape of the PL spectra spectra is feature ascribed to a localized
state.25 However, at the present time we don’t have enough data to
exclude the recombination at states located at the interface between
the nanocrystals and a native oxide (SiO2 ) grown by the air expo-
sure of the samples. Note that interface states must be present, be-
cause some of the layers presented regions with very low lumines-
cence emission, which supports the formation of states of different
nature either radiative or nonradiative.
Conclusions
Porous poly-SiGe layers were fabricated by electrochemical an-
odization of unintentionally doped polycrystalline SiGe layers ob-
tained by LPCVD and solid phase crystallization. The luminescence
of these as-anodized porous poly-SiGe structures, with no additional
treatments, has been demonstrated. A wide range of Ge fractions
(0 ⬍ x ⬍ 0.55) and anodization current densities (10-80 mA/cm2 )
was used. The composition of the porous films depends on the com-
position of the original polycrystalline layer, and on the etching
parameters. The morphology of the films seems to depend on the
crystalline characteristics of the starting material. For low current
densities, the composition of the porous poly-SiGe films show a
light Ge enrichment in relation with the starting polycrystalline SiGe
layer; the same behavior is observed for samples with high Ge frac-
tions anodized with higher current densities. Samples with low Ge
fractions anodized at high current density show a very substantial
Ge enrichment. The nanocrystal size decreases for increasing current
densities and etching times. The visible luminescence spectra were
not dependent on the composition and only showed a weak depen-
dence on the anodization process parameters, which excludes exci-
ton recombination inside the nanocrystals as the main radiative re-
combination mechanism. Luminescence can be interpreted in terms
of recombination at defects inside the nanocrystals or at interface
states associated with the interface nanocrystal/native SiO2 . New
 Journal of The Electrochemical Society, 151 共5兲 C326-C332 共2004兲
Figure 9. Monochromatic 共1.87 eV兲 PL maps of porous samples obtained from layers of 共a兲 x ⫽ 0 and 共b兲 x ⫽ 0.55 by anodization at 10 mA/cm2 for 20 s.
For x ⫽ 0, the scanned area is 1.2 ⫻ 2.2 mm2 and the intensity scale ranges from 0 to 1.77 in arbitrary units. For x ⫽ 0.55, the scanned area is 3.0
⫻ 5.6 mm2 and the intensity scale ranges from 0 to 2.9 in arbitrary units.
Figure 10. Raman spectra 共Ge-Ge band兲 at two different points of a porous
poly-SiGe sample obtained from a polycrystalline layer with x ⫽ 0.55 by
anodization at 20 mA/cm2 for 25 s. The two regions exhibit different PL
emission intensities in the monochromatic 共1.87 eV兲 PL map. Spectrum 共a兲
corresponds to a region of low PL intensity. Spectrum 共b兲 corresponds to a
region of high PL intensity. The distance between ticks in the vertical axis
represents 100 counts. The spectra have been shifted for a sake of clarity.
C331
research on porous SiGe layers undergoing post-growth treatments
are now in progress in order to elucidate the origin of the
visible luminescence emission and the possibility to get excitonic
recombination.
Acknowledgment
This work was funded by Spanish government through C. I. C. y
T. project MAT2001-2446-C04-01.
Universidad Politécnica de Madrid assisted in meeting the publication
costs of this article.
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