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Photonic crystal for gas sensing

Cite this: J. Mater. Chem. C, 2013, 1,
6087
Received 18th April 2013
Accepted 26th July 2013
DOI: 10.1039/c3tc30722k
www.rsc.org/MaterialsC
Hua Xu,ab Pin Wu,c Chu Zhu,a Abdelrahman Elbaza and Zhong Ze Gu*ab
Photonic crystal (PhCs) based sensing technology has gained more and more attention because of its
obvious advantages in sensitivity, stability, security, miniaturisation, portability, on-line use and remote
monitoring. Many PhC sensors have been proposed based on their novel structure and unique optical
properties. In this review, we will describe the recent progress in the use of natural and artificial PhC
materials for gas/vapor sensing, including Morpho butterfly wings and their mimicry of nanostructures,
porous silicon, Bragg stacks, colloidal crystals and inverse opal. Here we will discuss the PhCs with
different structures and their respective gas sensing properties, focusing on the description of the
functional structure of the PhCs materials and their sensing mechanisms.

1 Introduction
In the past decades, gas sensing has received increasing atten-
tion for its widespread applications in industrial emission
control, environmental monitoring, household security,
medical diagnosis and food quality control.1–4 Simply speaking,
a gas sensor is an intelligent device that can convert the type
and/or the concentration of gas/vapors into a physical signal
which can be obtained or processed by instrumentation. In a
a
State Key Laboratory of Bioelectronics, School of Biological Science and Medical
Engineering, Southeast University, Nanjing 210096, China
b
Suzhou Key Laboratory of Environment and Biosafety, Research Institute of Southeast
University in Suzhou, Suzhou 215123, China
c
School of Chemistry and Chemical Engineering, Southeast University, Nanjing
210096, China
typical gas sensing device, the sensing materials and the
transformational signal have been considered as two key
parameters that determine the performance of the sensor, such
as sensitivity, selectivity, response speed and so on. The tradi-
tional gas sensing devices commonly use metal oxide or con-
ducting polymer as sensing materials, and employ the electrical
and gravimetric properties as transformational signal. Some of
these gas sensing devices have been successfully commercial-
ized, although they need to be operated at high temperatures,
leading to complicated congurations and high cost, which
seriously restrict their development.
Many technologies have been developed to improve the
sensitivity, simplify the process and lower the cost of the gas
sensing devices, in which using nanostructured sensing mate-
rials and optical signal detection have been considered to be a

Hua Xu is currently a lecturer at Zhongze Gu received his PhD

the State Key Laboratory of Bio-
electronics. She received her
Bachelor degree in Applied
Chemistry at the Jiangsu Normal
University in 2000 and her PhD
degree in Organic Chemistry at
the Nankai University in 2006.
In 2006–2008, she worked as a
postdoctor in Prof. Zhongze
Gu's group in State Key Labora-
tory of Bioelectronics, Southeast
University. Her research inter-
ests include organic functional materials, photonic crystal mate-
rials, chemical sensors and biosensors.
degree in 1998 from the Univer-
sity of Tokyo under the direction
of Professor Akira Fujishima. He
started his academic career in
1998 at the Photochemical
Conversion Materials Project in
KAST as a researcher. From
2003, he has been a Cheung
Kong Scholars Professor of Bio-
logical Science and Medical
Engineering, Southeast Univer-
sity. Now he is the director of
State Key Laboratory of Bioelectronics, and the director of Labo-
ratory of Environment and Biosafety in Suzhou, China. His
research interests include bio-inspired nanomaterials, tunable
photonic crystal materials, biosensors, electrospinning and the
biomedical applications of nanobers.

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Journal of Materials Chemistry C
signicant promising approach.5–10 Nanomaterials possess high
surface area/volume ratios, which increase the sites for gas/
vapor adsorption and so as to increase the sensitivity of the
device because the interaction between the gas analytes and the
sensing part is higher. An optical sensing method is usually
straightforward and could achieve higher sensitivity, selectivity,
stability and on-line real time detection. Furthermore, it
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possesses greater security that avoids the electromagnetic
interference caused by the electrical signal of the sensor.
Various nanostructured materials, such as nanoparticles,
nanobers, and photonic crystals (PhCs), have been developed
for optical gas sensing. This paper reviews the application of
PhCs in developing advanced optical gas sensing technology.
PhCs are materials that possess periodicity in the dielectric
constant, which was proposed aer the milestone work of
Yablonovitch and John in 1987.11,12 These materials can affect
the motion of photons in a similar way that a semiconductor
crystal affects the motion of electrons. The periodic arrange-
ment of the dielectric materials within the PhCs will produce a
photonic band gap (PBG). Light of certain wavelengths or
frequencies located in the PBG is forbidden to propagate
through the PhCs while other light is allowed to travel.13,14 This
property enables PhCs to control light with amazing facility and
produce effects that are impossible with conventional optics.
Therefore, in the last decade, PhCs have been widely applied in
zero-threshold laser, low-loss resonators, optical switches,
waveguides, optical bers and so on.15–21
In recent years, PhCs have shown promising application in
gas sensing owing to their novel structure and unique optical
properties.22–27 PhCs are ideal materials for gas/vapor sensing
because they have high specic surface area for absorbing gas
analytes and their optical properties could be modulated easily
through external gas/vapor. Furthermore, PhCs provide a
useful platform for portable and remote sensing because of
their small volume and sharp spectral features that can be
probed using low power laser probes. Many PhC based sensors
have been developed and show obvious advantages in sensi-
tivity, stability, security, miniaturisation, portability, on-line
use and remote monitoring. The work herein will present an
overall survey of the basic concepts and up-to-date literature
results concerning the use of PhCs for gas/vapor sensing. It
includes (1) optical properties and sensing mechanism of
PhCs; (2) PhCs with different structure for gas/vapor sensing;
(3) photonic noses.
2 Optical properties and sensing
mechanism of PhCs
As mentioned above, the periodic arrangements of dielectric
materials within the PhCs can produce a PBG. The propagation
of light with the wavelength located in their PBGs is forbidden,
thus diffraction of such light will be observed, which exhibits a
brilliant structural color. The diffraction properties of the PhCs
can be described by Bragg's law:28,29
ml ¼ 2ndsin q (1)
6088 | J. Mater. Chem. C, 2013, 1, 6087–6098
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where m is the diffraction order, l is the wavelength of incident
light, n is the effective refractive index of the periodic structure,
d is the spacing between the planes in lattice, and q is the
glancing angle between the incident light and diffraction crystal
planes. When light propagates through PhCs consisting of
periodic variation of the dielectric constant, the incident light
with certain wavelength that matches the PBG will be reected.
When the reection peak is located in the visible region, PhCs
will show bright colors.
From eqn (1), it can be readily concluded that the centre
wavelength of the reection peak, at normal incidence of the
light, depends on the spacing between the planes in lattice (d)
and the effective refractive index of the periodic structure (n).
The photonic nanoarchitectures are multicomponent materials,
and their refractive indices are worked with the effective
medium theory. Based on this theory, the average refractive
index of the photonic nanoarchitectures takes the average value
of the refractive indices of all their components,25,30–34 which can
be approximately calculated by the following law:
P 2
neff2 ¼ n i Vi (2)
where ni and Vi are the refractive index and the volume fraction,
respectively, of the individual components (i) of which the
photonic materials are composed.
By combining eqn (1) and (2), it is not difficult to reach the
conclusion that the effective refractive index (n) increased when
the air inside the void space of the PhCs is replaced by a vapor
compound with higher refractive index, which would cause a
shi of the Bragg peak to longer wavelengths. A similar effect
will occur if the lattice constant of the PhCs (d) is increased due
to the swelling of the vapor. These are the main optical sensing
mechanism of the PhCs for the gas/vapor compound. Moreover,
some other characteristic parameters of the Bragg peak such as
its intensity and spectral width will be strongly affected. Since
the porosity of PhCs is approximately 30–40% of the total
volume and the pore structures are well connected, the mole-
cule can diffuse easily and rapidly among these pores.
Besides serving as a sensing material, PhCs have also been
used to enhance the intensity of the excitation light or uores-
cence with the wavelength located into their PBGs and thus
improve the sensitivity of gas sensing.
3 PhCs for gas/vapor sensing
Although these traditional gas sensors employing the electrical
properties as transformational signals have been commonly
commercialized, their obvious disadvantages, such as low
sensitivity and selectivity, high operating temperature, sensi-
tivity to environmental factors and high energy consumption,
all restrict their development. Optical gas sensors can achieve
higher sensitivity, selectivity and stability than these traditional
gas sensors with much longer lifetime. Their response time is
relatively short and their performance is insensitive to
temperature and environment change. However, their widely
commercialized applications are seriously restricted due to the
difficulty in miniaturization and relatively high cost.
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An optical sensor usually consists of three basic parts: the
radiation source, the interaction volume and the detector, as
shown in Fig. 1. For a conventional optical gas sensor, the
interaction of the dilute gases with light is rather weak, which
necessitates relatively long interaction paths in the range of 10 to
50 cm to improve the sensitivity. Such long interaction paths
require a large interaction volume and a relatively large sensor
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device. To solve this problem, the mirrors were introduced to
increase the effective interaction of the radiation and the gas. The
mirrors could multiply reect the light within the interaction
volume and thereby multiply the interaction between the radia-
tion and the gas, which enables a reduction in the interaction
volume (Fig. 1a). However, this results in a high cost for such a
system because of its high demands on the optical components
and strict fabrication processes. The use of PhCs to replace the
interaction volume in a conventional optical sensor can obtain
compact, robust and low-cost gas sensors, as shown in Fig. 1b.23
Due to the low group velocity mode, the interaction of light and
gas within the interaction volume composed of PhCs is enhanced
and the interaction path is effectively reduced. The size of such a
PhC-based optical gas sensor can be reduced to less than 1 cm,
which is less than an order of magnitude improvement in volume
as compared to conventional optical gas sensors. Therefore, PhCs
provide a useful platform for portable and remote sensing
because of their small volume and sharp spectral features, which
can be probed using low power laser probes.
According to their different structure, some typical PhC
materials for advanced optical gas/vapors sensing application
will be reviewed below, including one-dimensional buttery
wings and their mimicking of nanostructures, porous silicon,
Bragg stacks and three-dimensional colloidal crystals and
inverse opal colloidal crystal.
3.1 Morpho buttery wing and their mimic nanostructure
In nature, amazing living creatures, which exhibit striking
brilliancy of color, such as some butteries, beetles, and
peacocks, provide various nature-made PhC nano-
architectures.35–37 Such natural PhCs have been used as low cost,
selective optical vapor sensors. Morpho buttery wings are one
of the most studied biophotonic materials for vapor sensing.38,39
The brilliant iridescent colors of the wing scales in the Morpho
buttery arise from the hierarchical and highly ordered
photonic structures (Fig. 2). The chemical composition of the
buttery scales is chitin and the buttery scales are mainly
constituted from chitin and air. When vapor is introduced to
the buttery scales, the average refractive index of the PBG
materials in buttery scales changes and the reection spectra
Fig. 1 Comparison of a conventional (a) and PhC based gas sensors (b).
Reprinted with permission from ref. 23. Copyright (2011) Elsevier.
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Fig. 2 Principle of highly selective vapor response based on hierarchical
photonic structures and demonstrated using M. sulkowskyi iridescent scales.
Reprinted with permission from ref. 38. Copyright (2009), Nature Publishing
Group.
are shied. This offers a handy way of using the natural
photonic nanoarchitectures as gas/vapor sensors. Potyrailo
reported that the iridescent scales of the Morpho sulkowskyi
buttery could give a different optical response to different
individual vapors, thus providing information about the prop-
erty and the concentration of the vapors.38 A range of closely
related vapors, such as water vapor, methanol, ethanol and
isomers of dichloroethylene could be identied. The diverse
spectral response was explained by the combined action of two
mechanisms: physical adsorption and capillary condensation of
condensable vapors in the nanosize domains of the M. sulkow-
skyi scales (Fig. 2). By studying the vapor sensing mechanism of
the natural PhCs, Potyrailo further pointed out that the scale–
vapor interaction strength depended on the combined effects of
the surface properties of the structures and the properties of the
detected vapors, such as surface tension, molar volume,
molecular shape and molecular size of the vapor. Therefore, an
enhancement of sensitivity and selectivity of the vapor response
could possibly be achieved by the design of articial PhC
systems, which formed hierarchical substructures with higher
surface area and tailored the surface properties of certain
spatial periodicity for specic vapors.
Many studies have been carried out to replicate the nano-
structures from the wing scales of butteries for superior gas/
vapor sensing application.40–42 Huang et al. replicated the ne
structure of Morpho peleides buttery-wing scales through a low-
temperature atomic layer deposition (ALD) process.43 Aer
calcination to remove the template, an inverted Al2O3 structure
of the buttery wing was obtained. The as-prepared structure
retained not only the morphology of the original template, but
also the optical properties, such as PBG. Zhang et al. fabricated
ZnO replicas of the buttery wings by using zinc nitrate as the
precursor solution.44–46 The replicas exhibited the hierarchical
and porous microstructures of the wing and maintained faith-
fully the microstructure character of the original templates
down to the sub-micrometer scale. In a similar manner, various
other metal oxide replicas of the buttery wings were fabricated
by using metal salts or metal alkoxides as precursors, such as
TiO2,47 ZrO2,48 and Al2O3. Using buttery wings as templates,
Song et al. fabricated well-organized porous hierarchical SnO2
with connective hollow interiors by an aqueous sol–gel soaking
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process and subsequent calcination.49 The porous hierarchical
structure was constructed by a layer of exural wall that was
assembled by SnO2 nanocrystallites with a diameter of around
7.0 nm. The wall thickness was tunable under the control of the
concentration during impregnation as well as the immersion
time (Fig. 3). On increasing immersion time or concentration
during impregnation, the wall thickness increased and the
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detail-loss also increased. The SnO2 replicas of the buttery
wings exhibit a high sensitivity (49.8–50 ppm ethanol) and a fast
response and recovery time (11 and 31 s to 50 ppm ethanol,
respectively) to ethanol vapor due to unique porous hierarchical
architecture and small nanocrystalline building blocks. More-
over, the response was found to be controllable and dependent
on the wall thickness such that the increase of wall thickness
resulted in a slow response.
3.2 Porous silicon PhCs
The porous silicon PhCs were rst used for sensing various
condensable volatile organic compounds (VOC) vapors. When
the porous silicon PhC lm was placed in a closed chamber in
which the VOC vapors can be gradually introduced, the vapors
were adsorbed and then condensed in the inner pore walls due
to the capillary forces in conned spaces. Upon the introduc-
tions of vapor species in the inner pore walls, the average
refractive index of the porous silicon PhCs is changed, resulting
in a shi of the reection peak, or the corresponding modulated
response. On the basis of this principle, a variety of porous
silicon PhCs structures, including Bragg mirrors, Fabry–Pérot
lms,50,51 have been constructed and employed to detect various
VOC vapors, including ethanol, hexane and so on.52–55 Recently,
to achieve a remote VOC sensing system, the porous silicon
PhCs and the optical bers were integrated by the Sailor group
(Fig. 4).56 The porous silicon PhCs with 8 mm thickness and
diameters of 500 mm were fabricated using an electropolishing
reaction and affixed to the end of a cleaved silica-core optical
ber. Spectra are obtained by introducing white light into one
arm of a bifurcated optical ber, and measuring light reected
from the porous Si sample in the other arm with a spectrometer
Fig. 3 FESEM images of the SnO2 replica with increasing concentration during impregnation and immersing time. (a and d) Immersion for 14 h, (b and e) 18 h, (c and f)
24 h. Reprinted with permission from ref. 49. Copyright (2010) Elsevier.
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as shown in Fig. 4a. The reectance peak shi for isopropanol,
cyclohexane, trichloroethylene, and water is shown in Fig. 4b.
The magnitude of the peak shi is dependent on both the
refractive index and the amount of gas analytes captured in the
porous matrix. Such a conguration is promising for real-time
monitoring of toxic gases because they are facile devices, use
low power and can be used for remote detection.
To improve the sensitivity and selectivity of the sensors, the
surface properties of the porous silicon PhCs were optimized
and the porosity was further tuned for the noncondensable gas
sensing.57 Hydrophobic porous silicon PhCs could be achieved
by surface modication of the porous silicon PhCs with
hydrophobic silane. In this case, an organic vapor would readily
interact within the hydrophobic functionalized pores, resulting
in an obvious red shi in the reection peak and improvement
in the sensitivity of the porous silicon PhCs.58–60 On the other
hand, hydrophilic porous silicon PhCs with strong adsorption
sites for water on the surface could be realized via oxidation or
modication with hydrophilic silane, which could be used as a
humidity sensor. Similarly, the pH sensitive dye bromothymol
blue was infused into the oxidized porous silicon PhCs for
specic ammonia sensing.61 Introduction of ammonia gas to
the sensor caused a dramatic change in the reection spectrum
of the bromothymol blue-coated porous silicon PhCs, as shown
in Fig. 5. The absorption maximum of the indicator dye shied
to 636 nm due to the indicator dye in its deprotonated form and
the reection peaks in 644 nm was completely obscured, which
could be used as a signal peak to sense ammonia. The reec-
tance peaks at 812 nm were still observed because the dye had
no signicant absorbance at 812 nm, which can used as a
reference peak. The amount of NH3 could be further measured
by the ratio of the intensity of these two reection peaks.
The lattice constant expansion/contraction induced the
reection spectrum change of the porous silicon PhCs and this
was also employed for gas sensing. Porous silicon PhC lms
coated with Pd were fabricated by immersion plating, in which
Pd was used to trap and store hydrogen. Absorption of hydrogen
onto Pd-coating porous silicon lms induced a lattice expansion
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Fig. 4 (a) A porous silicon PhCs is attached to a silica-core optical fiber (bottom right) for the in situ monitoring of VOC. A spectrometer monitors the reflected light
spectrum from the photonic crystal (upper right). (b) Porous silicon sensor response to isopropanol, trichloroethylene, cyclohexane, and water in the 50–600 ppmv
range. Reprinted with permission from ref. 56. Copyright (2007) Wiley.
leading to a shi of the optical fringes and a decrease in the
reected intensity.62 This sensor was able to detect hydrogen at
a concentration as low as 0.17 vol% in a few seconds by moni-
toring either the optical thickness change or the change in
reected light intensity. Similar methods were employed for a
highly selective HF sensor by using oxidized porous silicon
PhCs lms.63 Upon introduction of HF vapors, some of the SiO2
on the surface of the porous silicon PhCs were converted to
volatile SiF4, resulting in a thinning of the porous layer. As a
result, the optical thickness of the PhC lm decreased and a
corresponding blue shi in the reection spectrum was
observed. Apart from the silicon oxide, the silicon hydride on
the surface of the porous silicon PhCs can react with Cl2 to
generate reactive silicon halides that evaporate from the surface
and/or react with air to convert to silicon oxide.64 This process
reduced the net refractive index of the material that is detected
as a blue shi in the spectra. Because of the specicity of the
chemical reactions, minimal analyte cross reactivity is observed
between the two types of gas sensors.
3.3 Multilayer PhCs lms
Similar to the porous silicon PhCs, the multilayer PhC lms also
have nanometer-scale pores for the absorption and condensation
Fig. 5 Absorption (dashed line) and reflection spectra (solid line) of the bromothymol blue-infused porous SiO2 PhCs. (a) In the absence of NH3. (b) In the presence of
NH3. Reprinted with permission from ref. 61. Copyright (2007) Wiley.
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of vapors with the help of the capillary force. The vapor adsorp-
tion and condensation phenomena within the porous networks
of the multilayer PhC lms varied their refractive index, and
hence changed their optical features.65 Fig. 6a shows the optical
response of 8-layer porous PhCs built using nanoparticles of TiO2
and SiO2 at different partial pressures of isopropanol.66 The shi
of the reection spectrum to higher wavelengths is due to the
condensation of the vapor into the pores as previously explained.
Fig. 6b shows the evolution of the reection spectrum and its
intensity obtained at different partial pressure for the iso-
propanol vapor. The gradual increase of the peak position gives
valuable information related to the changes of vapor concentra-
tion in the surrounding environment.
The Ozin and Miguez group further fabricated the meso-
structured TiO2–SiO2 Bragg stacks for high sensitivity and
selective vapor sensing because of more effective capillary
condensation within the mesoscale nanopores and the molec-
ular sieve functions of the mesoscale nanopores. The reection
maximum of the mesoporous TiO2–SiO2 Bragg stacks drastically
changed about 70 nm within seconds when exposed to toluene
vapor (p/p0 ¼ 0.86) and the color of the lm also immediately
changed from blue to yellow due to adsorption of toluene
into the pores.67,68 In addition, the selectively functionalize
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Fig. 6 (a) Reflection spectra of the eight-layered PhCs at different partial pressures of isopropanol vapor. (b) Evolution of both the maximum spectral position (blue
circles) and its intensity (red triangles) for this periodic stack at different partial pressures of isopropanol vapor. Reprinted with permission from ref. 66. Copyright (2008)
American Chemical Society.
mesoporous multilayer lms can control adsorption of vapor
molecules in a given type of layer. This can lead to a selective
vapor adsorption, which modulated by organic components
attached to the pore surface. Miguez selectively modied the
pores of the mesoporous multilayer titania lms with hydro-
phobic, bulky molecules such as dihexadecyl phosphate
(DHDP). The resultant mesoporous lms showed different
responses to water and heptanes due to the presence of a
hydrophobic residue partially inhibited water inclusion and
favored adsorption of a nonpolar molecule such as heptane.69
In an alternative approach to the construction of meso-
structured Bragg stacks, ordered mesoporous TiO2 thin lms
have been coupled to the surface or the inside of the nano-
particle-based Bragg stacks (Fig. 7a and b).70,71 The reection
spectra obtained from two multilayer lms coated with meso-
structured lm with pore sizes of 9 nm and 3.5 nm exposed at
different partial pressures of isopropanol are shown in Fig. 7c.
The reection peak of the lm with pore sizes of 9 nm dip and
shi from 517 nm to 542 nm with the increase of partial pres-
sure of isopropanol from 0 to 1. The variation of the resonant
mode position is much less signicant (from 614 nm to 627 nm)
for the lm with pore sizes of 3.5 nm, as can be clearly seen in
Fig. 7c. These results indicated the vapor absorption capability
will depend on the relationship between the size of the pore and
the size of the probe molecules. Similar results were observed
from the dense SiO2–TiO2 multilayer containing a mesostruc-
tured TiO2 middle layer. As shown in Fig. 7d, the optical shis
caused by vapor adsorption were larger for smaller molecules,
and were negligible for the largest probe tested (butanol), which
highlights that the accessibility strongly depended on the rela-
tionship between pore and analyte sizes. These results also
indicated that the average pore size and its distribution could
be tailored to allow target-molecule size selectivity to be
combined with the optical changes induced by the adsorption
and condensation properties and yield more specic sensors.
One-dimensional Bragg stacks based on a microporous
metal–organic framework (MOF) material and mesoporous tita-
nium dioxide were also fabricated to improve the sensitivity and
selectivity of the multilayer lm sensors.72 Zeolitic imidazolate
framework ZIF-8 and mesoporous titanium dioxide were chosen
as functional components with different refractive indices. MOF
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ZIF-8 was intended to impart molecular selectivity, while meso-
porous TiO2 was used to ensure high refractive index contrast
and guarantee molecular diffusion within the Bragg stacks. The
combination of microporous MOF material with mesoporous
titanium dioxide layers within one scaffold endows the 1D-MOF
PhCs with characteristic adsorption properties upon exposure to
various organic vapors. The experimental results show that the
multilayered photonic heterostructures are sensitive and selec-
tive towards a series of chemically similar alcohol vapors, such as
methanol, ethanol, iso-butanol and tert-pentanol.
3.4 Colloidal PhCs
3.4.1 Colloidal crystals (CC). Self-assembled colloidal PhCs
have a lower volume fraction of voids (26%) than other type of
PhCs, which reduces the amount of condensed vapors in the
diffractive media and thus affects the detection sensitivity. To
overcome this limitation, a full-peak analysis technique or
multivariate analysis of the spectrum has been employed to
improve the sensitivity of the colloidal PhC-based vapor
sensor.73,74 In addition, self-assembly of monodisperse nano-
particles into colloidal crystals provides a convenient method to
modify the building blocks before or aer the formation of
crystal structures to improve responsiveness to ambient gas. As
a result, the majority of research on colloidal crystals for gas
sensing has been focused on incorporating gas-sensing mate-
rials into the self-assembled PhCs structures. The responsive
materials can effectively absorb or react with the vapor/gas,
which induces a change in the refractive indices or the lattice
constants of the crystalline arrays, and the optical features.
Lu et al. used the layer-by-layer method to grow the metal–
organic frameworks (MOF) HKUST-1, a permanently microporous
MOF with the empirical formula Cu2(BTC)3, in the interstitial
spaces between ordered silica microspheres, yielding a composite
MOF–silica colloidal crystal (MOF–SCC) (Fig. 8a and b).75 When
exposed to carbon disulde (CS2), the stop band of the MOF–SCC
showed red shis up to 16 nm (Fig. 8c). This observation was
consistent with an increase in the effective refractive index of the
microporous MOF due to absorption of CS2. Since the refractive
index change increased with increasing adsorbed CS2, the shi
also depended predictably on the analyte concentration (Fig. 8c
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Fig. 7 SEM images of cross section of a dense SiO2–TiO2 multilayer (a) coated with a mesostructured TiO2 film and (b) containing a mesostructured TiO2 middle layer;
(c) reflection spectra obtained at different partial pressures of isopropanol from 1D PhC coated with a mesostructured coating possessing pores of average size 9 nm
(top) and 3.5 nm (below). (d) Reflectance spectra obtained at different partial pressures of methanol, ethanol, 2-propanol, and butanol from mesostructured optical
resonators with pores of average size 9 nm. (a and c) and (b and d) Reprinted with permission from ref. 70 and 71. Copyright (2011 and 2009) Wiley.

and d). In addition, due to the ability of HKUST-1 to absorb a wide as small as 0.015 nm can be resolved with a high-resolution
range of analytes, the sensor also responded to other vapors spectrometer, yielding detection limits as low as 2.6, 0.5, and
including water and ethanol (Fig. 8e). The stop-band peak shis 0.3 ppm for water, carbon disulde, and ethanol, respectively.

Fig. 8 SEM images of the MOF–SCC thin film: (a) top view at high magnification, and (b) cross-sectional view at high magnification. (c) Near-IR extinction spectra of
MOF–SCC thin film and unmodified colloidal crystal thin film before and after exposure to CS2; (d) responses of MOF–SCC to a series of CS2 vapors of various
concentrations versus time. (e) Dependence of stop band peak shift of the MOF–SCC thin film on the vapor concentrations of different solvents; reprinted with
permission from ref. 75. Copyright (2011) Wiley.

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Journal of Materials Chemistry C
Similarly, Mı́guez fabricated polymer–gel colloidal PhCs
composed of a silica microsphere array embedded in a matrix of
the crosslinked polyferrocenylsilane for vapor sensing.76 Upon
exposure to dichloromethane vapor, the samples were found to
undergo highly reproducible and repeatable changes in optical
spectra due to swelling of the polymer by vapor uptake. This
swelling changed the refractive index of the polymer networks,
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as well as caused an increase in the lattice spacing of the PhCs
at higher vapor pressures. Similar research was reported by
Song in which incorporation of water-sensitive polyacrylamide
(PAAm) gel into colloidal crystal structures was used for colorful
humidity sensing.77 The as-prepared PhC hydrogels exhibited
an obvious reversible color change to different humidities, and
the color change covered the whole visible range, as shown in
Fig. 9a. The PhC hydrogels may serve as an alternative
economical candidates to traditional humidity sensors because
of their visible humidity sensitivity, facile fabrication approach
and low-cost. Furthermore, the PhC hydrogels sensors appeared
to be mechanically stable under cyclic humidity variations
(Fig. 9b), which could be made in the form of a exible thin lm
and attached to many surfaces as an energy-saving humidity
indicator.
Besides colloidal crystal lm, three-dimensional colloidal
crystal beads (CCBs) were also modied with responsive mate-
rials for gas sensing.78 CdTe QDs and zinc(II) meso-tetraphe-
nylporphyrin (ZnTPP) were successively coated on the CCB
surfaces for colorimetric ammonia sensing, in which ZnTPP
was used as ammonia-sensing material and the QDs were used
as a background layer to improve colorimetric limitation and
quantitatively detect ammonia. A distinct color change of the
sensor was observed to ammonia with concentrations from 100
to 2500 ppm due to luminescence quenching of the ZnTPP layer
(Fig. 10). This ammonia sensor has the advantage of a porous
spherical structure, controllable pore sizes, readable colori-
metric detection by the naked eye, wide observation angle and is
especially applicable for the quick detection of ammonia leak-
ing from some narrow places.
3.4.2 Inverse opal CC. Compared to colloidal crystal
structures, inverse opals CC for gas sensing are preferred
because they have larger pore volumes for absorbing gas ana-
lytes, leading to an apparent change in the reectance or
transmittance spectra. The porous structure also improves the
diffusion of the analyte throughout the photonic structure, thus
Fig. 9 (a) Photographs of PAAm-poly(St-MMA-AA) photonic hydrogel exposed
to different humidities. (b) Reversible conversion of stop-band position of
photonic hydrogel in ten successive cycles of increasing then decreasing the
humidity. Reproduced from ref. 77.
6094 | J. Mater. Chem. C, 2013, 1, 6087–6098
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Fig. 10 Apparent colors of the QDs-ZnTPP modified CCBs sensor to different
concentrations of ammonia. Reprinted with permission from ref. 78. Copyright
(2013) Springer.
enhancing the response rate of the sensors. Jiang and Yang
fabricated macroporous polymer inverse opal CC structures
with 74% porosity by a silica colloidal crystal template
method.79 When exposed to ethanol vapor, the optical stop
band of the macroporous polymer lm exhibited a distinct red-
shi due to the increase of the effective refractive index induced
by capillary condensation of ethanol vapor in the inter-
connected macropores. The wavelength shi is linearly
proportional to the ethanol partial pressure, as shown in Fig. 11
inset. Furthermore, the response speed of the macroporous
polymer lm to ethanol vapor is less than 1 min due to larger
pore volume of inverse opals. However, the macroporous poly-
mer lm exhibited poor selective to variety of polar vapors, such
as ethanol and water.
Template replication for the preparation of the inverse
opal provided a simple, efficient approach to introduce the
gas-sensing materials into PhC structures for improved gas
sensing. Gu et al. fabricated Pt-doped WO3 inverse opals by
replicating a polystyrene colloidal crystal template with a
WO3 sol–gel, followed by Pt sputter–deposition.80 The as-
prepared Pt-doped WO3 inverse opals exhibited a rapid
wavelength shi as well as intensity change of the reective
peak in response to H2 stimulation. The change of spectra can
be explained by the reaction of H2 and Pt–WO3, which
changes the average refractive index of the Pt–WO3 inverse
opal and hence the reection spectra. The Pt–WO3 PhCs
also exhibited good recovery and high sensitivity to hydrogen
in the range of 100% to 0.1%. Associated with different
Fig. 11 Reflection spectra of the macroporous polymer film exposed to ethanol
vapor with different partial pressures. Inset is the dependence of the shift of the
Bragg diffraction peak on the ethanol partial pressure. Reprinted with permission
from ref. 79. Copyright (2011) American Institute of Physics.
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materials-induced selectivity, a series of inverse opal struc-
tured PhCs can be fabricated for specic responses for
different gases.81
Similar work reported by Song that fabricated the spi-
ropyran derivative (SP) dyed SiO2 inverse opals for reversible
acid–base vapor sensing.82 Besides a reversible change in
reection spectra, the uorescence spectra of SP dyed inverse
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opal also exhibited a switchable on/off ability under alter-
nating acid–base vapors. Further work reported by the same
group that inltrated polyaniline (PANI) into a TiO2 inverse
opal photonic crystal for simple and fast naked-eye detection
of NH3–HCl vapor.83 PANI has proven to be a sensitive element
for detecting gaseous NH3 and HCl, which could induce the
protonation–depronation process of the PANI. When exposed
to NH3 and HCl atmospheres alternately, the as-prepared PhCs
showed a reversibly color change between red and green,
which could be observed by the naked eye (Fig. 12). The color
change was derived from the shi of the stopband owing to the
variation of the refractive index of PANI in different acid and
base environments. Compared with traditional work, this
method realized the detection by the naked eye without
using special optical/electrical devices or apparatus and
had potential application in real-time monitoring of acid and
base vapors.
Inverse opal PhCs were also used to amplify uorescence
signal for trace trinitrotoluene (TNT) vapor detection.84 The
introduction of PhCs into the traditional TNT detection system
could magnify the uorescence signal up to 60.6-fold in
comparison with that of the control sample. Furthermore, the
quenching efficiency of the PhC-based sensor achieved 80%
aer exposure to TNT vapor for 300 s. The results suggested
that the uorescence-amplifying method based on PhCs has
enormous potential for the development of highly efficient
uorescence sensors toward detection of trace TNT or other
explosives.
Fig. 12 (a) Photographs of the as-prepared PhCs corresponding to different
exposure times to NH3 and HCl vapors. (b) The reflectance spectra of a PANI-
infiltrated TiO2 inverse opal exposed to NH3–HCl vapors. Reprinted with permis-
sion from ref. 83. Copyright (2012) Wiley.
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Journal of Materials Chemistry C
4 Photonic noses
Single gas sensors usually have the drawback of poor selectivity,
causing them to respond, not necessarily uniquely, to multiple
analytes, which is also known as cross-sensitivity. Therefore a
cross-sensitive sensor cannot serve as a unique identier or
signature for gas samples of completely unknown compositions.
Utilization of sensor arrays is the main method to solve this
problem. An array-based sensing technology that utilizes
multiple sensors, each of which has a partial specicity that
works in tandem to produce a unique composite response for
each analyte, has emerged as a powerful new approach towards
gas detection.85–88 Many arrays based on the modulation of elec-
trical and gravimetric properties have been developed and are
used as articial noses, known as “Electronic Noses”. Unfortu-
nately, successfully commercialized, electronic noses generally
suffer from being complex and are expensive. Recently, Ozin
group proposed and developed the concept of a photonic nose,
whose operating principle was based on the molecule-induced
modulation of the optical Bragg diffraction properties of a
photonic crystal.89,90 The photonic nose is a straightforward, low-
cost, environmentally friendly and defect-tolerant combinatorial
colorimetric sensor that is able to detect and discriminate vapor
species with a simple digital-camera color-imaging system.
Porous Bragg stacks consisting of alternating SiO2 and TiO2
nanoparticulate layers were functionalized with different
alkoxysilanes to create a array of photonic crystal “pixels” with
different surface energy characteristics (Fig. 13). The sensing
array serving as an articial nose was obtained by using sensing
units with distinct surface energy and molecular recognition
properties. Adsorption of vapor analytes into the pores of the
Bragg reectors led to signicant changes in color due to an
increase in the effective refractive index of the layers. Moreover,
the adsorption properties could be easily modulated by judi-
cious surface functionalization and the proper choice of
composition so that different overall color changes arose when
the same array was exposed to different vapor environments. As
a proof of concept, they exposed the functionalized Bragg stack
array to different saturated vapors, which yielded different color
Fig. 13 Scheme illustrating the data analysis process using pre- and post-
exposure RGB images as an input. Reprinted with permission from ref. 90.
Copyright (2011) Wiley.
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Journal of Materials Chemistry C
responses in each single functionalized photonic detector.
Soware color analysis of each pixel in the sensor array could
obtain unique color patterns for each vapor-phase species
(Fig. 13). On the basis of this photonic nose platform, not only a
series of alcohol and alkane vapors but also four different
bacteria strains could be easily identied by using principal
component analysis (PCA) as the pattern recognition method.
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Furthermore, the photonic nose platforms have been further
employed to address problems relevant to foodstuff monitoring
and drinking-water analysis.90
Besides 1D Bragg stacks, three-dimensional CCBs combined
with porphyrins have been used for photonic nose platforms.
Gu et al. fabricated a spherical porphyrin sensor arrays using
CCBs as the encoding microcarriers.91 The advantages of the
spherical sensor arrays were that the array fabrication is simple,
fast, inexpensive and repeatable because billions of identically
responding sensor elements could be fabricated simultaneously
in a homogeneous solution, and arrays had been produced by
simply combining different sensor elements. Because each
array was fabricated using only a small amount of the sensor
elements, this procedure could be used to fabricate thousands
of arrays that respond identically. However, a critical issue in
this spherical sensor array was that the sensors in the array were
formed in a chaotic manner, and it was difficult to discriminate
among the different sensors. To solve this problem, the reec-
tion peak of the CCBs served as the encoding signal to distin-
guish between different sensors and the change in uorescence
color of the porphyrin-modied CCB array served as the detec-
tion signal for discriminating among different VOC vapors
(Fig. 14a). VOC vapor detection by these spherical sensor arrays
displayed excellent discrimination among a very wide range of
compounds by using hierarchical cluster analysis (HCA) as the
pattern recognition method (Fig. 14b). This spherical sensor
array, with its simple preparation, rapid response, high sensi-
tivity, reproducibility, humidity insensitivity, and especially
with stable and high-throughput encoding, is promising for real
applications in articial olfactory systems.
5 Conclusions
In this review, we have summarized the recent developments in
the use of the PhC structures with different structure types for
Fig. 14 (a) Schematic illustration of the basic steps in the fluorescence color imagery analysis to methanol in a saturated atmosphere in the porphyrin-modified CCB
array. (b) Hierarchical cluster analysis (HCA) for six VOC vapors at their saturated vapor pressure at 298 K. Reprinted with permission from ref. 91. Copyright (2012)
American Chemical Society.
6096 | J. Mater. Chem. C, 2013, 1, 6087–6098
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gas/vapor sensing. The sensing mechanism largely relied on
modulation of the optical properties of the PhC with a change in
their effective refractive index or lattice constant through the
external gas/vapor. The large surface area of PhCs and their
relatively easily modied surface have resulted in a variety of
highly effective gas sensor congurations. Furthermore, PhCs
provide a useful platform for portable and remote sensing
functions because of their small volume and the sharp spectral
features that can be probed using low power laser probes, which
opens up a new way to design micro sensors and integrated
optical circuits.
Acknowledgements
This work was supported by National Basic Research Program of
China (Grants 2012CB933302), NSFC (Grants 21103020,
51102043 and 50925309), Suzhou Science and Technology
Department (Grants SYG201209, SH201110).
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