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Hybrid Metamaterial Absorber Platform for Sensing

of CO2 Gas at Mid-IR
Dihan Hasan and Chengkuo Lee*
pollution is currently regarded as the most
Application of two major classes of CO2 gas sensors, i.e., electrochemical and harmful form of environmental pollution
nondispersive infrared is predominantly impeded by the poor selectivity and which is caused by a myriad of natural and
large optical interaction length, respectively. Here, a novel “hybrid metamaterial” manmade agents. Among them, emission
absorber platform is presented by integrating the state-of-the-art comple- of greenhouse gases (e.g., CO2) causing
global warming has been a critical envi-
mentary metal–oxide–semiconductor compatible metamaterial with a smart,
ronmental concern over the last decade.[1,2]
gas-selective-trapping polymer for highly selective and miniaturized optical Apart from emission control, precision
sensing of CO2 gas in the 5–8 µm mid-IR spectral window. The sensor offers sensing of CO2 gas is indispensable for
a minimum of 40 ppm detection limit at ambient temperature on a small indoor air quality (IAQ) monitoring and
footprint (20 µm by 20 µm), fast response time (≈2 min), and low hysteresis. As heating, ventilation and air conditioning
systems, industrial storage and refrigera-
a proof-of-concept, net absor­ption enhancement of 0.0282%/ppm and wave-
tion, and medical applications such as cap-
length shift of 0.5319 nm ppm−1 are reported. Furthermore, the gas- selective nography. Many efforts have been invested
smart polymer is found to enable dual-mode multiplexed sensing for cross- for the development of application-specific
checking and validation of gas concentration on a single platform. Additionally, CO2 sensors. Two major approaches include
unique sensing characteristics as determined by the operating wavelength and (i) electrochemical sensing using gas-
bandwidth are demonstrated. Also, large differential response of the metamate- selective ceramics[3] and (ii) nondispersive
infrared (NDIR) sensing using optical ele-
rial absorber platform for all-optical monitoring is explored. The results will pave
ments, i.e., microheaters, filters, and infrared
the way for a physical understanding of metamaterial-based sensing when inte- sensors.[4] Although, electrochemical sen-
grated with the mid-IR detector for readout and extending the mid-IR function- sors are widely used in market and could be
alities of selective polymers for the detection of technologically relevant gases. ideally further downsizing for portable elec-
tronic applications, such sensors strongly
suffer from poor selectivity and large power
1. Introduction consumption and hysteresis. Current NDIR platform promises
lower hysteresis, but selectivity is still limited in a mixed sensing
Increasing rate of environmental pollution is causing monu- environment where various pollutant gases including water
mental and irreversible damage to the earth as the rapid urbani- vapor coexist interfering at the same operating wavelength. More
zation and industrialization take place across the globe. Air importantly, NDIR sensors require centimeter long optical inter-
action length with low roughness sidewall in order to achieve ppm
D. Hasan, Prof. C. Lee level detection limit with high signal-to-noise ratio (S/N ratio).
Department of Electrical and Computer Engineering Therefore, present NDIR devices are bulky and limited for per-
National University of Singapore sonalized applications. Recently, 10 000 ppm detection limit is
4 Engineering Drive 3, Singapore 117576, Singapore achieved in an NDIR setup with a ≈7.5 mm long optical interac-
E-mail: [email protected]
tion length, where it also reports characterization of metamaterial
D. Hasan, Prof. C. Lee
NUS Suzhou Research Institute (NUSRI) emitter.[5] While metamaterial emitters for producing radiation
Suzhou Industrial Park, Suzhou 215123, P. R. China of wavelength with high-quality factor have been investigated by
D. Hasan, Prof. C. Lee a few groups,[6,7] enhanced absorption characteristics in mid-IR
Center for Intelligent Sensors and MEMS spectrum by using metamaterials absorber for gas detection
National University of Singapore with high selectivity has not been reported. In contrast with
E6#05-11F, 5 Engineering Drive 1, Singapore 117608, Singapore
metamaterial emitter, metamaterial absorber enables the con-
Prof. C. Lee
version of light into heat for read out by the integrated system.
Graduate School for Integrative Science and Engineering
National University of Singapore With the aid of metamaterials absorber, the gas sensing system
Singapore 117576, Singapore can achieve high wavelength selectivity, polarization depend-
The ORCID identification number(s) for the author(s) of this article ence, and controlled light-matter interaction.[8–14] However, due
can be found under https://doi.org/10.1002/advs.201700581. to the small size of CO2 molecule (232 pm), the near field cou-
© 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, pling between the metamaterial absorber and gas is still limited.
Weinheim. This is an open access article under the terms of the Creative Besides, the all kind of surrounding gas molecules including
Commons Attribution License, which permits use, distribution and re- water vapor will again contribute signature peaks and wavelength
production in any medium, provided the original work is properly cited. shift in this sensing platform when we apply it in practical. It
DOI: 10.1002/advs.201700581 means the selective detection of particular gas is not achievable

Adv. Sci. 2018, 5, 1700581 1700581 (1 of 13) © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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in the metamaterial absorber-based NDIR sensing platform. 2. Hybrid Metamaterial Absorber Platform
By incorporating a gas-selective-trapping polymer into the
existing NDIR sensing platform, we can overcome this grand Figure 1 represents the mid-IR metamaterial platform for CO2
challenge of gas sensing. sensing application. The emerging issue of greenhouse
Here, we combine two different sensing mechanisms, i.e., CO2 emission is illustrated in Figure 1a for which massively
the infrared finger prints associated with the electrochem- deployable, CMOS compatible sensors are necessary. Concep-
ical response of a smart, gas-selective-trapping polymer and tual integration of the hybrid metamaterial platform for CO2
enhanced absorption characteristics of metamaterial absorber in sensing with the state-of-the-art NDIR system (Figure 1b) is pre-
the mid-IR spectra, into a “hybrid device” as a new miniaturized sented in Figure 1c.[20] Figure 1c shows the post-CMOS integra-
optical gas sensor.[15,16] The miniaturization is realized as the tion of gas-selective, enrichment layer (polyethylenimine, PEI).
gas-selective-trapping polymer layer physically captures and The representative metamaterial pattern in this work is
concen­trates the CO2 molecules of the surrounding area. Near-field shown in Figure 1d. AFM (atomic force microscopy) image in
coupling of the polymer with the metamaterial absorber enables Figure 1e and roughness plot in Figure 1f strongly suggest the
the sensitive detection of chemical transformation of the polymer uniformity of the spin-coated PEI film on metamaterial pat-
driven by the capture of gas molecules. The proposed approach terns. The metamaterial absorber is consist of metal-dielectric
exhibits ppm range of detection limit (40 ppm as reported in spacer-metal layers. The dimensional parameters (length: l and
this work) implying at least 250 times better sensitivity than the width: w) of the metal patterns at the top layer are shown in
previous work,[5] while the optical interaction length (1 mm) is Figure 1g. In this work, the width of the pattern is kept fixed at
reduced by approximately seven times and shows high selectivity ≈287 nm being limited by the critical dimension of the lithog-
against humidity and various other pollutant gases. Hence, our raphy process. The thicknesses of the top metal layer, dielec-
new approach is a promising solution for future gas sensing tric spacer, and bottom metal layer are fixed at 100, 200, and
systems. Here, we identify a suitable CO2 sensitive, amine- 200 nm, respectively. The resonant E-field distribution at the
based chemisorbent for the post-complementary metal–oxide– device plane (XY plane) and H-field distribution at the device
semiconductor (CMOS) integration in order to realize a “hybrid cross-section are given in Figure 1h,i, respectively, in which a
metamaterial” absorber platform. Previously 2D materials such plane wave light source is incident on the 3D structure from
as graphene and MoS2 with exotic properties show selective gas the top. The polarization of the incoming radiation is fixed
sensing features particularly at a very low concentration.[17] How- along x-axis while the probe wavelength is set to be 6.5 µm.
ever, such approach is predominantly limited to electrical detec- In particular, integration of metamaterial platform with
tion and does not work well in optical detection due to the weak such gas-selective smart material offers two specific features to
optical response of 2D materials. Also, certain plasmonic metal improve the performance of the gas sensor. First, it can over-
(e.g., Pd) can selectively form chemical compound with reac- come the weak near-field interaction between gas molecule in
tive agent and particularly allows sensing of chemically active free space and plasmonic metamaterial pattern.[21] Second, it not
gases (e.g., H2).[18] However, the abovementioned approach does only enables the effective utilization of the rich physics of meta-
not work for sensing the chemically inert gases such as CO2. materials for gas sensing applications but also provides a scal-
Although porous metal–organic framework can facilitate the able route for optical sensing of any gas on demand depending
trapping of CO2 molecules, the infrared absorption intensity of on the wavelength characteristics of the selective membrane.
the trapped molecules is typically low requiring long interac- For example, coupling with the slow light has been reported to
tion length to generate readable signals above the noise level. enhance the infrared absorption intensity by at least 1000 times
Recently a detection limit of ≈60 000 ppm is demonstrated by ultimately improving the linearity and range of detection
Wang and co-workers in a 5 mm long device based on such prin- of the hybrid optical sensor.[22] In general, gas sensing at
ciple.[19] Therefore, chemically active gas-selective polymer such infrared is based on Beer–Lambert law: I = I0 exp (−γ α L) where
as amine-based chemisorbent with rich mid-IR functionalities I is the transmitted light intensity and I0 is the incident inten-
has the potential for truly miniaturizing the CO2 gas sensor with sity, α is the effective absorption coefficient of the gas, which is
ppm range of detection limit. The CMOS platform further prom- determined by the gas concentration and is strongly dispersive.
ises scalable and repeatable integrated sensor manufactured at a L is the interaction length and γ is the enhancement factor deter-
very low cost. One critical challenge behind the integration is the mined by the sensor structure. In state-of-the-art NDIR system
compatibility between the CMOS compatible metal surface (Mo without any gas-selective enrichment layer, γ can be assumed
in this work) and gas-selective thin film. Here, we report stable to be equal to 1. Here, we propose that γ can be greater than
sensing characteristics of the platform implying strong adhesion 1 reducing the overall interaction length for sensing through the
between the two heterogonous layers for repeatable applications. near-field coupling of metamaterial patterns with the infrared
Furthermore, an added advantage of the gas-selective polymer absorption bands of the gas specific chemical species within
for dual-mode sensing is experimentally confirmed. Besides, we the gas-selective layer. Perfect absorption condition as the refe­
experimentally report unique sensing characteristics of the plat- rence can be further ensured in the hybrid system through
form at various ranges of gas concentration and the optimized metamaterial design principles for sensor operation above the
condition for maximum differential response. This work will pri- noise margin in the integrated system.[23,24] The heat convec-
marily focus on the detailed study of the proposed versatile plat- tion loss in the integrated system can be further overcome by
form from its optical physics and chemical functionalities’ point the matured technology of chip-scale vacuum encapsulation.[25]
of view. We believe, the findings will lay the solid foundation for Besides, we report the ultimate advantages of strengthening
the successful system-level integration of the platform in future. infrared absorption of the gas-selective polymer by surface

Adv. Sci. 2018, 5, 1700581 1700581 (2 of 13) © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 1. a) Increasing emission of CO2 as one of the emerging environmental risk factors for living beings demanding large-scale deployment of sensors
achievable only under low cost, CMOS platform. b) Conceptual diagram of state-of-the-art nondispersive infrared (NDIR) sensing platform. “Active meta-
material” absorber platform with the potential for physically trapping CO2 gas and thereby, reducing the gas cell length for miniaturized sensor is indicated
accordingly. c) Proposed “hybrid metamaterial” absorber integrated with thin film membrane for selective gas sensing. d) FESEM (field emission scanning
electron microscopy) image of the array of the metamaterial patterns (Inset: zoomed in view of the unit cell). e) AFM image of the PEI surface coated on
the metamaterial patterns. f) AFM height profile of the PEI surface. g) Crosswire metamaterial pattern for polarization independent sensing characteristics
h). i) 3D FDTD (finite-difference time-domain) simulated electric field and magnetic field intensity distribution along XY plane and XZ plane of the absorber
device, respectively, at the perfect absorber resonant condition. Confinement of H-field in the dielectric spacer region leading to antiparallel current flow
between the top metal and bottom metal at absorption resonance is marked by the white rectangular boundary. j) Coupling of metamaterial absorption reso-
nance mediated by thin film interference into the vibrational modes of CO2 selective layer for the sensing (adsorption and desorption) k). l) Energy diagram
representation and effect of coupling to closely spaced material vibrations on metamaterial resonance, respectively. Presence of infrared material vibrations is
strongly subject to gas adsorption and desorption providing multiple routes for the selective detection of CO2 gas.

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enhancement via near field coupling so as to maximize the self-recovery as the sampling gas leaves the chamber by diffusion
overall sensitivity.[26] Additionally, the advantage of metamate- (Figure S2, Supporting Information).
rial absorber for reflection-based all-optical monitoring with
large differential response is explored.
Figure 1j shows the coupling of interference in thin film 3.2. Proof-of-Concept Demonstration of CO2 Sensing
spacer with the gas-selective layer. Due to the presence of at Steady State
multiple, chemically active vibrational modes, such coupling
is unique for CO2 adsorption and desorption event. The A bare 8″ silicon wafer was cleaned and 200 nm of Mo followed
energy level diagram showing the multiple paths of coupling by the AlN thin film for the spacer and the top 100 nm Mo film
of metamaterial mode (λm) into the adjacent, closely spaced for the patterns were sputtered under high vacuum. Deep UV
(≈250–500 nm in this work) vibrational modes (λ1, λ2, and λ3) photolithography process was used to define the metamaterial
for sensing applications is shown in Figure 1k. Again, the patterns. Finally, Mo was dry etched to form the final absorber
quality factor of metamaterial absorbers at mid-IR is typically structure. The gas-selective layer is obtained by spin coating at
in the range of 5–10 at the corresponding 5–8 µm spectral various speeds. A maximum thickness of 300 nm was obtained
region and therefore can span over the closely spaced vibra- from the prepared solution at a speed of 1000 rpm. For char-
tional finger-prints. CO2-dependent coupling is illustrated acterization, high-resolution Fourier transformed infrared
in Figure 1l exhibiting the effective broadening of the back- (FTIR) microscope integrated with a heat stage and sealed gas
ground metamaterial mode. cell chamber was deployed. The reflected signal is normalized
with respect to a smooth gold surface. The incident light source
is unpolarized unless otherwise stated. The integrated setup is
3. Integration of CO2 Selective Polymer shown in Figure 2b,c. The calibration of the sensor is confirmed
by a commercial CO2 meter. The properties of the materials
with Metamaterial Absorber
chosen for the hybrid sensor are listed in Table 1. Mechanical
3.1. Material Characterization for CO2 Sensing matching is obtained between AlN and Mo on purpose to mini-
mize the hysteresis effect due to thermal stress over repeat cycles
The gas selective behavior of the enrichment material can be of thermal reset (desorption). Besides, high thermal conductivity
optically probed in details in the mid-IR spectrum. The CO2 of AlN is considered in order to ensure fast heat transfer between
selectivity is achieved due to its covalent interaction with the the absorber and the detector in the integrated system.[27]
amine rich polymer. The chemical reactions involved with Figure 2d shows the behavior of the PEI film on a metallic
the adsorption and desorption of CO2 in the active layer and substrate without any pattern as it is exposed to ambient CO2
the associated frequencies are described in Figure 2a. Clearly, sorption and thermal desorption. A strong contrast of intensity
mid-IR spectroscopy opens up the possibility of implementing (60%) is observed at around 3 µm due to the formation of the
sensors with multipath selectivity and sensitivity out of the unique infrared chemical species by the exposure to CO2. On the
smart material. Detailed chemical reactions involved as CO2 other hand, five distinct spectral points are identified within the
reacts with the primary and secondary amines of the branched range 5–8 µm which we leverage in this work for the sensor cali-
PEI polymer chain are as below bration. Figure 2e is the proof-of-concept demonstration of the
sensing behavior of the hybrid platform on a footprint of 20 µm
CO2 + 2RNH2 => RNHCOO− + RNH3+ (1) by 20 µm. The length (l) of the corresponding pattern is 2.3 µm
yielding maximal overlap with the closely spaced vibrational
CO2 + 2R 2 NH => R 2 NCOO− + R 2 NH2+ (2) modes. The pristine device almost maintains perfect absorption
condition (A = 1 − R) by design. The perfect absorption condition
CO2 + R 2NH + R′ NH2 => R 2NCOO− + R′ NH3+ still prevails in its hybrid form in both conditions, i.e., exposed to
(3) CO2 and thermally desorped. Notably, microheater-based thermal
(or R′ NHCOO− + R 2NH+2 )
swing integrated with metal-based metamaterial platform is
In the presence of humidity, an equimolar reaction takes achievable here for fully on-chip reset of the sensor via thermal
place as below desorption. The observed concentration-dependent modulation
of the net structural absorption can be further correlated with
R 2 NH + CO2 + H2 O => R 2 NH2+ + HCO3− (4) the light-to-heat conversion in the integrated system. In contrast
with the hybrid structure, the uncoated metamaterial absorber
We further perform the electrical charge characterization of shows negligible response toward the exposure of CO2 in Figure
the smart material under various CO2 conditions and confirm 2f. The refractive index (RI) induced shift can be calculated as
the selectivity behavior of the obtained thin film (Figure S1, ∆ λ = m(nCO2 − nN2 )(1 − e −2d /ld ) where m is the RI sensitivity
Supporting Information). The measured electrical results [in nm/RI unit (RIU)], d is the effective thickness of medium and
strongly correlate with the formation of infrared species with ld is the electromagnetic field decay length of the metamaterial
unique fingerprints at the surface of the PEI gas-selective layer. patterns in the order of few hundred nanometer.[28] In the case
In this work, we particularly focus on the infrared bands without the gas-selective layer, d >> ld, while the refractive indices
located in the range from 1300 cm−1 (7.692 µm) to 1700 cm−1 of CO2 and N2 are 1.0004 and 1.0002, respectively. The average
(5.882 µm) for the sensor calibration at steady state. Interestingly, RI sensitivity of the metamaterial absorber structures are experi-
the chemical fingerprints around 3055–3420 cm−1 show unusual mentally found to be 500 nm/RI unit. Therefore, the maximum

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Figure 2. a) Chemical reactions followed by the adsorption and desorption of the CO2 sensitive layer and frequency assignments for the possible
byproducts of the reaction path. Upon heating in a nitrogen environment, the formed species can recover back to original polyetheleneimine with
negligible loss. b) Schematic of the gas sensing setup and c) gas sensing setup used for the experiment. The volume of the gas chamber used is
100 cm3. Gas flow rate is maintained at 500 mL min−1 with N2 used as the carrier gas. d) Comparison between as prepared (exposed to 600 ppm CO2
in ambient) and thermally desorped (treated at 100 °C for 2 min) PEI film. e) Effects of as prepared and thermally desorped PEI film on the resonance
profile of the crosswire absorber structure. Five distinct frequency points are identified (pt1: 6.06 µm, pt2: 6.57 µm, pt3: 6.75 µm, pt4: 7.092 µm, and
pt5: 7.57 µm) for studying the gas sensing characteristics of the hybrid geometry. f) Response of the metamaterial absorber structure in the absence
of gas-selective layer as exposed to various CO2 concentrations at 70% ambient humidity.

wavelength shift expected is 0.1 nm while the observed shift in such definite trend can be observed at around the resonance
Figure 2f is ≈1 nm. The additional shift can be attributed to the wavelength of the structure clearly implying the random nature
adsorption of water vapor (water contents: ≈20 ppm v/v in the of the physical adsorption of foreign molecules. On the other
food grade CO2) by the lightly oxidized Mo surface at the given hand, the active device proposed in this work shows high sensi-
inlet pressure of the miniaturized gas chamber in this work.[29] tivity to CO2 concentration under the identical sensing condition.
Although a strong correlation between the intensity of the CO2 It is notable that a broadening phenomenon is observed
finger print and gas concentration is observed in Figure 2f, no when the background metamaterial is coupled to the group of

Adv. Sci. 2018, 5, 1700581 1700581 (5 of 13) © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Table 1. Material properties of the hybrid platform.

Material Melting point Young’s modulus Poisson ratio Coefficient of thermal Thermal conductivity
[°C] (E [GPa]) [µ] expansion: CTE (× 10–6 K–1) [W m−1 k−1]
Aluminum nitride 2200 344.8 0.287 4.6 285
Molybdenum 2620 329 0.32 4.8 140
PEI 95 2.9 0.44 56 0.23

vibrational modes in both cases. Under thin film assumption, absence of the wavelength selective loss in the dielectric layer.
such broadening can be contributed by the recurrent mode Subsequently, such enhanced interaction can lead to strong
splitting as expressed by the following equations[30,31] overlap of the absorption bands for a given line width of the
bands and cause effective broadening of the dips. Figure 3b
E m + E vib (E m − E vib )2 depicts the phenomenon as the strength of the oscillators is
E± = ± +ν2 (5) scaled up five times. Metamaterial absorber geometry properly
2 4
designed to cover the spectral locations of the available phonon
Here, Em and Evib are the energy state of the background modes of the polymer can therefore effectively enhance the
metamaterial mode and material vibrational mode, respectively, absorption that ultimately leads to the broadening of the under-
and ν is the coupling strength between the modes. Such cou- lying metamaterial absorber mode. The role of thin film inter-
pling can also lead to hybrid features that are spectrally shifted ference supported by the back metal reflector can be further
from the isolated vibrational modes. However, in the thick film verified by the experimental results in Figure 3c,d, where the
case for sensor applications, we also take into account the influ- back metal reflector is removed on purpose while the thickness
ence caused by the vibrational modes on the destructive inter- of the top PEI film is kept constant at 300 nm. The results as a
ference condition between the direct reflection from the function of the length (l) of the metamaterial pattern show no
air–device interface and the subsequent reflections as shown in strong evidence of coupling with the underlying resonance and
Figure 1g.[32] Although, in absorber case, the superimposed closely correspond to the characteristics of PEI film alone. It
reflection defined as R  = r + r 1 + r 2 + r 3 +  can be mini- implies significant screening of the weakly resonant patterns by
mized at a single wavelength for a given mode, additional the 300 nm film in the absence of back metal reflector. There-
decrease of reflection at adjacent wavelengths can be still fore, metamaterial absorber structure considered in this work
expected due to the multiple interactions within the absorbing not only provides the wavelength selectivity but also ensures
overlayer before the light escapes. Such phenomenon can strong interaction with the sufficiently thick gas-selective film
further aid the broadening behavior and is strongly supported as needed for the sensing application.
by the results in Figure 2. To investigate the effect, we analyti- We further conduct a representative simulation of the meta-
cally derive the reflection of the gas-selective polymer assumed material absorber structures using 3D finite-difference time-
to be deposited on a metallic substrate. The overall domain (FDTD) method. The results also correspond to the
reflection governed by the thin film interference can be defined overlapping of modes that ultimately leads to such broadening
as r = [r 12 + r 23 exp(2i β )] / [1 + r 12 r 23 exp(2i β )] where the (Figure S3a–f, Supporting Information). It is also observed that
subscripts 1, 2, and 3 denote the air, dielectric polymer, and the coupling into all of the modes reaches saturation at a par-
metal region, respectively, and β implies the propagation con- ticular thickness (Figure S3g, Supporting Information) while a
stant in the dielectric region. The gas-selective material is mod- given mode can reach saturation at lower thickness depending
eled by five Lorentz oscillators. The Fano-type resonances are on the spectral location of the background metamaterial mode.
5
Also, the field intensity distributions in Figure S3i–n in the
defined by ε = ε o + ∑ε lorentzωi2 /(ωi2 − 2iδoω − ω 2 ) where εo =
i =1
Supporting Information strongly indicate the magnetic compo-
2.2500 and δo is fixed at 8 × 1011 rad s−1, respectively. Two dif- nent of the hybrid modes with the potential for efficient light-
ferent oscillator strengths (εlorentz): 0.005 and 0.025 have been to-heat conversion for further integration. Finally, the role of
considered. The spectral positions of the five oscillators are absorption resonance of the metamaterial pattern on the cou-
fixed at (i) 6.25 µm, (j) 6.4 µm, (k) 6.75 µm, (l) 7.20 µm, and pling with closely spaced vibration modes can be confirmed by
(m) 7.5 µm. Figure 3a,b shows the thickness dependence of the the simulated comparison as the metamaterial pattern is absent
interference controlled reflection off the structure at εlorentz = in Figure S4 in the Supporting Information.
0.005 and εlorentz = 0.025, respectively. Clearly, a saturation of The uniformity of the characteristics of the hybrid device
reflection dip is observed in both the cases as the thickness over a large area is confirmed by the AFM imaging (Figure S5,
increases (marked by dashed black rectangles). In this par- Supporting Information) and focal plane array (FPA) imaging
ticular case, the spectral position and intensity of the reflection (Figure S6, Supporting Information). Again, the thickness-
dips are strongly determined by the extinction coefficients (k) of dependent spectra in Figure S5a,b in the Supporting Informa-
the lossy dielectric. It is obvious that the destructive interference tion show a good control over the post-CMOS process. Transient
condition supported by the back metal reflector in the presence data for thermal desorption further indicates the required time
of loss (k) can completely suppress the reflection and achieve to be around 2 min for complete reset (Figure S7, Supporting
perfect absorption. Complete suppression of reflection is other- Information). In the later section, we analyze the dynamic
wise not found to be achievable in two-layer geometry in the response of the hybrid sensor at the five selected spectral points.

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Figure 3. Thickness versus wavelength map of the reflection spectrum of the polymer-metal geometry. a) Oscillator strength εlorentz fixed at 0.0005.
b) Oscillator strength εlorentz fixed at 0.0025. c) Length dependence of the reflection spectra of the metamaterial patterns (C1–C10) coated with 300 nm
PEI film (as prepared, i.e., exposed to ambient CO2) when the back metal reflector is removed. d) Reflection spectra of the similar C1 structure coated with
300 nm PEI film at two different states: (i) as prepared (ii) thermally desorped showing no strong coupling with the background resonance of the pattern.

3.3. Geometry-Dependent Characteristics of the Sensing Platform Here, we scan across a broad spectrum (4–8 µm) by sweeping
and Its On–Off Switching Behavior in the Differential Spectrum the length (l) of the geometry for the study. For calibration, we
increase the CO2 concentration in continuous mode without any
In this section, we experimentally study the geometry-dependent thermal reset and measure at steady state. As seen in Figure 4a,
characteristics of the metamaterial absorber sensor by varying the a regular redshift is observed only for the C1 device. Such shift
length of the crosswire geometry. The perfect absorption condition is directly attributed to the broadband intensity difference that is
is satisfied only when the effective impedance defined as observed between 2.5 and 5 µm in Figure 2d due to the forma-
zeff = µ eff /ε eff becomes equal to the input impedance (zin) and tion of unique chemical species in the presence of CO2. Note
the electrical (dipolar) and magnetic resonance simultaneously lead that the spectral position of C1 resonance is 4.9 µm that falls
to the matching condition. However, in the presence of gas-selective within the aforementioned range. Here, we report a wavelength
top layer with multiple vibrational modes, it is challenging to achieve shift 0.5319 nm ppm−1 calculated from the difference between
perfect absorption condition across the whole spectrum without 0 and 40 ppm. Apart from the resonance shift, an obvious inten-
changing the spacer thickness. In particular, perfect absorption con- sity change as a function of CO2 concentration is observed in
dition (R = 1 − A) is required to achieve near infinity differential all the devices (C1–C5). The sensor, however, shows saturation
response (Rsens/Ro − 1) for sensing framework operating in the behavior in continuous mode with no thermal reset which will
reflection mode where Rsens is the reflection intensity at the be discussed in the following sections. Interestingly, this perfect
exposure of CO2 and Ro is the reflection intensity in the pure absorption condition can be only achievable in the C5 device
state. Differential response with high switching contrast is favorable as seen from Figure 4e. Of course, the physics become slightly
for fiber-based all-optical sensing of gas within a miniaturized different as the background metamaterial mode approaches
package. More importantly, perfect absorption condition assures (C6 and beyond) the group of vibrational modes under current
maximum sensitivity of the hybrid platform when it is integrated study. As stated before, significant broadening of the absorption
with the NDIR system as shown in Figure 1b by enabling its oper- band is clearly observed for such cases. We consider the hybridi-
ation above the noise margin of the thermoelectric transducer. zation to be maximum in the C9 device and explore it further for

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of the perfect absorber condition, the on–off switching raio in

the differential spectra reaches a maximum of 9.85 (a.u) in the
C5 device (Figure 5e) which again falls to 3.6 in the subsequent
C6 device as the perfect absorption condition is interrupted
(Figure 5f). Such high contrast in differntial reposne is particu-
larly suitable for optical gas sensing at low concentration and in
reflection mode. Additionally, a clear splitting is observed in the
difference spectra (C6, C7 in Figure 5f,g, respectively) that we
attribute to the strong overlap between the metamaterial mode
and one of the vibrational modes. Again, the switching contrast
reaches a maximum of 4.9 (C7) in this regime by satisfying the
perfect absorption condition to a maximal degree.

3.4. Multiplexed Sensing at Steady State

by the Proposed Platform

Multiplexed dual mode sensing is getting popular for NDIR tech-

nology where one wavelength is used for referencing the inten-
sity of the sensor and another wavelength for the calibration of
gas concentration.[33] Based on the experimental results in the
previous section, here we report a new multiplexing technique
incorporating the signal variation in the coupled and uncoupled
regimes. The supercell structure as shown in Figure 6a is con-
sist of two different unit cells, where one is designed to operate
in the uncoupled regime and the other is designed for the cou-
pled regime. We believe the potential of the gas-selective material
can be fully extracted through this manner by capturing both the
refractive index-dependent wavelength shift and coupling variation
into the vibrational modes for dual mode sensing. The representa-
tive simulation result showing the resonance characteristics of the
supercell in the presence of the hypothetical gas-selective polymer
is presented in Figure 6b. The respective resonance field profiles in
Figure 6c–f show no sign of near-field inter­action within the unit
cells. Figure 6g shows the proof-of-concept experimental results
for the multiplexed sensing. At the unit cell I region, a monotonic
wavelength shift is observed while at the unit cell II region, mainly
a strong intensity variation is observed. In particular, superposi-
tion of resonantly (unit cell II) and nonresonantly (unit cell I)
enhanced absorption bands at pt3 and pt4 spectral locations is
noted. Overall, the concentration-dependent change observed at
the two regions indicates the multifunctional characteristics of
the gas-selective material suited for metamaterial-based optical
sensing. One fundamental limitation of the scheme observed is
the side band overlap of the unit cell specific resonances that ulti-
mately leads to large reflection in the background. For example,
the minimum reflection observed around unicell I resonance is
Figure 4. Geometry-dependent gas sensing characteristics of the hybrid
absorber structures a–j) C1–C10 geometry, respectively. The dashed arrow 52.5% meaning 47.5% effective absorption. Such limitation can
line locates the spectral position of CO2 molecule trapped inside the PEI be possibly overcome by designing high Q nanostrcture ensuring
overlayer. The gray region indicates the spectral position of the metamate- minimal spectral overlap between the sidebands.[34]
rial absorption resonance in the background. Clearly, a significant spectral
broadening is observed (e.g., C9) as the absorption resonance overlaps
with the densely positioned vibrational modes of the gas sensitive layer. 3.5. Dynamic Sensing Characteristics and Selectivity
Also, the broadening increases as the gas concentration increases. Obvious
redshift is observed as well (C1) as the gas concentration increases.
3.5.1. Dynamic Behavior of Average Absorption
dynamic characterization. From quality factor’s point of view, the In this section, we analyze the dynamic behavior of the hybrid
C9 structure with its full width at half maximum of ≈1300 nm sensor considering the average absorption calculated as
can maximally overlap with the five absorption modes located λ2
within a spectral range of 1500 nm. As a direct consequence Aavg = 1 /( λ2 − λ2 ) ∫ (1 − R )dλ , where λ1 and λ2 are the beginning
λ1

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and end wavelength of the averaging interval, respectively.

Time-dependent average absorption extracted in 5–8 µm range
is provided in Figure 7a that accounts for the variation of the all
the vibrational modes. The abrupt decrease in the intensity at
every instance of gas injection is due to the carrier N2 induced
partial desorption and cleaning of CO2 induced infrared spe-
cies. At every injection, the outlet is kept open so as to drive
away the previous concentration from the chamber completely
while the steady state measurement is taken keeping the outlet
closed and ensuring the uninterrupted exposure of the sensor
to a given concentration at zero flow rate. This mimics the real-
life situation in indoor air quality monitoring and avoids the N2
flow rate induced partial desorption at steady state. The steady
state response therefore indicates the maximum signal output
of the sensor in response to a particular concentration. The
results indicate ppm level limit of detection with a response
time close to 2 min. The slope indicated (2.36 × 10−5 s−1)
implies the steady state condition achieved at various concen-
trations. The differential absorption calculated from the differ-
ence of two steady state conditions in Figure 7b shows the
potential of the platform for sensing in continuous mode. How-
ever, saturation behavior of the sensor is still observed which
we attribute to the limited capacity of CO2 storage within the
thin film and can be improved by increasing the thickness of
the film and prolonged desorption under N2 environment
before each measurement. It is notable that the sensor triggers
as soon as its exposed to a minute CO2 concentration (40 ppm
in this work) making the platform highly senstivite to the pres-
cence of the trace gas. We believe it is the adsorption of CO2 at
the upper surface followed by the formation of infrared species
that leads to such characteristics through the subsequent elec-
tromagnetic coupling. Furtheremore, the abrupt intensity
change is self-­ powered and therefore can be considered for
futuristic, event-driven air flow monitoring system.[35] Besides,
with the potential for integration with read-out electronics, it is
possible to perform the sensing on the rising edge even before
reaching the steady state, and thereby reduce the overall power
consumption.
Later, we breakdown the average absorption into five exact
bands (400 nm each) around the spectral points (pt1, pt2, pt3,
pt4, and pt5) and analyze the contribution from each under
resonant approxmiation. Clearly, all the bands except to pt3
show the sensing behavior. The normalized reflection spectra
extracted at pt2 and pt4 center wavelength in Figure 8b are
also in harmony with the trend of the calculated, band-specific
average absorption in Figure 8e,g. It is worthwhile to note that
the saturation characteristics is much improved in the case of
pt4 (7.092 µm) band that corresponds to NCOO skeletal vibration
indicating the higher capacity of this reaction path for CO2
Figure 5. Geometry dependence of on–off switching observed in the diffe­ sensing. The absence of any monotonic trend in the case of
rential spectra of the perfect absorber structures as a function of gas con- pt3 refers to the intricate dependence of the coupling on the
centration a–j) C1–C10 geometry, respectively. The gray region indicates the gas concentration. As the concentration builds up, a crossing
spectral location of the metamaterial absorption resonance in each case. behavior becomes clearly observable in Figure 8a that leads to
The peak switching contrast is observed to be in C5 geometry (≈9.85) as an
a nonmonotonic trend at this spectral location. The dynamic
outcome of the perfect impedance matching obtained in the hybrid geom-
etry for a given thickness of the gas-selective layer (≈300 nm). A pronounced behaviors are also collected at two different nonresonant wave-
splitting of the switching peak is observed (C6 and C7) that results from the lengths (Figure S8, Supporting Information). Although the
interplay between the coupling of closely spaced vibrational modes and the sensing behavior is observed by the trapped CO2 molecules
background metamaterial absorption resonance. In all cases, the switching (4.23 µm), no particular trend is observed at 5.6 µm at 116 ppm
contrast scales up with the increased gas concentration. and beyond. This is because of the crossing among the spectra

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Figure 6. Demonstration of multiplexed sensing on the proposed platform at steady state condition a) design of super cell composed of unit cell I
and unit cell II for multiplexed sensor b). Simulated resonance profile of the supercell geometry overlaid by the gas-selective layer. Polarization of the
incoming radiation is fixed along y-axis c). d) Electric field (at XY plane) and magnetic field (at XZ plane) distribution, respectively, when unit cell I is
resonant at 5.25 µm e). f) Electric field (at xy plane) and magnetic field (at xz plane) distribution, respectively, when unit cell II is resonant at 6.75 µm.
g) Steady-state sensing characteristics of the multiplexed platform. Inset: fabricated superpixel.

Figure 7. a) Dynamic behavior of average absorption in C9 geometry obtained by integrating the normalized absorption within the spectral window:
5–8 µm. b) Differential absorption at steady state fitted under 2 parameter exponential model (  f(x) = a*exp(b*x) + c*exp(d*x)) indicating saturation
behavior of the sensor as the gas concentration increases in continuous mode. The fitting values of a, b, c, and d are 0.04555, 0.0004665, −0.04551,
and −0.0691, respectively, with R-square value of 0.9993.

which is previously observed in Figure 4i as the concentration For the detection of gas at high concentration, we exploit the
builds up. The results, therefore, indicate the need for a judi- diffusion controlled sorption of gas within the thin film.
cious selection of the wavelength range to ensure reliable The time-dependent characteristics of the large area (100 µm by
sensing on the proposed platform. 100 µm) PEI film on metal as exposed to 1000 ppm concen-
tration followed by a flush of room emperature CO2 is shown
in Figure 9a. Characteristics at various important wavelenths
3.5.2. Dynamic Sensing Beyond Safe Level, Ambient CO2 (R1, R2, and R3) are shown in Figure 9b. Even though the
Concentration and Selectivity CO2 desorption is an endothermic process (i.e., requires
external heat), we clearly observe a fast recovery behavior at
In this section, we further report the dynamic sensing of CO2 certain wavelength (R3) when flushed with ambient CO2 con-
gas beyond safe-level, ambient CO2 concentration and selectivity centration at 75th second. This essentially indicates the weak
against a range of volatile organic components. The upper limit chemical binding strength between the amine branches and
for safe-level CO2 at the workplace is regarded to be 1000 ppm. excess CO2 molecule at concentration beyond the capacity of

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Figure 8. a) Steady-state normalized reflection of C9 absorber structure at different concentrations. b) Time evolution of normalized reflection at two
distinct spectral regions: pt2 and pt4 as the concentration increases in continuous mode. c) Extracted steady state normalized reflection. d–h) Time-
dependent average absorption as a function of gas concentration integrated over a bandwidth of 400 nm around pt1, pt2, pt3, pt4, and pt5 spectral
position, respectively. Increasing trend is observed for pt1, pt2, and pt5 whereas decreasing trend is observed for pt4. Average absorption is found to
reach a maximum at intermediate concentration (80 ppm) at pt3 location.

the thin film and opens up the possibility for the recovery of with increasing concentration (Figure 8d,e). A nonmono-
the hybrid sensor at room temperature. Here, we leverage the tonic trend is again observed at pt3 (Figure S9a, Supporting
diffusion controlled behavior for sensing of high concentra- Information) implying the effect of spectral overlap within a
tion CO2 using metmatierial absorber. As seen in Figure 9c, given absorption bandwidth (400 nm). The rising trend at pt4
a steady state absorption difference (5–6%) can be achieved in (Figure S9b, Supporting Information) also contradicts with
around 10 min even when the sample is pre-exposed to ambient the decreasing trend previously observed (Figure 8g). This
CO2 concentration (600 ppm) and humidity (72%) over a pro- indicates the sensing mechanism based on fast adsorption at
longed period of time (24 h) at room temperature (25°). Note the upper surface (for low concentration CO2) and slow dif-
that the initial state of the sensor differs from that in Figure 2e fusion of the chemisorbed CO2 in the bulk network (for high
as the condition prior to sensing is different. Interestingly, the concentration CO2) can be unique from one another on the hybrid
dynamic intensity difference can transiently increase by 225% platform. The trend of the dynamic absorption, in fact, shows
at the instance of gas injection due to the partial desorption strong dependence on the operating wavelength and the cor-
and eventually settles down to 75% at steady state. The partial responding bandwidth (Figure S10, Supporting Information).
disorption appears to be mainly associated with the removal The proposed mechanism, therefore, offers multiple routes
of the infrared chemical species at the upper surface of the for resolving CO2 concentration in various ambient condi-
material. The sharp decline in the time-dependent average tions. We believe, the low concentration characteristics will fit
absorption collected at the two different wavelengths (pt1: into emergency CO2 leak detection application in the refrig-
6 µm and pt2: 6.60 µm) plotted in Figure 8c also indicates this. eration/storage system while the high concentration charac-
The steady-state difference observed implies the usefulness teristics will serve for air quality monitoring at the industrial
of the perfect absorption condition of metamaterial absorber workplace.
for repeated gas sensing applications under ambient condi- The selectivity experiment conducted on the hybrid sensor
tion. The average absorption at pt2 steadily decreases from further shows the selectivity of the platform against a range of
the initial value (86.50%) to a final value (82.5%) instead of volatile organic compounds (Figure 10a,b). Among the five spec-
increasing as the kinetically slow diffusion takes place. Average tral points under consideration, only pt4 and pt5 experience the
absorption is found to increase from 52% to 58% at pt1 on transient effect of the volatile compound. Therefore, a careful
the other hand. However, at a lower concentration, average selection of the operating wavelength can still enable the selec-
absorption at both the wavelengths shows the rising trend tive detection of CO2 in a mixed pollutant environment.

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Figure 9. Characterization of 300 nm PEI film coated on a flat metal surface as exposed to a concentration of 1000 ppm followed by a flush with ambient
CO2 gas at 75th second. The initial condition is maintained at ambient CO2 concentration, i.e., 600 ppm a). Broadband mid-IR spectra of the three
consecutive cases b). Time evolution of the signals at three distinct wavelengths of the spectra. Fast recovery of the PEI film is clearly observed at the
bottom panel (R3) c). Dynamic response of metamaterial average absorption band (400 nm) around the two different wavelengths (pt1: 6 µm and
pt2: 6.60 µm) as exposed to 1000 ppm CO2. Left inset: Broadband mid-IR spectra at three instances: ti (initial condition: blue solid line), te (exposure:
red solid line), and ts (steady state: black solid line). Right inset: Differential spectra at two instances: te and ts indicating large switching contrast
achievable for detecting gas concentration above safety range.

Figure 10. a) Wavelength versus time mapping of resonance profile of hybrid metamaterial absorber structure (C9) as exposed to representative volatile
organic compound (acetone vapor) at the 58th second. The structure is pre-exposed to 177 ppm CO2 before acetone exposure. Presence of transient
vibrational modes of acetone is indicated accordingly. b) Extracted resonance profiles at three different instances. Transient interferences caused by
the acetone molecule are marked the gray region in the spectra. Only the pt4 and pt5 spectral locations are affected due to the transient coupling with
the δ CH3 finger print of volatile organic compound.

4. Conclusion metamaterial absorber platform. The hybrid metamaterial

absorber-based sensor further offers fast response time, large
In summary, we demonstrate a novel solution for miniatur- differential response for all-optical monitoring, and low hyster-
ized gas sensor with ppm range of detection limit and high esis and holds promise for direct integration with the existing
selectivity by coupling a smart, gas-selective material with the NDIR system. As an added advantage, a dual mode sensing

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