Sensors and Actuators B 202 (2014) 897–912

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Porous silicon chemical sensors and biosensors: A review

Farid A. Harraz a,b,∗
a
Promising Centre for Sensors and Electronic Devices (PCSED), Advanced Materials and Nano-Research Centre, Najran University, P.O. Box: 1988, Najran
11001, Saudi Arabia
b
Nanostructured Materials and Nanotechnology Division, Central Metallurgical Research and Development Institute (CMRDI), P.O. Box: 87 Helwan, Cairo
11421, Egypt

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

Article history: The use of porous silicon (PSi) as a sensor for detection of various analytes is reviewed. The optical or
Received 19 January 2014 electrical properties of PSi are key sensing parameters that have been used in many chemical and bio-
Received in revised form 23 April 2014 logical sensing applications. PSi is a promising candidate due to ease of fabrication, large surface area,
Accepted 5 June 2014
various accessible pore sizes and morphologies, controllable surface modification and its compatibility
Available online 20 June 2014
with conventional silicon processing technology. The adsorption of chemical or biological molecules into
the pores modifies the electrical and/or optical properties, allowing convenient and sensitive measure-
Keywords:
ment approach. In this review, we provide a critical assessment of the development of PSi as a promising
Chemical sensors
Biosensors
material for chemical and biosensing applications. Formation procedures of PSi with various pore sizes
Porous silicon and morphologies are firstly given. Surface properties and structural characteristics of the material are
Optical briefly described. The recent progress on utilization of such porous structures in chemical and biosensing
Electrical applications is then addressed in the context of surface chemistry effects and nanostructures, measur-
ing approaches, operating concepts and device sensitivity and stability. Finally, concluding remarks with
existing challenges that hinder the material for commercial use are highlighted.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction H-passivated surfaces [10,11]. The anodization can be conducted

Porous silicon (PSi), which forms on the surface of crystalline
silicon substrates by anodization in hydrofluoric acid (HF), was
first observed by Arthur and Ingeborg Uhlir in 1956 at the Bell
Labs during the investigation of electrochemical methods for pol-
ishing germanium and silicon wafers [1]. Under certain etching
conditions, they observed black, brown, or red deposits formed
on anodized silicon wafers. At that time, they did not realize its
porous nature, but they proposed that the deposits consisted of
a silicon suboxide. It is now well-established that the electro-
chemical etching of crystalline silicon in HF-based solutions could
lead to the formation of different nano/macro-pore arrays of PSi
[2–7]. Different procedures have been developed and established
for the synthesis of various PSi layers. These include physical,
physicochemical, chemical and electrochemical techniques [8,9].
The electrochemical approach is considered the most appropri-
ate technique to produce homogeneous porous layers and stable
∗ Correspondence to: Promising Centre for Sensors and Electronic Devices
(PCSED), Advanced Materials and Nano-Research Centre, Najran University, P.O.
Box: 1988, Najran 11001, Saudi Arabia. Tel.: +966 75428888; fax: +966 75428887.
E-mail addresses: fharraz68@yahoo.com, fharraz@cmrdi.sci.eg
either under galvanostatic or potentiostatic mode, however oper-
ation at a constant current is preferable as it gives a better control
of the porosity for the fabricated layers [12].
Over many years, the technological interest in PSi is essentially
related to its extremely large surface-to-volume ratio and high
tendency for oxidation. PSi has been applied in a wide range of
applications, such as an insulating layer in the silicon-on-insulator
(SOI) [13,14], as a sensing layer in chemical sensors [15–18], a sac-
rificial layer in micromachining [19,20], in optoelectronic [21,22],
photovoltaic device and biomedical applications [23,24], and more
recently as templates for nanofabrication [25,26] and many others.
A variety of pore sizes ranging from a few nanometers up to a few
micrometers can be obtained during the silicon etching process,
depending on different operating parameters including the concen-
tration of HF in the electrolyte, the current density, the presence
of a surfactant, type and density of silicon dopants and illumina-
tion process, whereas the etching time determines mainly the pore
length [27,28]. It is generally accepted that the electrochemical
anodization of silicon/fluoride system is a self-limiting process and
occurs only at the interface between PSi and crystalline silicon sub-
strate, and hence the already etched porous layer is unaffected by
further electrochemical etching [17]. The porosity of the produced
PSi arrays can be controlled and modulated by adjusting the applied

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898 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
current. According to IUPAC classification, different categories of
PSi with different pore sizes are recognized; pore-diameters below
2 nm are referred to micropores, structures between 2 and 50 nm
are so called mesopores and pore-diameters greater than 50 nm
belong to the macroporous regime [29,30]. Although the structure
and pore morphology of PSi arrays have been intensively studied
using different methods, it is not so easy to predict, with accuracy,
which kind of structure will be formed in each case.
As mentioned above, one of the promising uses of PSi is the
sensing application. The motivation of using PSi as a sensing mate-
rial is related to its surface reactivity as well as the extremely large
surface area of porous structures. The morphology of PSi is also
important for sensing applications because the pore diameter limits
the size of the species that can be captured into the pores. The struc-
tures are usually fabricated by forming a porous layer on a silicon
substrate and creating an electrical contact to both PSi surface and
the rear face of the substrate or contacting on porous surface only.
Using these structures, a gas sensor based on current changes due to
the dipole moment of the gas [31] and a humidity sensor based on
the changing current with humidity [32] has been demonstrated.
Photonic bandgap (PBG) structures based on PSi have remark-
able optical properties that can be exploited for biosensing
applications. The optical properties of PSi PBGs are sensitive to
small changes of refractive index in the porous layers. Such changes
in the optical properties have been utilized to detect various types
of molecules such as DNA [33], protein [34], Gram-negative bacte-
ria [35] and enzyme [36]. In our previous works, we have fabricated
one-dimensional photonic crystal based on PSi and utilized the
structures for sensing different types of organic vapors [17,18].
Commercial sensors based on metal oxides, on the other hand,
can detect various species with different concentration ranges with
expected good durability. However, most metal oxides suffer from
selectivity problems; the sensors have to be operated at different
temperature ranges to differentiate between target gases. There
is also a problem of lack compatibility of metal oxide sensors with
integrated circuit technologies, because integrated circuits are built
essentially on silicon. Based on the above, it is realized that PSi
stands out as an excellent platform for sensing applications. Gas
sensors based on PSi, for example, could be essentially operated
at room temperature. Another big advantage over metal oxide gas
sensors is that an integrated electronic monitoring system can be
implemented on the same substrate; PSi is compatible with the
existing micro-fabrication techniques in comparison with many
metal oxide gas sensor substrates.
In this review, a comprehensive overview on PSi fabrica-
tion techniques, its surface and structural properties, accessible
pore sizes and morphologies and its utilization in chemical and
biosensing applications are provided in order to identify the
state-of-the-art of such emerging/hot technology subject. General
concluding remarks and some arising challenges are also summa-
rized at the end.
2. Historical overview of porous silicon
Porous silicon has been first discovered by Arthur and Ingeborg
Uhlir in 1956 [1] during studies of the electropolishing of Si in aque-
ous hydrofluoric acid (HF)-based solutions. They observed that a
Si skeleton exhibiting a variety of deposit colors (black, brown or
red) was obtained. At that time these deposits were supposed to
be originated from some Si suboxide. One year after, Fuller et al.
[37] observed similar layers in HF-HNO3 solutions without apply-
ing electrical bias to the Si. Later on, such developing films received
detailed investigation by Turner [38] and Archer [39]. For many
years these films were not called PSi. The porous nature of these
layers was first reported by Watanabe et al. [40] who also reported
the possible conversion of such layers into thick oxide films [41].
In the 1970s, it was a pioneering Japanese work [42,43] that uti-
lized the porous layer for dielectric isolation of active Si devices.
Later, in the 1980s, the so-called full isolation by porous oxidized
Si (FIPOS) process was developed at NTT Labs, Tokyo [13]. Subse-
quently silicon-on-insulator (SOI) in integrated circuits technology
was introduced [44–46].
In 1990, Canham [47] observed intensive photoluminescence
(PL) of PSi in the visible spectrum at room temperature, a property
not found in bulk Si. At the same time, Lehmann and Gösele [48]
reported that the band gap of PSi widens compared with bulk Si and
they attributed this to what is called quantum confinement. Within
a year, both multi-color PL [49] and visible electroluminescence
(EL) [50] had been reported.
Much of the subsequent scientific research on PSi was directed
toward determination of the light emission mechanism and
many models have been suggested to explain the origin of this
phenomenon. Among these luminescence models are quantum
confinement in crystalline Si wires [47], hydrogenated amor-
phous Si [51,52], surface hydrides (SiHx groups) [53,54], siloxene
molecules (a Si/H/O based polymer) [55], defects (carriers local-
ized in the Si or in an oxide covered Si surface [56,57], and surface
states [58]. However, to date the origin of such luminescence phe-
nomenon is still controversial.
3. Fabrication techniques and formation models
Porous silicon could be fabricated using various procedures
including physical, physicochemical, chemical and electrochemi-
cal techniques. However, two main methods are typically widely
applied: (i) electrochemical etching and (ii) stain etching. The elec-
trochemical etching is known as the anodization approach and is
the basic method to fabricate PSi by the electrochemical dissolution
of Si wafers in aqueous or ethanolic HF electrolytes of concen-
tration ranging from 20 to 50 wt%. [59,60]. The method can be
conducted either galvanostatically or potentiostatically, however
operation at a constant current is preferable as it gives a better
control of the porosity and thickness for the fabricated layers. The
Si wafer acts as an anode and the counter electrode is usually a
platinum. The electrochemical cell should be made of HF-resistant
material, like Teflon. The anodic current density can vary from 1
to 100 mA/cm2 for a wide anodization period. At higher anodic
overpotentials, electropolishing occurs and the surface becomes
smooth and planer in morphology. In contrast to p-type Si sub-
strates, the n-type (especially low doped) has to be illuminated
during anodization to generate holes which are necessary for the
Si dissolution processes. Fig. 1 depicts a commonly used design for
an electrochemical cell made from an HF-resistant material, typi-
cally trifluoroethylene resin, with a Pt wire as a counter electrode
[61]. This cell is known as the o-ring cell and could provide a rea-
sonably homogeneous current density distribution on the silicon
working electrode. A copper plate is usually placed at the back side
of silicon acting as a current collector and providing the electrical
contact. The contact should be ohmic to obtain reproducible results.
On the other hand, stain etching could produce porous layers by
immersing the Si substrates in HF solutions containing some oxidiz-
ing agent (usually HNO3 ) [52]. Neither an external bias (for the p-Si)
nor illumination (for the n-Si) are required in this case, and the reac-
tion proceeds at the open circuit potential. The method is simpler
than the anodization, however the stain films are not homogeneous
and the layer thickness is only a few ␮m compared to about 100 ␮m
or more that can be obtained by anodization procedure.
Before the electrochemical etching, it is essentially important to
determine the most appropriate current density at which the pores
are safely formed. A typical current density-potential variation of
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
Fig. 1. Electrochemical cell used for the preparation of porous silicon in HF-based
electrolytes under anodic polarization and illumination of the n-type silicon elec-
trode (Ref. [61]).
the Si substrate while it was submerged in the anodizing solution
is shown in Fig. 2. The curve displays a characteristic behavior of
the Si/HF system using a moderately doped p-type Si in 1% HF solu-
tion. An initial exponential rise in current with applied potential
that reaches a maximum value could be detected. At increasingly
positive potential, the system would enter in the electropolishing
regime. The suitable current value at which porous layer is formed
should be within pore formation, region (I). At high potential val-
ues of region (III), electropolishing of the Si electrode occurs and
consequently formation of stable pores is not expected. Region
(II) is a transition stage, where the process of pore formation and
electropolishing compete.
The electrochemical etching of Si in an HF electrolyte in the
regime of pore formation, Fig. 2 (region I), proceeds via a two-
electron oxidation reaction according to the following equations
[62]:
Electrochemical step : Si + 2F− + 2 h+ → [SiF2 ]
− + 2−
Chemical step : [SiF2 ] + 4F + 2H → SiF6 + H2
Net reaction : Si + 6F− + 2H+ + 2 h+ → SiF6 2− + H2
The net reaction of the two-electron process of Eq. (3) pre-
dominates at lower potential and is the principal electrochemical
reaction leading to the pore formation in Si. However, if the system
is shifted to a high positive potential (electropolishing regime),
the electrochemical etching of Si is running ideally involving a
Fig. 2. Current density versus applied potential curve for the electrochemical etch-
ing of Si in an HF based solution, showing the regimes of pore formation and
electropolishing. The open-circuit potential (OCP) of the Si electrode is also shown
Adopted from Ref. [62].
899
four-electron oxidation reaction with no pore formation, according
to the following equation [62]:
Si + 6F− + 4 h+ → SiF6 2− (4)
Different theoretical models on the mechanism of the electro-
chemical etching of Si have been proposed including the current
burst model (CBM) [63] and the space charge region (SCR) model
[64]. Briefly in the CBM model, the current flow across the Si/HF
solution interface is spatially and temporally inhomogeneous. At a
high value of local field strength, the current burst (local current)
starts to flow, generating some oxide formation. At a certain oxide
thickness, it stops the flow and consequently the oxide is chemi-
cally dissolved. As long as the oxide layer is thin enough, such cycle
starts again resulting in pore formation. In the SCR model, the pore
formation involves the formation of a hydrogen-terminated space
charge region, which acts as a passivating layer.
4. Morphology and surface chemistry
4.1. Porous silicon single layers
Single (mono) layers of PSi are usually fabricated at a single
current value applied during the electrochemical etching. All the
properties of the PSi single layers (pore diameter, porosity, surface
morphology and microstructure, etc.) are strongly dependent on
the anodization conditions, including HF concentration, solution
pH and chemical composition, current density, dopant type and
level of Si wafer, crystallographic orientation, operating tempera-
ture, anodization time, stirring conditions and illumination.
4.1.1. Pore morphology
Indeed, a great variety of porous layer morphologies can be pro-
duced according to the previous conditions. The pore shape can
be cylindrical, ink-bottle, funnel, square cross-section, or pyrami-
dal [29]. The pore diameter can vary from the nanometer scale
up to micrometer scale. In n-type PSi the pore diameter is usu-
ally larger than in p-type PSi. The pore size, on the other hand,
(1) determines the adsorptive properties of the material and thereby
is of great importance in some application areas. According to the
(2)
pore size, the following classification of PSi layers is generally used:
micoporous (≤2 nm), mesoporous (2–50 nm) and macroporous
(3)
(>50 nm). Although, the structure and pore morphology have been
intensively studied using different methods, it is not so easy to pre-
dict, with accuracy, which kind of structure will be formed in each
case. Typical examples of SEM micrographs of PSi, mainly ordered
macropores (5 ␮m), medium-sized pores (120 nm) and mesopores
(20 nm) are presented in Fig. 3. For ordered macropores, [65], p-type
Si(1 0 0), 10–20  cm was used. Ordered etch pits were initially cre-
ated on Si surface by photolithographic pre-patterning technique
and subsequent alkaline etching process. The dissolution was con-
ducted, after removal of a SiO2 resist film, in a solution: (47 wt.%
HF/H2 O/2-propanol at current density 13 mA/cm2 for 60 min. For
medium-sized pores [10], 6 wt% HF + 8 mM KMnO4 + 3000 ppm
NCW-1001(surfactant) was used as anodizing solution with n-type
Si(1 0 0), 0.0100–0.0180  cm at 25 mA/cm2 for 125 s. For meso-
pores [66], a p-type Si(1 0 0), 0.0045–0.0060 was anodized in 28 wt%
HF/H2 O/ethanol solution at 50 mA/cm2 for 30 s. All of the above PSi
layers have been formed at a single value of applied current, and
consequently a single PSi layer with no porosity gradient within
the depth is often produced. However, if the applied current was
periodically varied during the anodization process, multilayers of
PSi could be obtained.
4.1.2. Pore diameter and applied current
The pore diameter of PSi is significantly dependent on applied
etching current density. An example of SEM images of Fig. 4 shows
900 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912

Fig. 3. SEM top views (−1) and cross-sectional-views (−2) of porous silicon layers with different pore diameters. (a) Ordered macropores: 5 ␮m, (b) medium-sized pores:
120 nm and (c) mesopores: 20 nm (Ref. [9]).

different pore diameters that have been obtained at different cur-
rent densities; 5, 10, 15, 20 and 25 mA/cm2 . The produced pore
morphologies for the cross-sectional views with the correspond-
ing top-view images are shown. A tiny pore sizes with a few
nm scale are obtained at 5 mA/cm2 . The pore size increases with
increasing current density to 10 mA/cm2 but still located below
50 nm with a lot of pore branches. The pore size reaches >50 nm
at 15 mA/cm2 with a relatively low pore wall roughness. Cylindri-
cal, well-defined pore arrays free from side pores (branches) are
obtained at 20 and 25 mA/cm2 . Such pores have pore diameter
around 100 and 150 nm, respectively and were found to propagate
along the <1 0 0> direction. A common observation of the depend-
ence of average pore diameter on etching current density is that
increasing current leads to increasing pore opening and reduction
of pore wall roughness. It is worth noting that applying current
density more than 25 mA/cm2 led to the collapse of the porous
structure. This is because the effective current density value at the
pore tip is certainly located in the electropolishing regime, since
the porous formation proceeds by the selective dissolution at the
interface.
4.1.3. Porosity and thickness
The porosity and thickness of the PSi layers are considered
among the most important parameters, which characterize the PSi
layer. The porosity is defined as the ratio of empty volume (volume
of the pores) to the total volume of the PSi sample. Determination

Fig. 4. Top and cross-sectional view SEM images showing the dependence of pore diameter on applied current density. All samples were anodized using 0.010–0.018  cm
n-type Si in 6 wt% aqueous HF + 8 mM KMnO4 + 3000 ppm NCW-1001.
Adopted from Ref. [25].
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912 901

Fig. 5. (a) Cross-sectional view SEM image of a multilayer showing meso/macropore structures. (b) Double-step current modulation recorded at two current density values
of (i) 5 and (ii) 25 mA/cm2 . The amount of transferred charge was kept constant in both steps. (c) Cross-sectional view SEM micrograph of a rugate structure fabricated by the
periodic variation of current density using a sinusoidal wave modulation. (d) The corresponding sinusoidal wave and porosity variation with a sketch for a rugate structure.
Adopted from Ref. [25].

of porosity is normally carried out by gravimetric measurements
according to the following equation [67]:
m1 − m2
P(%) =
m1 − m3
where m1 is the weight of Si before anodization, m2 the weight after
anodization, and m3 the weight after the removal of porous layer
in a molar NaOH. It is also possible to estimate the thickness of the
porous layer by applying the following formula:
m1 − m3
W=
S×d
where S is the exposed wafer area to HF solution during anodiza-
tion and d is the density of Si. The porosity can also be measured
by gas adsorption measurements. Depending upon the preparation
conditions, porosity values ranging from as low as 4% [68] in macro-
porous layers to above 95% in mesoporous material [69] have been
demonstrated. On the other hand, SEM can be used for the direct
determination of the PSi thickness.
4.1.4. Surface area and composition
The surface area of PSi, normally quoted as ‘specific surface area’,
is defined as the accessible area of solid surface per unit volume of
material. Gas adsorption measurement is the standard technique
for determining surface area and pore distribution [70]. Pore size
of 2–10 nm and specific surface areas of 90–230 m2 /cm3 charac-
terize heavily doped n-type PSi, however, lightly doped p-type PSi
shows 1–6 nm pore size and 460–780 m2 /cm3 in surface area [71].
The sample thickness in both cases is 20 ␮m. Due to the extremely
large surface area of PSi, the surface structure has been extensively
investigated by Fourier transform infrared (FTIR) spectroscopy [72].
The spectra revealed that the surface of freshly prepared layers is
almost completely covered by hydride species. In the first hours
after the formation of PSi, a rapid but partial oxidation can occur
through the formation of SiO2 . Further oxidation also takes place
(5) by the formation of Ox -Si-H groups.
4.2. Multilayers with different porosities
In Section 4.1.2, it was revealed that the pore size and mor-
phology are strongly dependent on applied current density. This
(6)
means that, basically, a wide range of porosities can be achieved in
the same silicon substrate and using the same anodizing solution.
Based on this experimental fact, a meso-macroporous multilayer
was fabricated by simply changing current density during the etch-
ing process. A double-step current modulation was applied to form
a multilayer structure in the same silicon substrate anodized in
a solution consisting of 6 wt% HF + 8 mM oxidant + 3000 ppm sur-
factant [25]. The potential-transient recorded during electrolysis
at 5 and 25 mA/cm2 is shown in Fig. 5(b). The same amount of
coulombs, 300 mC, was applied during the two-step etching pro-
cess. The resulting pore morphology is shown in Fig. 5(a). A classical
mesoporous layer is obtained at 5 mA/cm2 with a porosity,  = 14%,
whereas a medium pore size structure with a  = 52% is detected.
It is evident that the pore diameter and morphology changed
immediately with changing the current density. This means that the
electrochemical etching event occurs only at the interface between
the already formed porous layer and bulk silicon. Such multilayered
porous structure is advantageous because it should combine the
unique characteristics of both meso- and macropores and hence is
considered as a good candidate in the biosensing application after
careful control and justification of its morphology.
902 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
4.2.1. Types of photonic PSi multilayers
As mentioned above, hole supply is indispensable for pore for-
mation. A surface which is depleted of holes is passivated to the
electrochemical anodzation. While the pore walls are passivated,
the pore tips have to be active during the dissolution event. This
indicates the electrochemical etching process is a self-limiting, and
the dissolution of silicon is mainly restricted to a region next to the
substrate at the bottom of the pores [73]. Consequently, the porous
layer that has already been established persists intact during fur-
ther electrochemical etching. Therefore, a periodical variation of
the formation parameters with time will lead to a periodical vari-
ation of the porosity and refractive index with depth. This is an
easy approach to establish a one dimensional photonic crystal from
silicon by the electrochemical formation of a porous multilayer.
The produced photonic structure offers an elegant way to narrow
the broad photoluminescence band of PSi [74]. The reflectance of
PSi multilayers can reach values up to 99.5% due to the multi-
ple reflection and interference resulting from the refractive index
modulation [75]. Bragg mirrors [76], rugate filters [77], and micro-
cavities [78] are three main types of photonic multilayers which can
be formed by modulating the porosity with depth during the elec-
trochemical anodization of silicon in HF solution. PSi Bragg mirrors
(PSBMs) consist of a repetition of double layers having low and high
refractive index values. An optical thickness of /4 describes each
layer, where  is the resonant wavelength of the structure. By care-
ful design of mirrors, one could adjust the width and position of the
stop band. A sharp photonic band can be fabricated by increasing
the layer numbers and decreasing the index contrast (high refrac-
tive index-low refractive index). PSi rugate filters (PSRFs), on the
other hand, are characterized by sinusoidal variation of the refrac-
tive index with depth. PSRFs possess a gradual variation in porosity,
while the porosity in PSBMs varies abruptly layer by layer. In a
Bragg stack, the individual layers must be designed in a way they
are phase-matched, while rugate filters do not have such a require-
ment and thus they are simpler to fabricate. The third type is the
PSi microcavity (PSM) which considered as the most efficient way
to modify the emission properties of PSi. By placing an active layer
with optical thickness of ∼ or /2 between two Bragg mirrors,
the reflectance/emission properties can be remarkably improved.
The resulting structure is known as Fabry–Perot interference
filter.
In our previous studies, we have fabricated rugate filters on
heavy- and low-doped p-type Si in ordinary anodizing solutions
composed of HF/EtOH with the purpose to detect various chem-
ical vapors [17,18]. The produced pore diameter located in the
mesoporous range (2–25 nm). A kind of rugate structure in silicon
with wider pores was fabricated by changing current density sinu-
soidally between 5 and 25 mA/cm2 during the etching process. A
100-cycles of the current signal was applied with a 3 s period for
each current wave. The 5 min total etching time produced around
4.5 ␮m layer thickness. Porosity of the structure was estimated
gravimetrically using single porous layers, as in case of multilayer
formation mentioned above in Fig. 5(a). Values of 14% and 52%
were obtained corresponding to lower and higher current densi-
ties, respectively. Fig. 5(c) is an SEM micrograph of the side view of
the produced rugate structure. The corresponding sinusoidal wave
and porosity variation with a sketch for a rugate structure are also
shown in Fig. 5(d). One can observe a porosity variation in <1 0 0>
direction; i.e. the direction of pore propagation. This actually would
lead to different refractive index profiles; the lower the porosity,
the higher is the refractive index. This unique porous structure
is a convenient material from which one fabricates and develops
silicon-based chemical and biosensors. The larger pore diameter in
such structure is most suitable for specifically large molecules and
is expected to enhance the infiltration process during the sensing
application as will be addressed in the following sections.
5. Porous silicon in sensing applications
The large internal surface area, wide range of accessible and
adjustable pore size and compatibility with existing silicon-based
technologies make PSi an extremely versatile material for chemical
and biosensing applications.
5.1. Sensor construction and operating principles
The prime objective of a sensor is to produce either discrete
or continues signals, which are related to the presence of specific
analyte. The sensing principle is based essentially on monitor-
ing the variation of PSi electrical or optical properties due to the
incorporation with chemical or biomolecules. Due to its particu-
lar properties, the PSi can be efficiently used as a transducer to
convert the effect of analytes into either an electrical or optical
signal [79]. Precision and accuracy are two decisive factors for
efficient transduction. The huge surface area enables an effective
incorporation of the analytes, however it presents also a reactive
surface that must be adequately passivated in order to achieve
the required chemical stability and to avoid device degradation.
Hence the stabilization of PSi via a suitable surface chemistry proce-
dure is an indispensable step for fabricating a stable sensor device.
Among the techniques that commonly used to functionalize PSi
surface are the oxidation [80] and surface-derivatization (hydrosi-
lylation) [81]. Selection of a proper pore size is also an important
key property to achieve an efficient sensor. The most commonly
used transduction approaches include piezoresistance, piezoelec-
tricity, capacitive, resistive, tunneling, thermoelectricity, optical
and electrochemical methods [82]. In this review, we classified the
PSi-based sensors depending on the analyte type (chemical ana-
lytes: either in liquid or gas state) and biomolecules. We focus
only on addressing the transducing mechanism in optical, electrical
and electrochemical contexts. Some related examples of such sen-
sors and its performance evaluation are detailed in the following
sections.
5.2. Chemical sensors
In this section, recent progress in the field of optical/electrical
chemical sensors based on PSi structures is reported. The sensing
of various chemical analytes in either liquid or gas state through
optical or electrical means is summarized.
5.2.1. Optical chemical sensors
PSi mulilayers exhibit a so-called Fabry–Perot fringe pattern in
the reflectivity spectra. In general, changes in optical properties of
PSi have been used to detect target analytes in two ways: either
by monitoring the quenching of PSi photoluminescence (PL), or by
observing the shift in the fringe pattern resulting from changes in
the average refractive index of the porous matrix. Fig. 6 depicts
the reflectometric sensing modes which have been reported for
PSi-based sensors [83]. Briefly, the fringe pattern is shifted to a
longer wavelength (red-shifted) when the refractive index of a tar-
get analyte infiltrated into the pores is increased, Fig. 6(A). In a
case of decreasing the average refractive index, one would expect
a blue shift (shorter wavelength) of the pattern, Fig. 6(B). The
decrease in refractive index in sensing mode (B) is induced by
the oxidation of PSi skeleton upon interaction with target ana-
lytes. For the analytes that are not able to infiltrate into the pores,
changes in the amount of reflected light resulting from changes
in the refractive index contrast at the PSi interface are observed,
Fig. 6(C).
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
Fig. 6. Reflectometric sensing modes using PSi. (A) Increase of the average refractive index leads to a red-shift in the pattern (longer wavelength). (B) A blue shift (shorter
wavelength) is due to a decrease in the average refractive index. (C) Adsorption or binding of the analyte to the PSi interface changes the refractive index contrast and
decreases the amount of reflected light (Ref. [82]).
PSi unique structure has the capability to collect vapors via
microcapillary condensation [17]. Such a phenomenon could be
described by Kelvin Equation [84]:
V
r=
RT ln(P/P 0 )
where r is the pore radius,  represents the surface tension at the
liquid/vapor interface, V is the molar volume of liquid, R is the uni-
versal gas constant, P is the actual vapor pressure, and P0 is the
vapor pressure at temperature T. This relation indicates that the
PSi is an appropriate sensor-based material for detection of vapors
like volatile organic compounds (VOCs), organophosphate nerve
agents, ammonia, and hydrofluoric acid [85]. The research interest
of PSi optical gas sensors was initially stimulated by the work of
Zangooie et al. in 1997 during detection of vapors using spectro-
scopic ellipsometry [86]. In our previous works [17,18], we have
fabricated PSi rugate filters as a one-dimensional photonic crystal
and investigated its ability to sense various vapor species, including
methanol, ethanol, acetonitrile, 2-propoanol, n-heptane and ethyl-
ene dichloride. The dependence of the resonant wavelength of the
filters on the period of the electric current wave form applied during
the electrochemical etching process, together with optical photos
of filters is depicted in Fig. 7(A). Reflectance spectra of the sensing
event, along with theoretical and observed relative shifts in res-
onant wavelength vs. refractive index are also shown in Fig. 7(B)
and (C) [17]. An experimental setup was employed to check the
durability of the fabricated sensor. The sample was placed in a
cell into which air saturated with ethanol vapor was introduced.
The cell had an optical window to measure reflectance spectra in
situ. An electric current was allowed to pass through the silicon
substrate to heat the sample. The reflectance spectra were in situ
collected during repeated cycling of the electric current between on
and off states under continuous exposure to the saturated vapor.
The durability of the filter was tested by allowing the structure to
undergo many cycles of adsorption and desorption of vapor-phase
ethanol molecules. In order to stabilize the structure against oxida-
tion expected from cycling and environmental exposure, the filter
was subjected to electrochemical oxidation in an aqueous sulfuric
acid electrolyte. The treatment dramatically improves the stability
of the sensor; a relative blue-shift of only <0.4% was observed after
100 adsorption/desorption cycles. The sensitivity of the sensor was
also affected by electrochemical oxidation.
Sailor’s research group has intensively investigated the
sensing of various VOCs using PSi based 1D photonic crys-
tals with different surface chemistry modifications. They studied
903
the sensing of isopropyl alcohol (IPA) and heptane in air
using sub-millimeter PSi-based rugate filters in the concentra-
tion range 50–800 ppm [87]. The proposed sensors have been
studied as a function of surface chemistry: ozone oxidation,
(7) thermal oxidation, hydrosilylation (1-dodecene), electrochemical
methylation, reaction with dicholorodimethylsilane and thermal
carbonization with acetylene. The thermally oxidized and the
dichlorodimethylsilane-modified materials showed the greatest
stability under atmospheric conditions. The surface of PSi rugate
filters was modified by the chemical hydrosilylation of terminal
alkenes in the presence of a concentration gradient of diazonium
salt initiators and used successfully as a simple visual sensor the
detection of small quantities of ethanol in water, ethanol concen-
trations of between 0 and 8% with a resolution of 1% was obtained
[88]. Differential adsorption of a test analyte (2-acetoxybenzoic
acid or diphenyl ether) in functionalized PSi nanostructures was
recently elaborated [89]. In a recent report, the group investigated
in detail the sensing behavior via condensation and evaporation
of vapors of isopropanol, heptane, and cyclohexane into meso-
porous silica photonic crystals, which was monitored by optical
reflection spectroscopy as a function of sensor temperature [90].
Mulloni and Pavesi succeeded to discriminate between vapor ana-
lytes with similar refractive index, by developing an optical sensor
based on PSi microcavity structures [91]. For a similar purpose as
to increase the specificity of PSi gas sensor, single component opti-
cal sensor based on photonic crystal was recently developed for
the identification and quantification of organic vapors at ppm con-
centrations [92]. In a recent work, the fabrication of chemically
patterned PSi photonic crystals toward their use as an internally
referenced organic vapor sensor has been reported [93]. They used
photoresist patterning and surface silanisation for the sensor to
produce patterns of hydrophobic and hydrophilic regions. Apart
from VOCs, sensing of hydrogen gas has been demonstrated using a
PSi-palladium composite film via optical interferometric approach
[94].
The zero-point drift of the reflectivity spectra generated by
temperature, humidity or fluctuation in light intensity was a
challenging task of developing PSi optical sensor. King et al. have
corrected such unavoidable background noise by introducing a
reference channel directly onto the PSi based ammonia sensor [95].
Such internally referenced channel concept was also employed
during the detection of HF and Cl2 using reactive PSi photonic
crystals [96]. This kind of internally referenced remote sensor was
fabricated to contain either surface oxide or surface Si-H species,
and analyte detection was based on irreversible reactions with
904 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912

Fig. 7. (A) The dependence of the resonant wavelength on the period of the electric current wave form, with corresponding photos of photonic crystals. (B) Reflectance
spectra of PSi rugate filters before and after exposure to saturated vapors of various organic species. (C) Theoretical and observed relative shifts in resonant wavelength vs.
refractive index.
Adopted from Ref. [17].

aqueous HF or Cl2 gas analytes, respectively. Fig. 8 shows the
reflectance spectra of oxidized PSi photonic crystals measured
during the sensing of aqueous HF. A fiducial marker consisting
of polystyrene was added to the above PSi photonic crystals
to enable a self-referenced sensor that can be probed with a
free-space optical detector. Their findings revealed that the silicon
oxide chemistries are stable in ambient environments and could
provide good discrimination of HF relative to corrosives, whereas
the reactivity of the silicon hydride chemistry probably limits its
environmental sensing applications to short-term assays.
5.2.2. Electrical chemical sensors
The highly sensitive, reactive surface of PSi and the ability to
record the changes in its electrical properties, along with its capac-
ity to adsorb a wide range of different analytes, are key parameters
that help greatly in its utilization as electrical sensors. Generally,
the capacitance and conductance changes of PSi arrays could be
principally employed to detect various concentrations of chemical
compounds. In the literature, different metallic contact configura-
tions were reported and could be created by metal deposition to the
sensor device as follows; (i) to the PSi surface and to the backside of
the bulk silicon substrate [97], (ii) contacts onto the PSi surface only
[98], and (iii) contacts onto the backside of the silicon wafer [99].
As example of this kind of electrical sensor is a couple of papers
published recently by Li et al. using PSi with intermediate-sized
pores (∼100–200 nm) for sensing NH3 and NO2 gases [100,101].
Two electrical contacts of Pt thin films were deposited onto the PSi
surface by RF magnetron sputtering. Dynamic response curves of
such PSi gas sensor measured at room temperature versus various
concentrations of NH3 and NO2 gases are plotted in Fig. 9. The sen-
sor showed high response, fast response–recovery characteristics,
good reproducibility and excellent repeatability.
In another report, an electrical sensing of organic and ionic
chemical solutions using thermally oxidized macroporous silicon
sensor has been investigated [102]. A new type of gas sensor that
enables simultaneous monitoring of the electrical and optical
properties of the sensor structure and based on a PSi optical inter-
ference filter layer has been developed recently [103]. The sensors
were subjected to ethanol and dimethyl formamide vapors, and
their ability to differentiate between the studied gases was demon-
strated. Li et al. [104] reported a capacitive ethanol gas sensor
based on nano-porous pillar arrays created on silicon. A capaci-
tive humidity sensor based on ordered macro-PSi with a thin film
metal oxide deposition has been demonstrated [105]. The transport
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
Fig. 8. Reflectance spectra of an ozone-oxidized porous Si sample containing an
impregnated polystyrene fiducial marker, before and during exposure to aque-
ous HF (1.5%). The spectrometer optics encompassed both the polymer-filled and
the unfilled regions of the fi lm equally, spectra were acquired at the ozone oxi-
dized porous silicon/polystyrene infused porous silicon interface. A cross-sectional
schematic of the structure containing the polystyrene fiducial marker is shown in
the inset. From top to bottom: reflectance peak of sample in deionized water, after
1 min, 2 min, and 10 min exposure to 1.5% HF. Spectra were obtained on samples
submerged in either water or 1.5% aqueous HF (Ref. [95]).
mechanisms were investigated in free-standing PSi membranes
for liquids and gases [106]. The effects of thermal annealing on
the characteristics of the electrical contacts of PSi gas sensors have
been previously studied [107]. The development of a sensitive
PSi electrical sensor which utilized photoluminescence-induced
metallization as a means of obtaining a highly efficient electrical
contact on front surface has been demonstrated for the detection
of HCl, NH3 , and NO at the 10 ppm level [108]. For more details,
the potential of electrical PSi gas sensors has been reviewed in Ref.
[109], focusing on sensing mechanisms of different sensor designs,
sensing behavior of different gas molecules including H2 O, ethanol,
methanol, isopropanol, COx , NOx , NH3 , O2 , H2 , HCl, SO2 and PH3 .
Fig. 9. Dynamic response curves of PSi sensor measured at room temperature versus various concentrations of: (a) NH3 and (b) NO2 .
Adapted from Refs. [100,101].
905
Archer et al. [99] observed changes in conductance upon
exposure to different organic solvents using (∼1 ␮m pore diam-
eter, 20 ␮m pore thickness) of PSi layers with backside electrical
contacts. The reported results illustrated a reversible response,
however the electrical macro-PSi sensor sensitivity was low with
no investigation done on sensor durability. Recently, we have fab-
ricated meso-PSi layers with top Ag electrical contacts and utilized
the structures as electrically based sensor for detection of different
organic solvents at room temperature [110]. The PSi nanostructure
that is generated in an electrochemical etching of crystalline silicon
in HF-based solution was ≈4.5 ␮m thick with an average pore size
of 30 nm. Fig. 10 shows the SEM images of the produced meso-
PSi structure, together with schematic diagram of the electrical
contacts with a photograph of the sensor. The as-fabricated sen-
sor was exposed to different polar and non-polar organic solvents
in liquid state, including ethanol, methanol, acetonitrile, acetone,
chloroform, n-hexane and toluene. Our electrical sensor exhibits
highly sensitive, reversible response during the real-time measure-
ments of capacitance and conductance. Excellent repeatability of
the device was obtained after six cyclic tests toward liquid ethanol,
demonstrating sensor stability. Fig. 11 shows real-time capacitance
and conductance of the sensor measured at room temperature
after exposure to liquid ethanol, together with the cycling behav-
ior of the sensor. The long-term stability of the sensor was also
observed after four weeks storage. The observed response could
be understood in terms of change in surface charge upon solvent
infiltration into the mesoporous structure. It is worthy to mention
that electrical PSi-chemical sensor is considered inexpensive and
easy-to-handle approach compared to the corresponding optical-
based sensor, however it is generally agreed that sensors based on
optical measurements give faster response time, and are safer to
implement than those employing electrical measurements, espe-
cially when dealing with flammable gases, vapors, or explosive
atmosphere, as well as they are amenable in remote sensing appli-
cations. Table 1 summaries the sensing parameters achieved for
various chemical molecules using different PSi structures.
5.3. Biosensors
5.3.1. Optical biosensors
The resonance photonic structures of PSi along with its highly
functional surface chemistry provide excellent, flexible platform
for sensing a variety of biomolecules. Generally, the sensing prin-
ciple of optical biosensors relies on an increase in the composite
refractive index of the porous photonic structure upon infiltration
906 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912

Fig. 10. Scanning electron micrographs of (a) cross-sectional and (b) top-view as inset of mesoporous silicon layer produced from p-type silicon by galvanostatic anodization.
(c) Schematic cross-sectional view of the porous silicon sensor. The electrical contacts are made on the front of the porous layer by colloidal Ag paint. (d) Close-up photograph
of the sensor (Ref. [110]).

of target analytes into the pores, and consequently monitoring the
red-shift (higher wavelength) in resonance peak. In this section,
different strategies for PSi application in biosensing are reviewed
with addressing some key developments on the subject.
The first report on utilization of PSi as a biosensor was pub-
lished by Lin et al. in 1997 [116]. They fabricated single PSi layers
whose Fabry–Pérot fringes in the reflectivity spectrum could be
shifted upon binding of DNA and proteins as biomolecules onto
the functionalized PSi surface. It was demonstrated also that the
functionalized PSi surface could be used as a transducer and be inte-
grated with various biological molecules including small molecules
such as biotin, steroid digoxigenin, short DNA oligonucleotides
and proteins (streptavidin and antibodies). The sensing perfor-
mance of the above PSi single layer, in terms of sensitivity, was
compared to a microcavity-based photonic crystal employed by
Anderson et al. [117]. The reflectance changes upon sucrose infiltra-
tion were experimentally and theoretically addressed. They found
that the photonic structures exhibited higher sensitivity for refrac-
tive index changes compared to the single layer-based sensor. Later
on, Ouyang et al. [118] fabricated a microcavity photonic struc-
ture to investigate the immobilization of small biotin biomolecules
with an ultimate objective of capturing and sensing streptavidin
(a type of protein). In that work, a systematic optimization of the
etching parameters for macro-PSi microcavities was done to allow
the detection of macromolecule infiltration. The SEM images of the
microcavity together with the corresponding measured and calcu-
lated reflectance spectra are shown in Fig. 12. The sensitivity of
such microcavity was found to depend on pore size, porosity and
layer thickness. The outstanding sensing performance of the devel-
oped macro-PSi sensor was demonstrated by infiltration of rabbit
immunoglobulin G (IgG) and detection of biotin/streptavidin inter-
action with a detection limit of 0.3 ng/mm2 . Based on these findings,
they have demonstrated a label-free assay of protein affinity to a
biotin functionalized PSi surface. Following the work of Ouyang
et al. [118], a series of microcavity-based biosensors for immo-
bilization of glutathione-S-transferase into the porous structures
was fabricated and reported by DeLouise et al. [119]. By measur-
ing the enzyme activity, the amount of immobilized enzyme could
be indirectly quantified and correlated to the microcavity opti-
cal response. Low detection limits in the range of 50–250 pg/mm2
were obtained for the optimized PSi sensor devices. By develop-
ing the above works, selective and label-free quantitative detection
of protein interactions using macro-PSi biosensors based on sili-
con photonic bandgap structures were further demonstrated [120].
Various PSi photonic crystals have been also investigated and
used as biosensor platforms [121–123]. Again, these multilayered

Fig. 11. (a) Real-time capacitance (C) and conductance (G) of sensor measured at room temperature after exposure to liquid ethanol. The vertical up-arrow indicates the
injection of ethanol into the sensor device and the down-arrow indicates the evaporation of ethanol from device. (b) Cycling behavior of the sensor after injection of
consecutive ethanol doses; six cyclic tests are shown only, demonstrating stability of the sensor (Ref. [110]).
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
Fig. 12. (a) Cross-sectional SEM images of a macroporous silicon microcavity (high-porosity layers formed using a current density of 40 mA/cm2 , low-porosity layers formed
using a current density of 34 mA/cm2 . (b) Top Bragg mirror of the microcavity, showing the complete opening of the pores. (c) Measured (black) and simulated (gray)
microcavity spectra (Ref. [118]).
PSi-based biosensors offer the advantages of easy preparation, large
surface area, possibilities for label-free detection and compatibility
with existing microelectronics technology.
An exciting work reported by DeLouise’s research group [124]
is highlighted here, where the label-free detection of a broad range
of opiates has been successfully achieved. They determined the
shift in wavelength by tracking the liquids infiltration with known
refractive index values and measured the reflectance spectra
normal to the surface as depicted in Fig. 13. The findings essen-
tially indicated that the label-free PSi immunosensor technique
is appropriate to screen for common opiates in real patient urine
samples and consequently supports its potential for future devel-
opment in various clinical assays. This is actually considered as a
step-forward toward commercial application of PSi-based sensors.
Kilian et al. have observed different photonic behavior during
the detection of peptide-modified PSi optical filters employed for
sensing protease activity [125]. Instead of observing a red-shift in
the reflectance spectra, they detected blue shifts of the reflectance
peak. Exposure of the peptide-modified crystals to the protease
causes a change in the refractive index, resulting in a blue shift of
the resonance peak (shorter wavelength), indicating the cleavage
of organic material within the pores of PSi matrix. They have been
able to detect an enzyme concentration as low as 37 nM. Apart
from the above detection strategy via reflectance observation,
optical biosensors based on naked eye detection for protease
activity has been developed by Orosco et al. [126]. The sensor was
fabricated from PSi photonic crystals, coated with a thin film of
zein as a natural hydrophobic protein and was capable of detecting
picomole quantities of protease. Further development of such
optical concept was achieved by Gao et al. [127] for label-free
colorimetric detection of gelatinases on PSi photonic films. In that
work, gelatin was used as the substrate protein, forming a thin layer
onto PSi surface. Digestion of gelatin by the gelatinase produced
small molecules that penetrating the pores and could induce color
changes detected by the naked eye, see Fig. 14. Using this sensor
907
design, the authors have demonstrated the successful detection
of matrix metalloproteinase-2 (MMP-2) – an important gelatinase
closely associated with tumor aggressiveness and metastatic
potential – with concentrations varying from 0.1 to 1000 ng/mL in
samples with volumes as small as 1 ␮L. The merit of such a devel-
oped sensor is the ability to detect gelatinase without the use of
costly antibodies or fluorescent chemical agents with a low detec-
tion limit. Another example of optical biosensor is the sensing of
different glucose levels (2–10%) using PSi microcavity based device
which is recently demonstrated by Patel et al. [128]. The effective
refractive index and optical thickness of the photonic structure
changed as a result of capillary adsorption of glucose molecules
which results in the wavelength shift in the reflectivity spectrum.
The measured sensitivity was 3.146 nm/concentration (%).
5.3.2. Electrical and electrochemical biosensors
In electrical PSi-based sensors, the creation of electrical contacts
on the PSi surface by an appropriate metal deposition technique
is a pre-requested step to measure the changes in capacitance
or conductance upon analyte attachment to the porous surface.
An example of this type of biosensor is the work of Archer et al.
[129,130] using macro-PSi layers as substrate material to transduce
DNA hybridization into a change in conductance. They fabricated a
coplanar electrical contact configuration to allow a complete expo-
sure of the porous layer to the sensing species without the need
to the top-contact or electrolytic solution. They attributed the con-
ductance change to the change in the space charge region of the
crystalline silicon and the dielectric constant of the pores. The sen-
sor sensitivity was found to depend on the interacting surface area
of PSi, layer thickness, and the number of available binding sites
(probe concentration).
As an example of electrochemical sensor, Lugo et al. [131]
investigated the possible use of PSi layers to transduce the
hybridization of DNA into a chemical oxidation of guanine by
Ru(bpy)3 2+ , the reduced form that could be consequently detected
908 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912

Fig. 13. Principle of PSi photonic sensor: (a) cross-sectional SEM of PSi Bragg mirror architecture. Inset depicts schematic of an opiate analog functionalized PSi. (b) In the
absence of free drug in urine, maximum Ab binds to surface attached opiate analog resulting in (c) a maximum wavelength shift response. (d) Opiates in urine compete with
surface attached opiate analog for Ab binding sites, resulting in a proportional decrease in the wavelength shift response (e).
Adapted from Ref. [124].

electrochemically. Voltammetric technique was employed for the
DNA detection using PSi modified with nucleic acid as a working
electrode. The set-up of the measurement system together with the
electrochemical behavior is depicted in Fig. 15. The cyclic voltam-
mograms measured at different concentrations of target DNA
(curves 2–5 = probe–target sequence) and different targets (curve
1 = probe-mismatch and curve 6 = probe–probe sequence) are
shown in Fig. 15 (B). A significant increase in current was observed
for curves 2–5, where target DNA undergoes hybridization to the
complementary DNA. In the bottom, one could observe a linear
relation between the anodic peak current and the concentration
of target DNA sequence between 0.5 × 10−10 and 500 × 10−10 M.
the detection limit using this technique is 5 × 10−11 M. Another
effective approach to develop PSi biosensors is via amperemetric
and potentiometric characterization. In amperometric biosensors,
the main concept is to use the redox reaction that takes place
when the target molecule is introduced in the electrochemical cell
[132]. However, the main parameter in potentiometric biosensors
is the potential difference between the cathode and anode in the
electrochemical cell. These biosensors are greatly dependent to
the level of solution pH. Examples of these PSi biosensors are
the potentionmetric and amperometric urea sensor [133] and
the detection and estimation of triglycerides using a PSi based
potentiometric biosensor [134]. The potential of this sensor for
estimating the total amount of triglycerides in oil and blood sam-
ples is described with a sensitivity of 30 mV/pH unit. Furthermore,

Fig. 14. Detection of MMP-2 on a completely dried chip after loading glycerol onto each sampling spot. (A) An optical image of the chip. (B) Spectra of the reflected light
taken from spots that have been loaded with (from bottom to top) blank control, 1000 ng/mL deactivated MMP-2, 0.01, 0.1, 1, 10, 100, and 1000 ng/mL MMP-2 samples.
Adapted from Ref. [127].
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912 909

Fig. 15. (A) Electrochemical system set-up: PSi is the working electrode, a Pt wire is the counter electrode and an Ag/AgCl is the reference electrode. Inset shows the different
parts of working electrode. (B) Cyclic voltammograms of different concentrations of target DNA: (2) 0.5 × 10−10 M, (3) 100 × 10−10 M, (4) 200 × 10−10 M, (5) 500 × 10−10 M.
Curve 1 shows the CV for the probe-mismatch target DNA sequence (0.5 × 10−10 M) and curve 6 for the probe DNA sequence (0.5 × 10−10 M). The anodic current changes with
the concentration of the target DNA are shown in the bottom. In all cases, 0.1 ␮M of Ru(bpy)3 2+ was used.
Adapted from Ref. [131].

various PSi layers with mesoporous structures or medium sized
pores have been employed successfully as electrical biosensors for
the detection of glucose, bacteria, alanine aminotransferase (ALT)
and aspartate aminotransferase (AST) [135–137]. Additionally, PSi
with various architectures including single macroporous layers,
macropores with photonic lamellar gratings and composite PSi-
crystalline silicon cantilevers have been demonstrated for sensing
different chemical and biological agents [138–141].
within a meso-PSi matrix and used the substrate successfully for the
SERS detection of both Cy3 and rhodamine 6G at a single molecule.
Gold nanostructures deposited into the nanopores of PSi template
could also offer a promising, active SERS substrates as observed
recently by Fukami et al. [146]. Additionally, PSi-coated with Ag
or Au nanocrystallites have been used as ultrasensitive platform
for SERS [147–149]. Table 2 summaries the sensing parameters
obtained using various PSi structures that frequently employed in
biosensor applications.

5.3.3. Sensing via surface enhanced-Raman scattering (SERS)

The plasmonic properties of metal nanoparticles have been
widely employed to develop PSi-based biosensors that exhibit
enhancement of Raman scattering. The exciting observation in
the development of SERS field was the success to detect single
molecules in 1997 by two independent research groups [142,143].
The extremely large internal surface area of PSi and its surface reac-
tivity with open porous structure are decisive properties that help
to fabricate highly sensitive SERS substrates. Incorporating noble
metals such as (Au, Ag, Pd and Cu) into PSi would form nanocom-
posites that principally combine the ability of metal to amplify
Raman scattering signals with vast surface area that allows strong
enhancement for the detection of target molecules. Here, we briefly
describe the work of Chan et al. [144] as an example of utiliza-
tion of hybrid structure of PSi coated with Ag for the detection of
two target small molecules, rhodamine 6G and adenine. Rhodamine
6G is a dye molecule commonly investigated using SERS approach
due to its distinguish Raman features and good adsorbability onto
Ag nanoparticles. Adenine is of biological importance because it is
the nitrogen base of a DNA nucleotide, deoxyadenosine monophos-
phate. The Raman spectra of 114 ␮M rhodamine 6G collected from
various PSi substrates with different porosities ranging from 52
to 77% porosity are shown in Fig. 16. As the porosity increases,
the Raman intensity also increases. Seven orders of magnitude
Raman enhancement are observed for the highest porosity sample.
Fig. 16. Surface-enhanced Raman spectra of 114 ␮M rhodamine 6G dye molecules
In that work, they concluded that the fabrication of PSi deposited
on Ag-deposited PSi substrates with different porosities. The Raman intensity
Ag substrates could represent a new approach to the creation of increases with increasing the porosity. SEM top-view image of PSi is shown in the
SERS-active substrates that is proven to be efficient and reliable. In inset.
a recent report, Virga et al. [145] have synthesized Ag nanoparticles Adapted from Ref. [144].
 910
Table 1
Summary of sensing parameters of various chemical molecules using porous silicon architectures (where n/a, not applicable).

Porous layer Analyte Key property Detection range Sensitivity Response time Ref.

1D photonic crystal Volatile organic compounds Optical: reflectance 50–800 ppm 50 ppm 4 min [87]
1D photonic crystal Ethanol in water Optical: visual 0–8% by volume 1% by volume 2 min [88]
Fabry–Pérot films-coated Pd H2 gas Optical: reflectance 0.17–1.71% by volume ∼0.2% by volume A few seconds [94]
1D photonic crystal NH3 gas Optical: reflectance 15–1300 mg m−3 124 mg m−3 ∼5 min [95]
1D photonic crystal HF(aq) , Cl2(g) Optical: reflectance 0.11–6.8 mass% 0.11 mass% for HF(aq) 10 min [96]
Single-macropores Organic vapors Electrical: conductivity 4% gas/air I/I0 = 32 ∼20 min [98]
Single-medium-sized pores NH3 gas Electrical: resistance 6–100 ppm 6 ppm ∼80 s [100]
Single-medium-sized pores NO2 gas Electrical: resistance 0.1–1.5 ppm 0.1 ppm 60 s [101]
Nano-porous pillar arrays Ethanol gas Electrical: capacitance 0–500 ppm 50 ppm 15 s [104]
Ordered macropores-Ta2 O5 coating Humidity (RH) Electrical: capacitance 0–100% RH <22% RH 300 s to 100% RH [105]
Single-micropores O2 gas Electrical: conductivity 100 ppm I/I0 = 11 ∼10 min [107]
∼3 min

F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912

Single-macropores HCl, NH3 , NO Electrical: impedance 10–100 ppm 0.1%/ppm for NH3 , NO [108]
Single-mesopores or microcavities NO2(g) , ethanol in red wine Optical: reflectance Up to 15% (v/v ethanol) 0.2% (v/v ethanol) 3 min [111,112]
Single-micro-mesopores NO, NO2 , organic molecules, CH4 , CO gases Optical: photoluminescence 1–10 ppm (NO), 60–180 ppb (NO2 ) 2 ppm (NO), 70 ppb (NO2 )Ref. 114 10 min [113–115]

Table 2
Summary of sensing parameters of various biomolecules using porous silicon architectures (where n/a-not applicable).

Porous layer Analyte Key property Detection range Sensitivity Response time Ref.

Single-mesopores DNA, proteins Optical: reflectance 2 × 10−15 –2 × 10−6 M 9 fg/mm2 40 min [116]
Single-Bragg mirror-microcavity Sucrose Optical: reflectance 0.05–1.0 wt.% 0.05% <5 min [117]
Microcavities Streptavidin protein Optical: reflectance 1 mg/mL in 20 mM 0.3 ng/mm2 60 min [118]
buffer
Microcavities, 1D photonic crystals Enzyme, protein Optical: reflectance 50–250 pg/mm2 50 pg/mm2 (enzyme), 90 min (enzyme) [119,120]
(enzyme) 130 fmol (protein)
Double-porous layers Sucrose, bovine serum albumin (BSA) Optical: reflectance 1 mg/mL (BSA) in 1 mg/mL ∼20 min [121]
0–100 mg/mL sucrose
Bragg mirror Hydroxysafflor yellow A Optical: reflectance 1–3 ␮g/mL 0.78 ng/mL 2h [123]
Bragg mirror Opiates Optical: reflectance 1–10,000 ng/mL 300 ng/mL 60 min [124]
1D photonic crystal Protease enzyme Optical: reflectance 3.7 nm–37 ␮M 37 nM 4h [125]
Protein coated-1D photonic crystal Protease Optical: reflectance, naked eye 0–28.6 pmol 7 pmol 60 min [126]
1D photonic crystal Gelatinases: matrix metalloproteinase-2 Optical: naked eye, reflectance 0.1–1000 ng/mL 0.1 ng/mL 12 h [127]
Single-mesopores and macropores DNA hybridization Electrical: conductance, 5–25 ␮M 100 nM ∼5 min [129,130]
impedance
Single-medium sized pores DNA Electrical: electrochemical 0.5 × 10−10 –500 × 10−10 M 5 × 10−11 M 15 min [131]
Single layer-mesopores Glucose Electrical: current–voltage 1–1000 ␮g/L n/a 20 min [135]
(I–V)
Single layer-mesopores Bacteria Electrical: (I–V) 2.5–100 ␮g/mL n/a 30 min [136]
Single-medium sized pores Alanine aminotransferase (ALT) Electrical: electrochemical 1.3–250 U/L 0.145 mA/(U/L) 20 s [137]
Single layer-mesopores-coated Ag Rhodamine 6G, adenine Surface enhanced-Raman 114 nM-114 ␮M 114 nM n/a [144]
scattering (SERS)
Single layer-mesopores-coated Ag Cyanine, rhodamine 6G SERS 10−4 –10−14 M <10−11 M 3 min [145]
Single layer-medium sized pores-coated Au 4-4 bypiridine SERS 100 ␮M n/a 60 min [146]
Single layer-mesopores-coated Ag Cyanine, horseradish peroxidase SERS 10−4 –10−10 M 10−8 M n/a [148]
 F.A. Harraz / Sensors and Actuators B 202 (2014) 897–912
6. Future prospects of PSi sensors and author’s views
Over the past two decades there have been many advances in
the use of PSi layers in sensing devices as the PSi-based structures
are proving to be an interesting platform for sensing applications.
The ability to fine tune the pore size, porosity and surface func-
tionalization of PSi allows one to fabricate sensor devices capable
of detecting very low analyte concentrations of chemical, gases
and biological molecules. The significant growth of interest in PSi
sensors has started from the huge internal surface area, surface
reactivity and its unique optical and electrical properties. These
entire advantages make the PSi-based sensing systems a very
promising research area that would bring new discoveries, with
real potential applications in related-sensing fields. However, some
arising challenges still exist, hindering the material for commercial
use. These include:
(i) fabrication of efficient ohmic contacts for electrical sensors,
(ii) surface stabilization against corrosion to enhance the sensor
recyclability and long-term stability,
(iii) formation of ordered pores or patterning of PSi to avoid the
non-uniformity of the random porous structures,
(iv) selectivity: the capability to quantify and identify the amount
of analyte in a complex mixture,
(v) zero point drift in optical sensors,
(vi) fouling: the accumulation of impurities that often led to degra-
dation of sensitivity, and
(vii) device engineering: a suitable device design is required for
each application to achieve excellent sensing performance.
Based on the above, major developments in surface chemistry
are needed to further stabilize the PSi films particularly in aqueous
solutions and biological fluids, to help attach specific recognition
molecules and to provide antifouling capabilities for the surface.
Besides that, hybrid structures of PSi may be designed by incor-
porating other metal or metal oxide nanoparticles or conducing
polymers inside the pores, so that to allow two or more properties
combined in a single material for developing future sensing appli-
cations. As long as the researchers are working to solve the above
challenging tasks, “smart” PSi-based sensor devices are expected to
emerge, which in turn would maximize the possibility for commer-
cial use. Of course, the rapid advancement of the state-of-the-art
in characterization tools for nanomaterials would also enhance the
nanosensors-related research. The research field of PSi-related sen-
sors is a mulidisciplinary that is why various research skills on
different backgrounds are required for tangible achievements on
the subject.
7. Conclusions
PSi is a very promising and versatile material for sensing appli-
cations. The ability to control the pore size, morphology, porosity,
layer thickness, large surface area and the ease to functionalize
the surface gave the researchers worldwide the possibilities for
sensing various chemical species, gases and biomolecules. In this
review article, recent progress in the field of optical and electri-
cal PSi sensors for detection of various chemical species, gases and
biomolecules has been summarized. Basic principles and sensing
mechanisms which are now in use for PSi sensors have also been
addressed in detail. Remarkable efforts had been done to detect tar-
get molecules in real time with minimal or with no sample damage.
Researchers working in the field are trying to improve the design
and sensing schemes for both optical and electrical-based sensors.
Research works are going on for producing fast response time,
sensitive, selective, long-term stability, and portable PSi sensor
911
devices. The future will show if PSi will find its way from research
labs into commercial applications.
Acknowledgments
Author would like to acknowledge the support of the Ministry
of Higher Education, Kingdom of Saudi Arabia for this research
through a grant (PCSED-019-12) under the Promising Centre for
Sensors and Electronic Devices (PCSED) at Najran University, King-
dom of Saudi Arabia.
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5349.
Biography
Farid Harraz received his Ph.D. from School of Energy Science of Kyoto Univer-
sity, Japan in 2003. Currently, he is an associate professor at Promising Centre for
Sensors and Electronic Devices (PCSED), Advanced Materials and Nano-Research
Centre, Najran University, Saudi Arabia. His research area focuses on development
of nanomaterials for energy and sensing applications.