# Effect of HF Concentration on Physical and Electronic Properties of Electrochemically Formed Nanoporous Silicon

Authors: Pushpendra Kumar; Peter Lemmens; Manash Ghosh; Frank Ludwig; Meinhard Schilling
Journal: Journal of Nanomaterials
 (2009)

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## Abstract

The most common fabrication technique of porous silicon (PS) is electrochemical etching of a crystalline silicon wafer in a hydrofluoric (HF) acid-based solution. The electrochemical process allows for precise control of the properties of PS such as thickness of the porous layer, porosity, and average pore diameter. The effect of HF concentration in the used electrolyte on physical and electronic properties of PS was studied by visual color observation, measuring nitrogen sorption isotherm, field emission type scanning electron microscopy, Raman spectroscopy, and photoluminescence spectroscopy. It was found that with decrease in HF concentration, the pore diameter increased. The PS sample with large pore diameter, that is, smaller nanocrystalline size of Si between the pores, was found to lead to a pronounced photoluminescence peak. The systematic rise of photoluminescence peak with increase of pore diameter and porosity of PS was attributed to quantum confinement. The changes in nanocrystalline porous silicon were also clearly observed by an asymmetric broadening and shift of the optical silicon phonons in Raman spectra. The change in electronic properties of PS with pore diameter suggests possibilities of use of PS material as a template for fundamental physics as well as an optical material for technological applications.


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## Body

## 1. Introduction

Porous silicon (PS) has attracted great interest both
from fundamental physics [1–3] point of view as well as its technological
applications in biological and chemical sensors, light emitting diodes,
microdevices, and photoelectric solar batteries [4–8]. The PS can be prepared by
the electrochemical anodization etching technique [9], stain etching processes [2]
in a hydrofluoric acid-based solution, and a hydrothermal etching technique [10]
in a hydrofluoric acid free solution. Depending on the etching parameters, for
example, current density, HF concentration, substrate doping type, and level, the
physical properties of PS can be varied [11]. Therefore, porous silicon is also
particularly suitable in order to study the influence of spatial confinement on
fundamental properties of pore condensed matter as a function of pore geometry
parameters [12–15]. The conditions for the formation of PS on all types of
substrates in terms of current density and HF concentrations were reported by
Zhang et al. [16], where they have
shown that the formation of PS occurring during anodization was found to be
dependent on the nature of electrochemical reactions. Numerous theories on the
formation mechanisms of PS have been reported since its discovery. Beale et
al. [17, 18], Smith et al. [9, 19],
Zhang et al. [16, 20], and
Unagami [21] have proposed models to interpret the mechanisms responsible for
producing porous silicon. Even though the mechanisms were different, almost all
the investigators believed that the existence of holes is a prerequisite in
proceeding the electrochemical polishing or formation of porous silicon. The discovery
of the photoluminescence (PL) of PS by Canham in 1990 [22] has triggered a
large-scale investigations on PS materials including their
interfaces, structure, temperature dependence, and electroluminescence
properties [23–27]. The electroluminescence property of PS was
reported by Lehmann and Gösele [28], where
they have shown that the red color of PS changes to yellow color by increase in
applied current density during etching and this change in color was attributed
to quantum confinement effect in silicon nanocrystalline between the pores. There are many theoretical evidence that quantum confinement due to
nanoscale-sized crystallites of Si results in the occurrence of PL in PS layers
[29–32]. Quantum size effects lead
to an increase in the band gap of the nanocrystals compared to single-crystal
silicon which could explain the visible luminescence properties [33]. To
further explore the occurrence of PL in PS, we have systematically studied the
quantum confinement effect in three different pore diameter PS samples. In this
paper, we report the effect of the composition of etching electrolyte on
physical and electronic properties of PS. The systematic studies of different
pore diameter PS was carried out by using the Brunnauer-Emmer-Teller model (BET)
on nitrogen absorption/desorption isotherm, photoluminescence, scanning
electron microscopy, and Raman spectroscopy.


## 2. Experimental Details

PS layers were prepared by electrochemical anodic
etching of a highly dopedP-type 〈100〉 oriented silicon
substrate with a resistivity of 0.01–0.02Ωcm. The
electrochemical cell was made of Teflon and the base plate was made of
aluminum. A silicon wafer was mounted at the base plate by using an O-ring
that allowed 7.0 cm2 of the Si surface to be exposed to the electrolytes
consisting of three different concentrations of 3 : 7, 4 : 6, and 6 : 4 by volume 48%
hydrofluoric acid (HF): 98% ethanol, respectively. Prior to each experiment,
the Si wafers were ultrasonically cleaned in propanol and acetone. The etching
current density 14.5 mA/cm2 was applied for 30 minutes. The
thicknesses of the porous layers determined with an optical microscope were in
the range of 20–25μm. The
prepared PS was then fixed into the homemade all-metal gas handling system (BET
setup) that is equipped with a membrane pressure gauge of 1000 mbar full scale
to study the physical properties of PS by measuring adsorption/desorption
isotherms of N2 in porous silicon at 77 K. The PL measurements were done
using a Hamamatsu TG-SWNIR, C9405CA spectrometer, and a laser diode exciting the
sample at a wavelength of 405 nm. Raman scattering experiments were
performed using the excitation line λ=532nm of a semiconductor laser in a quasibackscattering geometry. The laser power
of 5 mW was focused to a 0.1 mm diameter spot on the PS surface. The scattered
spectra were collected by a DILOR-XY triple spectrometer and a nitrogen cooled
charge-coupled device detector. For the measurements, the samples were placed
in a sample chamber which was evacuated or, alternatively, filled with helium
gas in order to suppress the low frequency Raman scattering by air and to
prevent possible laser-induced oxidation of PS layers. All measurements were
carried out at room temperature. The changes in surface morphology of three
different PS samples were investigated by using a field emission-type scanning electron microscope (FE-SEM)
(SUPRA35, Carl Zeiss NTS GmbH).


## 3. Results and Discussion

During electrochemical etching of silicon, the pore forms in silicon by
anodic polarization in aqueous HF solution, depending on the electrode
potential and HF concentration. Many theories for pore formation mechanism
have been reported in the literature [9, 17–21]. In general,
the porous silicon formation is considered to result from the inhomogeneous dissolution
of the silicon surface due to competing reactions: silicon oxide formation
followed by dissolution of the oxide versus a direct dissolution of silicon by
HF [34]. The illustrative equation of the overall process during the PS
formation can be expressed as follows:  (1)Si+2HF+2h+→SiF2+2H+,SiF2+4HF−→H2+H2SiF6. The etching rate is determined by the holes (h+)
accumulation in the adjacent regions of the HF electrolyte and Si atoms.The porous silicon was formed in homogeneously mixed
electrolyte composed of 3 : 7, 4 : 6 and 6 : 4 by volume 48% hydrofluoric acid: 98%
ethanol with constant applied etching current density of 14.5 mA/cm2 for 30 minutes. The mesoporous silicon prepared with different concentrations
of HF was characterized by nitrogen sorption isotherms, field emission-type
scanning electron microscope, photoluminescence spectroscopy, and Raman
spectroscopy.


### 3.1. Physical Properties of Porous Silicon

The physical properties of sample (a) (prepared in electrolyte
composition of 30% of HF and 70% of ethanol by volume, i.e., 3 : 7), sample (b)
(prepared in electrolyte composition of 40% of HF and 60% of ethanol by volume,
i.e., 4 : 6) and sample (c) (prepared in electrolyte composition of 60% of HF and
40% of ethanol by volume, i.e., 6 : 4) were investigated by measuring of nitrogen
adsorption/desorption isotherm at 77 K. Figure1 shows the nitrogen sorption
isotherm for the all three samples. In Figure 1 we plot the filling fraction f=N/N0, where N refers to the number of adsorbed N2 molecules and N0 to the number of particles necessary for a complete
filling of the porous layer, versus the reduced vapor pressure Pr=P/P0, where P0 represents the bulk vapor pressure of
nitrogen at 77 K and P the vapor pressure as measured with a capacitive
pressure gauge of 1000 mbar full scale after each adsorption step. In Figures 1(a)
and 1(b) three regions can be identified to study the physical properties of
these samples. The first step, that is, reversible multilayer growth on the pore
walls at small-reduced pressures gives access to the specific surface of the
porous host (surface per pore volume) via a generalization of the Langmuir monolayer
growth model towards heterogeneous adsorption of multilayers, established by Brunauer et al.  (BET model) [35].
The second part is a hysteretic region between adsorption and desorption branch
where the pores are filled by a capillary condensation process. The hysteresis
between adsorption and desorption branches is also typical for capillary
condensation. The third part, that is, plateau indicates the complete filling
of the pores, and the amount of liquid corresponding to the volume of the gas
adsorbed allows the determination of porosity. The
surface area and pore diameter were determined by using the BET equation given as follows: (2)P/P0υ(1−P/P0)=1υmc+c−1υmcPP0, where υ is the amount adsorbed at pressure P,P0 is the saturation pressure, υm is the amount adsorbed in a monolayer, and c is a constant related to the molar heat of adsorption of the first layer.Adsorption (ads.)∖desorption
(des.) isotherms of N2 at 77 K in PS
for the sample (a) (prepared with 3 : 7 ⇔ HF : ethanol), sample (b) (prepared with 4 : 6 ⇔ HF : ethanol) and sample (c) (prepared with 6 : 4 ⇔ HF : ethanol).
(a)(b)(c)Equation (2) has been used in gas sorption isotherms in porous matrix to
determine the υm and c from the slope and the intercept of
the straight line obtained from a plot of (P/P0)/υ(1−P/P0)
as a function of P/P0 shown in Figures 2(a)–2(c). The pore diameter, porosity, and specific surface area
of sample (a), (b), and (c) calculated from the nitrogen isotherm shown in Figure
1 by using BET analysis shown in Figure 2 are listed in Table 1. The pore
diameter and porosity of mesoporous silicon were found to decrease with an
increase of the HF concentration in the used etching electrolyte at constant
applied current density. The theoretical and experimental details concerning
decrease
of pore diameter and porosity with increase of HF concentration in etching
electrolyte have been reported by many researchers [16, 20]. In sample (c),
which has a pore diameter of 3 nm, the hysteresis was not found as shown in Figure
1(c) indicating that the very small-pores are not filled by capillary
condensations. The behavior of the sample (c) isotherm may be understood in
terms of a simple model; during multilayer adsorption at pore walls the pores
become filled by a meeting of the adsorbed films from opposing walls as also
reported in literature [36].Table 1
Variation of physical properties, shift, and broadening in
phonon peak of samples (a), (b), and (c).
Sample detailsElectrolyte (HF : ethanol)Pore dia.
(nm)Porosity
%Specific surface area
(m2/cm3)Raman shiftcm−1Peak widthcm−1(a)3 : 710544065168.3(b)4 : 68454335184.9(c)6 : 43309005194.2BET plots
of sorption isotherm of samples (a), (b), and (c).
(a)(b)(c)These observations were also supported by scanning
electron microscopy. An FE-SEM was utilized to study the surface morphology
of sample (a), (b), and (c). The pores in sample (a) are clearly observed, as
shown in Figure3(a). The pore diameter in sample (a), as obtained from Figure
3(a), was in the range of 8–12 nm. The pore diameter in sample (b) as obtained
from Figure 3(b) was found in the range of 6–10 nm while in sample (c) as
shown in Figure 3(c), the pore diameter is not so clear but could be expected in
the range of 2–4 nm. Since it is difficult to have good contrast for very small-pores by microscopy techniques therefore the aforementioned BET technique has
been frequently used to study such a small-pore matrix. The pore diameters
obtained from SEM are in agreement with the values obtained from nitrogen
sorption isotherms.FE-SEM plan views of sample (a), (b), and (c).
(a)(b)(c)


### 3.2. Visual Color Observations and Photoluminescence Study

In Figures4(a)–4(c) we show the color observation of
samples (a), (b), and (c): sample (a) shows the red color in transmission mode,
sample (b) violet color, and sample (c) is of grey color and opaque in
transmission mode. With changing the pore diameter from 3 nm to 10 nm the color
of porous silicon changes from grey to red. The different color of porous
silicon due to pore diameter was also reported by Lehmann and Gösele [28], where they have shown that with increase in pore
diameter, that is, decrease in silicon region between the pores results the shift of
red color to yellow. These observations are also supported by our
photoluminescence measurements. Photoluminescence is directly related to the
electronic structure and transitions. Differences in the electronic behavior
between bulk and low-dimensional semiconductors arise due to the difference in
the electron density of states, g(E). For example, g(E)
of a bulk semiconductor has a continuous dependence g(E)~E1/2,
whereas in two-dimensional semiconductors it has a step-like dependence on
energy. In one-dimensional semiconductor structures it diverges as E−1/2 and for zero-dimensional semiconductor it is a delta function of energy. The
characteristic change of the band gap with decrease in size of the
nanostructures can be studied using by the observation of the blue shift in the
photoluminescence peak position [37]. Thus, photoluminescence is useful in the
study of quantum confinement of electrons in low-dimensional materials [38, 39].
In Figures 5(a)–5(c) we show the PL spectra of samples (a), (b), and (c). It can be
seen from Figure 5 that sample (c) which has a pore diameter in the range of 3 nm does not show any PL peak. With an increase of the pore diameter however, the
PL signal starts to appear. In Figure 5(b) we can see a small intensity of PL
peak while in sample (a) as shown in Figure 5(a) we see a strong PL peak
around at 735 nm. Bulk silicon has an indirect band gap and does not show any
photoluminescence peak while porous silicon has direct band gap and shows a
photoluminescence peak at around 750 nm. Several mechanisms
have been suggested to explain the appearance of this luminescence signal, such
as defects that localize carriers at extrinsic centers or surface states
providing radiative recombination centers, surface hydrides (SiHx groups) or the formation of siloxene (an Si–O–H based polymer), or quantum confinement
effects of the excitons caused by their spatial confinement within the
Si-nanocrystallites. The latter mechanism was proven to be the origin of the
observed luminescence [40, 41]. The absence of PL from sample (c)
indicates that porous silicon with the pore diameter of 3 nm or less than that
behaves as bulk silicon where the silicon crystallites size between two pores
are too large to lead to an efficient quantum confinement. The absence of PL
signal from sample (c) and a strong signal from sample (a) indicates that the quantum
confinement effect in narrow silicon regime between two pores results in strong
PL signal.Visual color observation of
samples (a), (b), and (c).
(a)(b)(c)Figure 5
Photoluminescence spectra
of samples (a), (b), and (c).


### 3.3. Phonon Dynamics in the Si Pore Walls

In order to
explain the dramatic increase of the PL signal of the sample (a) compared to
sample (b) and (c), we have investigated the structural information of the
porous layer using Raman spectroscopy. Photoluminescence and Raman spectra of
porous silicon give the information of a cross-sectional view of silicon
nanocrystallites which remains between the pores, through the quantum
confinement effect. Raman spectroscopy has extensively been used to study the
structural, mechanical, and physical properties of PS [42].  It is an emission technique that involves
inelastic scattering of incident laser photons with crystal or molecular
vibrations and results in spectral peaks that are shifted from the incident
light. PS is composed of wires or dots of nonuniform dimensions. When the size
of c-Si is reduced to smaller dimensions, the shift and asymmetric broadening in
Raman peak is observed. A respective theoretical and experimental analysis of
Raman scattering for smaller dimension materials can be found in the literature
[43, 44]. In Figure 6 we show the phonon frequency of porous silicon samples
(a), (b), and (c). A peak shift was observed from 519 to 516cm−1 and
a broadening of the peak width full width at half maximum (FWHM) from 4.2
(symmetric) to 8.3cm−1 (asymmetric) with increases in pore diameter
from 3 nm to 10 nm, respectively. The shift of the phonon peak towards lower
wave number and broadening of the peak width with increase in pore diameter and
porosity is attributed to the confinement of optical phonons in nanodimensional
Si crystallites between the pores [45, 46]. On the basis of physical properties
obtained by BET and FE-SEM and information received from photoluminescence and
Raman spectroscopy, it is revealed that the appearance of strong PL peak with
increase in pore diameter is due to quantum confinement effect. Contributions
to PL from any kind of defect, localized state, or chemical bonding are unlikely.
Following the discussion above, it could be understood that PS can be used in two ways, first as a porous matrix template like in sample (c) with a small-pore diameter to study embedded guest molecule’s confinement effect in PS,
second PS itself as an optical material where a type of sample (a) could be utilized
to study the optical properties of PS.Figure 6
Raman spectra of samples (a), (b),
and (c).


## 3.1. Physical Properties of Porous Silicon

The physical properties of sample (a) (prepared in electrolyte
composition of 30% of HF and 70% of ethanol by volume, i.e., 3 : 7), sample (b)
(prepared in electrolyte composition of 40% of HF and 60% of ethanol by volume,
i.e., 4 : 6) and sample (c) (prepared in electrolyte composition of 60% of HF and
40% of ethanol by volume, i.e., 6 : 4) were investigated by measuring of nitrogen
adsorption/desorption isotherm at 77 K. Figure1 shows the nitrogen sorption
isotherm for the all three samples. In Figure 1 we plot the filling fraction f=N/N0, where N refers to the number of adsorbed N2 molecules and N0 to the number of particles necessary for a complete
filling of the porous layer, versus the reduced vapor pressure Pr=P/P0, where P0 represents the bulk vapor pressure of
nitrogen at 77 K and P the vapor pressure as measured with a capacitive
pressure gauge of 1000 mbar full scale after each adsorption step. In Figures 1(a)
and 1(b) three regions can be identified to study the physical properties of
these samples. The first step, that is, reversible multilayer growth on the pore
walls at small-reduced pressures gives access to the specific surface of the
porous host (surface per pore volume) via a generalization of the Langmuir monolayer
growth model towards heterogeneous adsorption of multilayers, established by Brunauer et al.  (BET model) [35].
The second part is a hysteretic region between adsorption and desorption branch
where the pores are filled by a capillary condensation process. The hysteresis
between adsorption and desorption branches is also typical for capillary
condensation. The third part, that is, plateau indicates the complete filling
of the pores, and the amount of liquid corresponding to the volume of the gas
adsorbed allows the determination of porosity. The
surface area and pore diameter were determined by using the BET equation given as follows: (2)P/P0υ(1−P/P0)=1υmc+c−1υmcPP0, where υ is the amount adsorbed at pressure P,P0 is the saturation pressure, υm is the amount adsorbed in a monolayer, and c is a constant related to the molar heat of adsorption of the first layer.Adsorption (ads.)∖desorption
(des.) isotherms of N2 at 77 K in PS
for the sample (a) (prepared with 3 : 7 ⇔ HF : ethanol), sample (b) (prepared with 4 : 6 ⇔ HF : ethanol) and sample (c) (prepared with 6 : 4 ⇔ HF : ethanol).
(a)(b)(c)Equation (2) has been used in gas sorption isotherms in porous matrix to
determine the υm and c from the slope and the intercept of
the straight line obtained from a plot of (P/P0)/υ(1−P/P0)
as a function of P/P0 shown in Figures 2(a)–2(c). The pore diameter, porosity, and specific surface area
of sample (a), (b), and (c) calculated from the nitrogen isotherm shown in Figure
1 by using BET analysis shown in Figure 2 are listed in Table 1. The pore
diameter and porosity of mesoporous silicon were found to decrease with an
increase of the HF concentration in the used etching electrolyte at constant
applied current density. The theoretical and experimental details concerning
decrease
of pore diameter and porosity with increase of HF concentration in etching
electrolyte have been reported by many researchers [16, 20]. In sample (c),
which has a pore diameter of 3 nm, the hysteresis was not found as shown in Figure
1(c) indicating that the very small-pores are not filled by capillary
condensations. The behavior of the sample (c) isotherm may be understood in
terms of a simple model; during multilayer adsorption at pore walls the pores
become filled by a meeting of the adsorbed films from opposing walls as also
reported in literature [36].Table 1
Variation of physical properties, shift, and broadening in
phonon peak of samples (a), (b), and (c).
Sample detailsElectrolyte (HF : ethanol)Pore dia.
(nm)Porosity
%Specific surface area
(m2/cm3)Raman shiftcm−1Peak widthcm−1(a)3 : 710544065168.3(b)4 : 68454335184.9(c)6 : 43309005194.2BET plots
of sorption isotherm of samples (a), (b), and (c).
(a)(b)(c)These observations were also supported by scanning
electron microscopy. An FE-SEM was utilized to study the surface morphology
of sample (a), (b), and (c). The pores in sample (a) are clearly observed, as
shown in Figure3(a). The pore diameter in sample (a), as obtained from Figure
3(a), was in the range of 8–12 nm. The pore diameter in sample (b) as obtained
from Figure 3(b) was found in the range of 6–10 nm while in sample (c) as
shown in Figure 3(c), the pore diameter is not so clear but could be expected in
the range of 2–4 nm. Since it is difficult to have good contrast for very small-pores by microscopy techniques therefore the aforementioned BET technique has
been frequently used to study such a small-pore matrix. The pore diameters
obtained from SEM are in agreement with the values obtained from nitrogen
sorption isotherms.FE-SEM plan views of sample (a), (b), and (c).
(a)(b)(c)


## 3.2. Visual Color Observations and Photoluminescence Study

In Figures4(a)–4(c) we show the color observation of
samples (a), (b), and (c): sample (a) shows the red color in transmission mode,
sample (b) violet color, and sample (c) is of grey color and opaque in
transmission mode. With changing the pore diameter from 3 nm to 10 nm the color
of porous silicon changes from grey to red. The different color of porous
silicon due to pore diameter was also reported by Lehmann and Gösele [28], where they have shown that with increase in pore
diameter, that is, decrease in silicon region between the pores results the shift of
red color to yellow. These observations are also supported by our
photoluminescence measurements. Photoluminescence is directly related to the
electronic structure and transitions. Differences in the electronic behavior
between bulk and low-dimensional semiconductors arise due to the difference in
the electron density of states, g(E). For example, g(E)
of a bulk semiconductor has a continuous dependence g(E)~E1/2,
whereas in two-dimensional semiconductors it has a step-like dependence on
energy. In one-dimensional semiconductor structures it diverges as E−1/2 and for zero-dimensional semiconductor it is a delta function of energy. The
characteristic change of the band gap with decrease in size of the
nanostructures can be studied using by the observation of the blue shift in the
photoluminescence peak position [37]. Thus, photoluminescence is useful in the
study of quantum confinement of electrons in low-dimensional materials [38, 39].
In Figures 5(a)–5(c) we show the PL spectra of samples (a), (b), and (c). It can be
seen from Figure 5 that sample (c) which has a pore diameter in the range of 3 nm does not show any PL peak. With an increase of the pore diameter however, the
PL signal starts to appear. In Figure 5(b) we can see a small intensity of PL
peak while in sample (a) as shown in Figure 5(a) we see a strong PL peak
around at 735 nm. Bulk silicon has an indirect band gap and does not show any
photoluminescence peak while porous silicon has direct band gap and shows a
photoluminescence peak at around 750 nm. Several mechanisms
have been suggested to explain the appearance of this luminescence signal, such
as defects that localize carriers at extrinsic centers or surface states
providing radiative recombination centers, surface hydrides (SiHx groups) or the formation of siloxene (an Si–O–H based polymer), or quantum confinement
effects of the excitons caused by their spatial confinement within the
Si-nanocrystallites. The latter mechanism was proven to be the origin of the
observed luminescence [40, 41]. The absence of PL from sample (c)
indicates that porous silicon with the pore diameter of 3 nm or less than that
behaves as bulk silicon where the silicon crystallites size between two pores
are too large to lead to an efficient quantum confinement. The absence of PL
signal from sample (c) and a strong signal from sample (a) indicates that the quantum
confinement effect in narrow silicon regime between two pores results in strong
PL signal.Visual color observation of
samples (a), (b), and (c).
(a)(b)(c)Figure 5
Photoluminescence spectra
of samples (a), (b), and (c).


## 3.3. Phonon Dynamics in the Si Pore Walls

In order to
explain the dramatic increase of the PL signal of the sample (a) compared to
sample (b) and (c), we have investigated the structural information of the
porous layer using Raman spectroscopy. Photoluminescence and Raman spectra of
porous silicon give the information of a cross-sectional view of silicon
nanocrystallites which remains between the pores, through the quantum
confinement effect. Raman spectroscopy has extensively been used to study the
structural, mechanical, and physical properties of PS [42].  It is an emission technique that involves
inelastic scattering of incident laser photons with crystal or molecular
vibrations and results in spectral peaks that are shifted from the incident
light. PS is composed of wires or dots of nonuniform dimensions. When the size
of c-Si is reduced to smaller dimensions, the shift and asymmetric broadening in
Raman peak is observed. A respective theoretical and experimental analysis of
Raman scattering for smaller dimension materials can be found in the literature
[43, 44]. In Figure 6 we show the phonon frequency of porous silicon samples
(a), (b), and (c). A peak shift was observed from 519 to 516cm−1 and
a broadening of the peak width full width at half maximum (FWHM) from 4.2
(symmetric) to 8.3cm−1 (asymmetric) with increases in pore diameter
from 3 nm to 10 nm, respectively. The shift of the phonon peak towards lower
wave number and broadening of the peak width with increase in pore diameter and
porosity is attributed to the confinement of optical phonons in nanodimensional
Si crystallites between the pores [45, 46]. On the basis of physical properties
obtained by BET and FE-SEM and information received from photoluminescence and
Raman spectroscopy, it is revealed that the appearance of strong PL peak with
increase in pore diameter is due to quantum confinement effect. Contributions
to PL from any kind of defect, localized state, or chemical bonding are unlikely.
Following the discussion above, it could be understood that PS can be used in two ways, first as a porous matrix template like in sample (c) with a small-pore diameter to study embedded guest molecule’s confinement effect in PS,
second PS itself as an optical material where a type of sample (a) could be utilized
to study the optical properties of PS.Figure 6
Raman spectra of samples (a), (b),
and (c).


## 4. Conclusions

By a combination of volumetric sorption isotherms,
visual color observation, photoluminescence, scanning electron microscopy, and
Raman spectroscopy, we studied the effect of HF concentration on physical and
electronic properties of porous silicon. It was found that porous silicon with
pore diameter of 3 nm or smaller does not show any photoluminescence while pore
diameter of 10 nm shows a PL peak of large intensity. From this we can conclude
that the porous silicon is not
only a potential candidate for new silicon-based optoelectronic devices but it
also enables the study of the electronic interaction on a nanometer scale
caused by quantum confinement effects.



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*Source: 728957-2009-05-14.xml*