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3
rd
Iranian Conference on Photonics Engineering
International Center for Science, High Technology &
Environmental Sciences, 8-9 February 2011.


Synthesis and Characterization of p
+
Porous Silicon Layers for
Optical Waveguide Applications




Abstract: Using porous silicon is an attractive
preposition for making optical waveguides because of
its porosity controllability which leads to tuneable
refractive indices. In this study, we prepared a series of
p
+
porous silicon samples electrochemically at different
conditions. Then we investigated the effect of
fabrication parameters on the morphology and
structural features of fabricated PS layers by FESEM
and AFM analysis. The observed relationships among
the fabrication parameters, geometry and morphology
were discussed, and a simplified model is suggested.

Keywords: AFM, FESEM, Morphology, Optical
Waveguides, Porous Silicon

1 Introduction

Porous silicon is a material which has new aspects
for photonic devices fabrication and it is
compatible with established standard
microelectronics technology that enables advances
in silicon-based devices [1]. PS is characterized by
porosity, pores and Si branches size, and their
distributions. These individualities can be varied
by controlling the current density, the type and
concentration of dopant, the crystalline orientation
of the wafer, and the electrolyte concentration [2].
The accurate control of layer porosity and
thickness allows the modification of optical
properties of porous silicon (like refractive index)
and causes it attractive for a multitude of
applications in advanced optoelectronics
technology such as photonic crystals [3],
microcavities, waveguides [4], and photodetectors
[5]. In our previous work, we investigated the
photoresponse of Metal/PS/Si structure, where it
was shown that the highest photosensitivity
(photocurrent) is at the wavelength of 540 nm
[6].
2 Experimental Procedure

PS single layer samples were fabricated of single
crystalline Si wafers single polished boron-doped
(100) of resistivity 0.005-0.01 cm by
electrochemical anodization in different
conditions. Electrolyte used in our experiment had
composition of HF (40%) and Ethanol (99%) in
1:1 (S
1
) and 5:3 (S
2
) volume ratios. Before
fabrication, back side of the wafers were coated
with Al and then annealed in an oven with 300
o
C
temperature to improve ohmic contact and
homogeneity of the layer [6]. Then they were
covered by silicon paste to protect them from acid
attack. All samples were cleaned in CCl
4
and
ethanol before anodization. Samples were placed
in vertical PVC cell and Pt electrode was used as a
cathode. Anodization current density and duration
was adjusted to be constant during process by the
use of galvanic power supply. Process is done in a
room temperature and room light. An ultrasonic
device was used to remove hydrogen bubbles to
improve homogeneity of the film.
Thickness and porosity of the fabricated layers
were measured by gravimetric method. In this
method before fabrication of layers the weight of
the sample was measured and termed as m
1
. Then
anodization was performed and samples were
rinsed in deionized water after the reaction and
then dried by clean air. Then prepared samples
weighted to determine m
2
. Next, they stirred in
NaOH 1 M to dissolve PS layer completely and
A.Shokrollahi

abbas2516@gmail.com
M.Zare

mar.zare@gmail.com
F.E.Seraji

feseraji@itrc.ac.ir



178
finally the net weight (m
3
) was measured. Porosity
is defined and calculated as the fraction of voids in
the PS layer, i.e. . The
thickness of the formed PS layer is also:
where S is the area of
sample and is density of Si .
Surface morphologies of PS were examined by
Hitachi-S-4160 Field Emission Scanning Electron
Microscope. Moreover, the mean pore size and
thickness of film were obtained from FESEM
imaging.
The roughness and mean value height of PS film
and original Si polished wafer were also
characterized by AFM.

3 Experimental Results

3.1 PS layers characterization using
gravimetric method
The porosity and thickness of the PS layer depends
strongly on fabrication parameters like current
density, duration and electrolyte composition [7].
Characteristic of various PS samples with different
anodization parameters are presented in table 1.

Table 1. PS layers characteristics
Layer
thickness
(m)
Porosity
(%)
HF:EtOH Etching
time
(s)
Current
density
(mA/cm
2
)
Sample
NO
3.70 51 5:3 100 100 1
4.25 60 5:3 100 200 2
6.40 67 5:3 100 300 3
5.50 60 5:3 200 200 4

Comparison of samples 1, 2 and 3 of Table 1
shows dependence of porosity on current density
when duration and concentration of electrolytes
were kept constant. These results show how the
porosity and thickness of the layer increases from
51% to 67% and 3.70 m to 6.40 m respectively,
when current density is raised from 100 mA/cm
2
to
300 mA/cm
2
in constant etching time. The
refractive index of the layer also depends on
porosity using Bruggman method [8]. Therefore,
we could tune refractive index by controlling
porosity.
Dependence of thickness on etching time is also
identified in samples 2 and 4 of Table 1. Current
density and electrolyte concentration was also kept
constant for these two samples. It appears that
when etching time is raised for 100 s, the thickness
of PS layer is also incremented from 4.25 m to
5.50 m. This observation is consistent with the
report [9] that after initial pore formation, change
of pore diameter is not observed and the depth of
the porous silicon layer becomes deeper.
3.2 PS layers characterization using FESEM
Field Emission Scanning Electron Microscopy was
used to study the structural and morphological
quality of the prepared layers. Cross-sectional view








Fig.1. Cross-sectional SEM images of porous silicon formed in the p
+

silicon wafer in electrolyte containing of HF and ethanol in 5:3 ratio at
current density of a) 200 mA/cm
2
in 100s, b) 300 mA/cm
2
in 100s, c)
200 mA/cm
2
in 200s. d) enlarge view of a). of porous silicon layer
prepared at current density of 200mA/cm
2
(sample 2) and 300 mA/cm
2

(sample 3) in (S2) electrolyte are depicted in Fig. 1(a) and (b),
respectively.
a
b
c
d



179
Moreover, the image of sample 4 with current
density of 200 mA/cm
2
and anodization time of
200 s is shown in Fig 1(c) for better comparison
with sample 2 that has the same condition except
for duration. The pattern provided in Fig. 1(d) was
obtained at an enlarged scale from a certain PS
area in Fig. 1(a). From the cross-sectional image
shown in Fig. 1, formation of vertical aligned
porous structures perpendicular to the PS surface
and distinct interface of porous and original silicon
layers are observed. Comparison of Figs.1(a) and
1(b), appeared that higher current density in
constant anodization time in the same electrolyte
has caused higher porosity (and consequently
lower refractive index) and slightly thicker layer in
consistent with results in part 3.1. The diameter
and depth of pores also increases with increasing
current density.
To investigate the effect of anodization time on
morphological and structural features of prepared
PS layer, Fig 1(c) is shown in comparison with Fig
1(a) that has the same condition except for
duration. It appears that improving anodization
time leads to thicker PS layer in agreement with
the results in part 3.1.
We find that the morphology of PS has not
changed in Figs 1(a) , 1(b) and 1(c) and vertically
aligned structures in (100) direction are observed
in three images.
The pore diameters of such anodized Si material
were evaluated, ranging from 30 to 50 nm in all the
samples. This observation agrees with the report
that etching of highly doped Si in aqueous
electrolytes always produces n+/p+ mesopores
[10].

3.3 PS layers characterization using AFM

The topography of the PS films was characterized
using atomic force microscopy (AFM). For this
purpose, several samples with different
circumstances have been examined: a) Si wafer
before anodization, b and c) two PS films etched at
two different electrolytes (S
1
, S
2
) in the same
current density and time.
As can be seen in Figure 2(a) in crystalline Si the
surface is almost smooth and homogen, except for
some regions where crystallites spikes are
unevenly observed. The rms roughness and mean
height of Si surface is 0.260 nm and 1.420 nm,
respectively.
Fig. 2(b) and (c) shows clearly that the etching of
Si in an ethanoic solution of different HF
containing at current density of 200 mA/cm
2
for
100 s leads to a well defined mesoporous surface
and the roughness and inhomogenity of the surface
is increased as expected.
The average roughness of PS surface in Fig 2(b),
obtained with 1:1 HF and ethanol electrolyte, is
0.98 nm while in Fig 2(c), the roughness is 3.89
nm for 5:3 HF:ethanol electrolyte.





Fig 2. 3D-Top view of single crystalline p
+
-type Si wafer polished
(100) of resistivity 0.005-0.01 cm. b) PS layer formed in 1:1
HF:ethanol solution anodized at J=200 mA/cm
2
for 100 s. c) PS layer
formed in 5:3 HF:ethanol solution anodized at J=200 mA/cm
2
for 100
s.

As appeared in Figs 2(b) and 2(c), pores and Si
structures are intensive and arranged in good order
in sample anodized in S
1
. Although in sample
prepared in S
2
, the surface is covered of large
crystallites, furthermore in some regions a macro
structure is appeared abruptly and a vast hole can
be seen nearby. Consequently, the rms roughness
in sample etched in greater HF concentration is
more than the sample in S
1
electrolyte.
a
b
c



180
Comparison of Figs 2(b) and 2(c) also shows the
sample with greater acid concentration would be
expected to yield the larger pores and crystallites
sizes. Moreover, mean depth of pores in Fig 2(b) is
4.34 nm that was fairly decreased compared to
sample Fig 2(c) which is 26.06 nm.

4 Discussion

According to the results shown in our experiment,
the formation of porous silicon is determined by
the competition of oxidation of the silicon surface
and etching of oxidized Si. Silicon is oxidized to
Si(OH)
4
or SiO
2
with the reaction with OH
-
in our
experiment, and the oxidized form of silicon is
dissolved in HF. Therefore, reaction equations are
summarized as follows [11]:
Si + 4OH
-
+ nh
+
Si(OH)
4
+ (4-n) e
-
(1)
Si(OH)
4
SiO
2
+ 2 H
2
O (2)
SiO
2
+ 6HF H
2
SiF
6
+ 2H
2
O (3)
Eqs. (1) and (2) describe the oxidation of silicon
via Si(OH)
4
. Then, oxidized silicon is etched by
HF, and pore is formed by Eq. (3).
During the anodization, the silicon surface is
etched by the competition of oxidation and etching
process. In our experiment the resistivity of the Si
wafer is very low and the current density is high
so, oxidation occurs rapidly. Anions such as F
-
and
OH
-
, are attracted to the silicon anode during the
anodization process. Because electronegativity of
F
-
is stronger, F
-
ion accumulates more near the
silicon surface [12]. When current density
increases, first two reactions accelerate and
because of enough F
-
ions in the Si/electrolyte
interface the porosity and etch rate raise. Besides,
the increase in HF concentration in our experiment
may accelerate F
-
ion distribution near the silicon
surface. Therefore, when HF concentration
increases, the pore formation occurs rapidly and
deep pores are developed.

5 Conclusion

We have explored the effect of fabrication
conditions on porous silicon films formed by
anodization of p
+
silicon at high current density in
ethanoic HF by different methods.
The gravimetric method and FESEM show the PS
layer thickness is in the micrometer range and it
improve with increasing anodization time. It is
recognized that porosity of the layer becomes more
when applied current density is increased.
The FESEM and AFM analyses indicate that the
films are mesoporous but may exhibit a variety of
macromorphologies in higher percentage of HF in
electrolyte. Increment in acid concentration, also
causes an increase in the roughness of the surface
and mean depth of holes.
We interpret our results in such a way that the
formation of porous silicon depends on two
reactions. First oxidation of the silicon surface and
then etching of oxidized Si.
Increasing both of applied current density and HF
concentration may accelerate pore formation due to
rise of oxidizing species and etching species,
respectively.
The dependence of refractive index on porosity of
the PS layer is a valuable relation which able us to
use the results obtained in this paper for fabricating
optical waveguides.

Acknowledgements

This paper has been performed using financial support of Islamic
Azad university of Khomeinishahr. The authors would like to express
their sincere thanks to them.

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