Plasmonics (2020) 15:457–466

https://doi.org/10.1007/s11468-019-01035-3

Ultrahigh Sensitivity Surface Plasmon Resonance–Based

Fiber-Optic Sensors Using Metal-Graphene Layers
with Ti3C2Tx MXene Overlayers
V. R. Sudheer 1 & S. R. Sarath Kumar 2 & S. Sankararaman 1

Received: 8 May 2019 / Accepted: 10 September 2019 / Published online: 14 November 2019
# Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
Precise detection of volatile organic compounds (VOCs) using high-sensitivity fiber-optic probes is highly desirable for rapid
screening in the fields of medicine and food processing. A novel spectral surface plasmon resonance (SPR)–based fiber-optic
sensor incorporating metal/graphene/Ti3C2Tx MXene layers for the detection of VOCs such as acetone and ethanol is proposed in
this study. For the detection of acetone, optimum sensitivities of 5150, 4500, and 4200 nm/refractive index unit (RIU) are
obtained using simulations, for sensors with Au, Ag, and Al, respectively, as metal layer. The highest sensitivity achieved at
reasonably good detection accuracy is 19,750 nm/RIU, using a Au/graphene/Ti3C2Tx sensor, for VOCs with refractive index
1.434.

Keywords Two-dimensional materials . Volatile organic compounds . Hybrid nanostructures . Sensitivity

Introduction
Accurate sensing of the presence and concentration of volatile
organic compounds (VOCs) is of significance in the areas of
medicine and food processing [1]. High sensitive detection of
VOCs [2–4] in human breath can not only give an indication
of the health condition of individuals but also help in the early
diagnosis of diseases like cancer [5] and diabetes [6–8].
Similarly, the quality of processed food, meat products, and
fruits can also be revealed by the analysis of volatile chemicals
released by them [9, 10]. Today the ultrasensitive detection of
VOCs needs expensive and time-consuming techniques such
as gas chromatography and mass spectroscopy. Since VOCs
are comprised of organic components of low molecular
weight and high vapor pressure, traditional gas sensors with
limited surface adsorption capabilities fail to detect them with
sufficient accuracy. Hence, novel materials with high
* S. R. Sarath Kumar
sarath.sr.nair@gmail.com
* S. Sankararaman
drssraman@gmail.com
1
Department of Optoelectronics, University of Kerala, Karyavattom,
Thiruvananthapuram 695581, India
2
Department of Nanoscience and Nanotechnology, University of
Kerala, Karyavattom, Thiruvananthapuram 695581, India
sensitivity for the detection of VOCs are being explored. For
example, two-dimensional (2D) layered materials such as
MXenes have been employed recently [11] in chemi-
resistive gas sensors to achieve enhanced sensitivity in detect-
ing VOCs. Similarly, a new class of sensor materials based on
hybrid nanostructures is being developed to overcome the
limitations of conventional gas sensors in rapid and accurate
detection of VOCs [12].
Integration of the functional aspects of individual 2D
nanomaterials such as MXenes, graphene, transition metal
dichalcogenides, and black phosphorous into novel nanostruc-
tures holds the key in developing next-generation sensors that
can help in accurate detection of VOCs. MXenes derived from
the Mn+1AXn (MAX) phases (where M is an early transition
metal, A is a group 13 or 14 element, and X is carbon or
combination of carbon and nitrogen) by the selective removal
of A sub-layers are a family of 2D layered materials that have
attracted considerable attention in recent years. The large spe-
cific surface area and anisotropic conductivity of charge car-
riers, together with environmental friendliness and excellent
chemical stability, make MXenes unique. The presence of
surface dangling bonds enables MXenes to attract various
functional groups. Hence, MXenes find application in energy
conversion [13], energy storage [14, 15], optoelectronics [16,
17], biosensors [18–20], catalysis [21, 22], electrochemical
sensors [23, 24], and gas sensors [11], to name a few.
Ti3C2Tx, where T represents a surface functional group, is
458
one of the most studied MXenes. It is used as an active hy-
drophilic layer for sensors of various kinds [11, 18, 24–26]
unlike other hydrophobic 2D materials (such as graphene or
transition metal dichalcogenides) that are often difficult to
functionalize. The unique electronic, physical, and optical
properties of graphene make it suitable for applications in
sensing substrates [27, 28] and flexible display screens [29].
Graphene-based hybrid photonic devices have also been
attracting huge interest in recent years [30–33]. The huge mo-
bility of graphene (106 cm2 V−1 s−1) allows fabrication of
metal-graphene interfaces with a strong coupling of charge
carriers leading to an enhanced electric field. This helps in
devising high-sensitive sensors by integrating highly function-
alized Ti3C2Tx MXene as a top layer to the metal-graphene
hybrid nanostructure.
Optical sensors based on surface plasmon resonance (SPR)
have been routinely used for rapid and accurate detection of
physical, chemical, and biological agents [34–37]. Such sen-
sors make use of resonant absorption of electromagnetic en-
ergy that occurs between the p-polarized surface plasmon
wave and the p-polarized light incident at the metal-
dielectric interface. The fact that the resonant absorption is
highly sensitive even to infinitesimally small changes in the
refractive index of the surrounding media makes SPR an ex-
cellent tool for sensing applications. Among the different
kinds of SPR-based sensors, fiber-optic SPR sensors
[38–40] have attained larger significance due to their small
size and light weight and the ability for strong confinement
of light. The simplest fiber-optic SPR sensor is obtained by
coating a single layer of metal such as Au, Ag, Al, or Cu on a
small region of the fiber where the cladding is removed.
Sensitivities as high as 3500, 2800, 3100, and 2300 nm/
refractive index unit (RIU) have been reported, respectively,
for a single Au, Cu, Ag, and Al layer of 50-nm thickness for
sensing analytes having a refractive index in the range 1.343
to 1.353. Typically, the use of bimetallic layers results in en-
hanced sensitivity as compared with the use of a single metal
layer. Further enhancement is possible by exploiting the en-
hanced surface adsorbance of the 2D layered materials used as
top layer to specific analytes.
In this study, a fiber-optic SPR sensor made of a hybrid
metal/graphene/MXene structure for sensing VOCs of bio-
medical importance is proposed. The key performance param-
eters of the proposed sensor are analyzed using simulations
based on theoretical models. The study highlights the need for
optimization of the thickness of different layers in order to
attain enhanced sensitivity.
Experimental Considerations and Theoretical Model
An SPR-based fiber-optic sensor comprising of metal,
graphene, and MXene layers, as illustrated in Fig. 1, is con-
sidered for theoretical modeling to extract key sensing
Plasmonics (2020) 15:457–466
Fig. 1 Schematic of a typical spectral SPR setup, together with the
proposed sensor consisting of a metal layer, graphene layer, and MXene
layer deposited in order, over a region of the optical fiber where the
cladding has been removed. Optical detection of analytes such as
acetone or ethanol, which adsorb on to the MXene layer, is possible
from the resonance wavelength which depends on the refractive index
of the analyte
parameters. Essentially, the sensor makes use of the
Kretschmann configuration under wavelength interrogation
mode (also known as the spectral SPR mode) [41]. In order
to realize the proposed SPR sensor, the cladding needs to be
removed for a length L from a plastic clad silica (PCS) fiber of
core diameter D. The exposed silica region is to be coated with
a thin film of metal having appropriate thickness followed by
few layers of graphene and finally few layers of Ti3C2Tx. The
top Ti3C2Tx layer of the sensor is exposed to the sensing
media of refractive index, nS. Hence, the sensing probe com-
prises a four-layered structure, as illustrated in Fig. 1. In this
study, modeling is carried out with Au, Ag, or Al as the metal
layer of the sensor. For the analysis, we consider a collimated
white light focused at an angle on the face of the fiber, close to
the axial point of the fiber axis. A graph plotted with transmit-
ted output power and wavelength gives information on the
resonance wavelength. From the graph, the sensitivity and
other key parameters of the sensor are calculated.
Since the spectral SPR method has been adopted, due con-
sideration on the wavelength dependence of the different ma-
terials constituting various layers of the sensing mechanism is
essential. The wavelength dependence of the refractive index
of the silica core of the PCS fiber is calculated as defined by
the Sellmeier relation [42] as
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a1 λ2 a2 λ2 a3 λ 2
nð λ Þ ¼ 1 þ 2 2 þ 2 2 þ 2 2 ð1Þ
λ ‐b1 λ ‐b2 λ ‐b3
where λ is the wavelength in μm and a1, a2, a3, b1, b2, and b3
are Sellmeier coefficients with values of a1 = 0.6961663, a2 =
0.4079426, a3 = 0.8974794, b1 = 0.0684043, b2 = 0.1162414,
and b3 = 9.896161.
Plasmonics (2020) 15:457–466 459

The Drude dispersion model quantifies the wavelength de- undergone by the ray incident at an angle θ inside the fiber
pendence of the dielectric constant of the metals with the core, and is given by [43]
relation [43].
L
N ref ðθÞ ¼ ð6Þ
λ λc
2 DtanðθÞ
εm ðλÞ ¼ εmr þ iεmi ¼ 1− ð2Þ
λ2p ðλc þ iλÞ
where L is the length of the sensing probe and D is the diam-
where λp and λc are, respectively, the plasma and collision eter of the fiber core. For the analysis, we have taken L
wavelengths of the metal; εmr and εmi are the real and imagi- as1.5 cm and D as 600 μm.
nary parts of the dielectric constant of the metals. The values
[44, 45] of λp and λc for Au, Ag, and Al are furnished in N-Layer Matrix Method In this study, since the sensing probe
Table 1. consists of four layers along with the sensing media of refrac-
The dispersion relation of graphene is obtained [46] using tive index nS, the N-layer matrix method [42, 43] has been
experimental data as utilized to determine the value of Rp accurately. The charac-
teristic matrix for an N-layer structure can be expressed as [49]
c
nðλÞ ¼ 3:0 þ i λ ð3Þ
3 h i h i
1 cos β k ði sin β k Þ=qk
−1 M ¼ ∏Nk¼2 Mk ¼ M 11 M 12
¼ ð7Þ
where constant c = 5.446 μm and the wavelength is M 21 M 22 iqk sin β k cos β k

expressed in μm.  1=2

ðεk −n21 sin2 θ1 Þ
1=2
μk
The expression for the refractive index of Ti3C2Tx as a with qk ¼ εk cosθk ¼ εk and
function of the wavelength is obtained by fitting the experi-
mental data for wavelength dependence of real part of refrac- 2π 2πd k  1=2
βk ¼ nk cosθk ðZ k −Z k−1 Þ ¼ εk −n21 sin2 θ1 ð8Þ
tive index and extinction coefficient [47] to yield λ λ

nTi3 C 2 ¼ nreal imaginary

Ti3 C 2 þ nTi3 C 2 ð4Þ where εk, nk, μk, and dk are, respectively, the dielectric constant,
refractive index, permeability, and thickness of the kth layer.
Ti3 C2 ¼ b0 þ b1 λ þ b2 λ þ b3 λ þ b4 λ , where b0 = −
2 3 4
with nreal The reflection coefficient, rp, of the incident wave through
−5
0.19797, b1 = 0.02469, b2 = − 5.68844 × 10 ,b3 = 3.83996 × the N-layer structure is given by [43]
10−8, and b4 = 6.91253 × 10−24, and
nimaginary ¼ p0 þ p1 λ þ p2 λ2 þ p3 λ3 þ p4 λ4 þ p5 λ5 , where ðM 11 þ M 12 qN Þq1 −ðM 21 þ M 22 qN Þ
Ti3 C 2 rp ¼ ð9Þ
P0 = − 1.88758, P1 = 0.03794, P2 = − 1.46823 × 10−4, P3 = ðM 11 þ M 12 qN Þq1 þ ðM 21 þ M 22 qN Þ
2.19295 × 10−7, P4 = − 1.09322 × 10−10, and P5 = 3.72845 ×
10−25. and the corresponding reflectance is Rp = |rp|2.
The normalized transmitted power of the SPR-based sensor All the sensors are so designed that the SPR wavelength
with a white light source can be expressed as [48]. (λR) lies in the visible region (300–800 nm) of the spectra, as
shown in Fig. 2a. The quality of any SPR sensor can be judged
π
= N n21 sinθcosθ
ðθÞ by three main parameters: (a) sensitivity, given by change in
∫θCr2 RP ref  2 dθ
1‐n21 cos2 θ λR for given change in nS (given by [41] S ¼ ΔλΔnS ); (b) spectral
R

Ptrans ¼ 2
ð5Þ
π=
N ðθÞ n sinθcosθ width [43] of the SPR curve; and (c) range of refractive index
∫θCr2 RP ref  1 2 dθ
1‐n21 cos2 θ values over which sensing is possible within the given wave-
length range. Sensitivity is a major parameter which deter-
where Rp is the net reflection coefficient of the ray incident at mines the quality of sensing. The more the shift in λR for a
the core-metal interface. θcr = sin‐1(n2/n1) is the critical angle unit change in n (c.f. Fig. 2b), the more accurate will be the
of the fiber, n2 being the refractive index of the cladding of the sensing. Similarly, the width of the dip in SPR curves (spectral
fiber. N ref (θ) corresponds to the number of reflections width) is also very important for an SPR sensor. The accuracy
of detection of λR increases with sharpness of the SPR curves
Table 1 Plasma and collision wavelengths of Au, Ag, and Al (i.e., with decrease in spectral width). Hence, the full width at
half maximum (fwhm) of the dip is also considered as a nec-
Metal Plasma wavelength, λp (m) Collision wavelength, λc (m) essary metric for the SPR-based sensor. However, as illustrat-
Au 1.6826 × 10−7 8.9342 × 10−6
ed in Fig. 2a, for certain curves, the high wavelength arms of
the dip can be so shallow that the fwhm cannot be properly
Ag 1.4541 × 10−7 1.7614 × 10−5
defined. A saving grace in such cases is the fact that the accu-
Al 1.0657 × 10−7 2.4511 × 10−5
racy of detection of λR depends only on the width of the lower
460 Plasmonics (2020) 15:457–466

1.0
attaining reasonably good sensitivity and SNR (or FOM) in
(a) practical sensors.
0.8 After analyzing the SPR curves of the different combina-
tions of constituent layers employed in our study, we propose
b four benchmark levels for these parameters that can ensure
0.6
accurate sensing results for different nS. They are as follows:
Normalized Transmitted Power

(i) λR must lie in the visible range; (ii) the sensitivity yielded
0.4 a by the sensor in any configuration or for any nS should be of
minimum value 3000 nm/RIU; (iii) only those SPR curves
0.2 c whose long wavelength part is at least 0.1 unit above the
minimum value of the dip should be considered to ensure that
the DA is sufficient enough for practical sensing; and (iv) DA
0.0 should be at least 5 nm−1.
1.0200 400 600 800

(b)
0.9
Results and Discussion
0.8

0.7
nS= 1.373
nS= 1.375
0.6
0.5
0.4
R
0.3
200 400 600 800
Wavelength (nm)
Fig. 2 a Typical SPR curves obtained for different layers of metal/
graphene/MXene. The variation in sharpness of the curves is evident.
For curve (a), it is possible to measure fwhm (marked by horizontal
orange line), while it is impossible for curves (b) and (c) (incomplete
horizontal orange lines). The proposed alternative (please refer text),
marked by horizontal blue lines, works fine for all the three curves. b
Representative curves showing the shift in λR with change in nS of 0.002
RIU
part of the dip of the transmission curve. Therefore, it is suf-
ficient that a reference width in the transmission dip be defined
such that it serves the purpose equivalent to that of fwhm. In
this study, we calculate the spectral width at a reference level
of 0.1 unit above the minimum value of the dip [50]. However,
we consider inverse of spectral width (detection accuracy
(DA)) since infinitesimally small changes in spectral width
can be effectively represented by the inverse quantity. A sim-
ilar approach has been reported [50] wherein the authors have
preferred to calculate DA at 0.1 unit above the minimum value
of dip in a normalized SPR spectrum. In fact, a signal to noise
ratio (SNR) of the SPR sensors is often defined [43] as a
product of change in λR and change in DA. A figure of merit
(FOM) of SPR sensors, which is defined as the ratio of sensi-
tivity to spectral width, is also often invoked to outline the
demerits of larger spectral widths. Hence, it is imperative that
design optimizations need to be performed for simultaneously
For the purpose of simulation, we consider acetone [51] as the
ambient sensing medium (nS = 1.358 RIU), unless otherwise
specified. A wide range of sensing media (nS = 1.02–1.45
RIU) are also considered for each of the sensor configurations.
Simulations are performed for a change in RI of 0.002 RIU,
corresponding to changes in analyte adsorbed to the Ti3C2Tx
surface. The shifts in the λR, the sensitivity, and the DA are
calculated for the SPR curves obtained for the different thick-
nesses of the metal, graphene, and Ti3C2TxMXene layers, and
the results are presented below.
1. Au/Graphene/MXene
In this configuration, a thin film of Au is considered as the
metal layer. Normalized transmitted power as a function of
wavelength for different thickness of Au is shown in Fig. 3a
for sensors having fixed thickness of graphene (four layers,
each of thickness 3.4 Å [52]) and MXene (single layer of
thickness 9.5 Å [53]). The redshift of λR with increasing thick-
ness of Au is as expected. The calculated sensitivity and DA
for these sensors with different thicknesses of Au are shown in
Fig. 3b. Sensitivity increases with increase in the thickness of
Au and approaches a saturation value of ~4000 nm/RIU. The
value is comparable to that obtained for MoS2-based gas sen-
sors [52]. The increase in spectral width with thickness of Au
is found to decrease DA and SNR (evidenced by the broaden-
ing of the SPR curve, as shown in Fig. 3a, for higher thickness
of Au). Figure 3c, the variation of sensitivity and DA with
refractive index nS of the sensing medium, suggests the pos-
sibility of achieving exceptionally high sensitivities in excess
of 10,000 nm/RIU with 10 nm of Au. In comparison, the
reported optimum sensitivities are 3500 nm/RIU for
graphene-metal hybrid sensor and 6200 nm/RIU for Cu/
graphene/MoS2 sensor [52]. Sensitivity is found to increase
progressively with nS up to a maximum of nS = 1.434 and
beyond that λR shifts to the infra-red region. DA is found to
Plasmonics (2020) 15:457–466 461

1.0 4500
(a) (b)
Normalised Transmitted Power

Detection Accuracy (nm )

32

-1
4000

Sensitivity (nm/RIU)
0.8
3500
24
0.6 3000

Au-10 nm 2500 16
0.4 Au-20 nm
Au-30 nm 2000
Au-40 nm
0.2 1500 8
Au-50 nm
Au-60 nm
Au-70 nm 1000
0.0 0
200 400 600 800 10 20 30 40 50 60 70
Wavelength (nm) Thickness of Au (nm)

Ti3C2Tx-0 Layer
20000 (c) 50 (d)
5000 Ti3C2Tx-1 Layer

Detection Accuracy (nm )

Detection Accuracy (nm )

-1
-1
Ti3C2Tx-2 Layers 40

Sensitivity (nm/RIU)
Sensitivity (nm/RIU)

16000 40 Ti3C2Tx-3 Layers

Au-10 nm 4500
12000 30
Au-40 nm
Au-70 nm 20
8000 20 4000

4000 10
3500

0 0 0
1.0 1.1 1.2 1.3 1.4 1.5 0 4 8 12 16
Refractive Index, ns Number of Graphene Layers
Fig. 3 a Wavelength dependence of transmitted power as a function of DA on the refractive index of analyte, for sensors having four layers of
varying thickness of Au as the metallic layer, for a sensor having four graphene and a single layer of Ti3C2Tx, shown here for three different
layers of graphene and a single layer of Ti3C2Tx, for an analyte having thicknesses of Au. d Sensitivity and DA as a function of number of layers
refractive index, nS = 1.358. b Variation of sensitivity and DA as a of graphene, for different layers of Ti3C2Tx, keeping thickness of Au as
function of thickness of Au for sensors having four layers of graphene, 40 nm and nS as 1.358
a single layer of Ti3C2Tx, and nS = 1.358. c Dependence of sensitivity and

decrease sharply implying a deteriorating SNR. Evidently, the Therefore, after fixing thickness of Au as 40 nm, the effect
range of nS for efficient sensing is very small. The sensitivity of varying the number of graphene and MXene layers is ex-
is found to increase further with increase in thickness of Au. plored for nS = 1.358. Figure 3d shows the simulation results
When the thickness of the Au film is changed to 40 nm, the for variation of sensitivity and DA with the number of layers
sensitivity is found to vary largely, effecting sensing up to a of graphene for different layers of Ti3C2Tx. It is clearly ob-
maximum nS of 1.383 beyond that λR shifts to the infra-red served that the sensitivity increases progressively with in-
region. A maximum sensitivity of 6100 nm/RIU is observed crease in number of graphene and Ti3C2Tx layers. It is indeed
with 4 layers of graphene and a single layer of Ti3C2Tx, with a noticeable that a single layer of Ti3C2Tx yields sensitivity
respectable value of DA. With 70-nm thickness of Au, the ~3300 nm/RIU even, without graphene layers. λR is found
magnitude of the dip of the SPR curve is so low that it prevents to exhibit a bathochromic shift and a decrease in the magni-
reliable sensing. If the low intensity curves are considered, the tude of the dip of the SPR curves (not shown) with increase in
sensing range will be very narrow limiting nS from about 1.4 number of graphene and Ti3C2Tx layers. The increase in sen-
to 1.36. The variation in sensitivity with nS values of 70 nm sitivity is offset by a decrease in DA. Analysis of the sensitiv-
and 40 nm of Au closely follows the same pattern with only ity, DA, and sensing range with different combinations of the
slight difference in sensitivity values as also evident from thickness of Au, graphene, and Ti3C2Tx for different nS values
Fig. 3b. The proposed sensor does not produce any reasonable leads to the observation that four layers of graphene with
SPR output beyond 70 nm of Au. From the above results, 40 nm of Au coating and a single layer of Ti3C2Tx provide
considering the sensing range, sensitivity, and DA, the Au improved sensing capabilities, for a sensing range of nS = 1.01
thickness of 40 nm seems to be the optimized choice. to 1.383, with λR in the visible region. The curves shown in
462 Plasmonics (2020) 15:457–466

Fig. 3 also act as a guideline for designing sensors for detect- 30–50 nm, and thereafter again decreases. This behavior indi-
ing gases and liquids having nS in excess of 1.4. Glycerol, cates that it is possible to enhance sensitivity and SNR simul-
which is routinely used in food industry, for instance, has a taneously in Ag-based sensors. The plot of variation of sensi-
refractive index of 1.474 [54]. An extremely high sensitivity tivity with refractive index for three different thicknesses of
of 19,750 nm/RIU is obtained for sensing nS = 1.434. Ag, with four layers of graphene and a single layer of Ti3C2Tx,
is shown in Fig. 4c. For the sensor having 10-nm-thick Ag, the
2. Ag/Graphene/Ti3C2Tx sensitivity observed is below 2000 nm/RIU, for nS less than
1.4. When nS is varied from 1.010 to 1.393, λR is found to be
in the range 229–400 nm. Further, DA is found to decrease
In this configuration, Au is replaced by Ag. Normalized progressively with the nS of the measurand. When 40-nm
transmitted power as a function of wavelength for different thickness of Ag is used, λR is observed to be in the visible
thicknesses of Ag is shown in Fig. 4a for sensors having four region for nS values up to a maximum of 1.393 beyond which
layers of graphene and a single layer of MXene, for nS = sensing becomes impossible. The sensitivity is found to in-
1.358. As the thickness of Ag increases, the dip of the SPR crease slowly up to about nS = 1.15, beyond which a steady
curves shifts to longer wavelengths, with a drastic decrease in exponential-like increase is observed. Sensitivity greater than
magnitude. The calculated sensitivity and DA, with variation the benchmark value (3000 nm/RIU) is observed only for nS
in thickness of Ag, are shown in Fig. 4b. Evidently, sensitivity greater than 1.33. With four layers of graphene and a single
increases with increase in thickness of Ag and approaches a layer of Ti3C2Tx, a maximum sensitivity of 7500 nm/RIU is
saturation value of ~ 3500 nm/RIU, while DA shows an initial observed. The DA is found to increase progressively with nS
decrease, followed by an increase of Au thickness in the range up to ~ 1.3 where the sensitivity is not appreciable. Beyond

1.0 4000 24
(a) (b)
Normalised Transmitted Power

3500

Detection Accuracy (nm )

-1
Sensitivity (nm/RIU)

0.8
3000

0.6 2500 16
2000
0.4 Ag-10 nm
Ag-20 nm 1500
Ag-30 nm 1000
0.2 Ag-40 nm 8
Ag-50 nm 500
Ag-60 nm
0.0 0
200 400 600 800 10 20 30 40 50 60 70
Wavelength (nm) Thickness of Ag (nm)
50 5000
Ag-10 nm Ti3C2Tx-0 Layer
(c) (d)

Detection Accuracy (nm )

8000 Ti3C2Tx-1 Layer
Detection Accuracy (nm )

-1
Ag-40 nm
-1

Ag-70 nm Ti3C2Tx-2 Layers 40

Sensitivity (nm/RIU)
Sensitivity (nm/RIU)

40 4500 Ti3C2Tx-3 Layers

6000
30
4000
4000
20
20
3500
2000
10
3000
0 0
1.0 1.1 1.2 1.3 1.4 1.5 0 5 10 15 20 25
Refractive Index, ns Number of Graphene Layers
Fig. 4 a Wavelength dependence of transmitted power as a function of nS = 1.358. c Variation of sensitivity and DA with nS, for sensors having
varying thickness of Ag as the metallic layer, for a sensor having four four layers of graphene and a single layer of Ti3C2Tx, for three different
layers of graphene and a single layer of Ti3C2Tx, for adsorbing species thicknesses of Ag. d Dependence of sensitivity and DA on the number of
having nS of 1.358. b Sensitivity and DA as a function of thickness of Ag layers of graphene, for different layers of Ti3C2Tx, keeping thickness of
for sensors having four layers of graphene, a single layer of Ti3C2Tx, and Ag as 40 nm and nS as 1.358
Plasmonics (2020) 15:457–466
nS = 1.3, the DA is found to decrease rapidly offsetting the
increase in sensitivity. Analysis of the sensing probe with
70-nm thickness of Ag showed that measurement of λR could
not be done up to an nS value of about 1.3 since the dip of the
output SPR curve is very low. For nS ranging from 1.3 to
1.387, sensing is possible with sensitivity in the range 1800–
8000 nm/RIU, with values of DA too low to mention. Hence,
40 nm is arrived as the optimal thickness of Ag.
In order to study the effect of varying graphene and MXene
layers on the sensing parameters, simulations are performed
by keeping thickness of Ag fixed at 40 nm for nS = 1.358.
Figure 4d shows the variation of sensitivity and DA for sen-
sors with varying numbers of graphene and MXene layers.
From the figure, it is clear that the sensitivity increases, while
DA decreases with increase in number of graphene and
Ti3C2Tx layers. With no graphene layer, sensitivities of
3050 nm/RIU, 3200 nm/RIU, and 3350 nm/RIU are observed
for one, two, and three layers of Ti3C2Tx, respectively. It is
observed that λR shifts to longer wavelengths (not shown), in
accordance with the increase in the number of graphene and
Ti3C2Tx layers. A high sensitivity of 4500 nm/RIU and rea-
sonably good DA are observed for a sensor having a single
layer of Ti3C2Tx, which also ensured λR is in the visible range
for a wider range of nS.
3. Al/Graphene/Ti3C2Tx
In this configuration, Al is used as the metal layer coated
just above the core in the cladding removed portion of the
optical fiber. Analysis is performed for different values of
refractive indices, thickness of Al, and number of graphene
and Ti3C2Tx layers, to observe the effect on sensitivity and
DA of the SPR curve and the sensing range. Figure 5a shows
the normalized transmitted power as a function of wavelength
for different thicknesses of Al for sensors having fixed thick-
ness of graphene and MXene. A redshift of λR and decrease in
dip of the SPR curves are observed with increasing thickness
of Al. The calculated sensitivity and DA for these sensors with
different thicknesses of Al are shown in Fig. 5b. Sensitivity
increases with increase in thickness of Al and approaches a
saturation value of ~ 3700 nm/RIU. The DA is found to in-
crease with thickness of Al reaching a maximum for 40 nm;
beyond which, it is found to decrease. For thickness in excess
of 60 nm, the dip is observed to be too low for accurate deter-
mination of DA.
The variation of sensitivity and DA with refractive index
for three different thicknesses of Al, with four layers of
graphene and a single layer of Ti3C2Tx, is shown in Fig. 5c.
For a thickness of 10 nm of Al, and nS ≤ 1.15, the SPR curves
showed a λR below 200 nm (uv region), while for nS ≥ 1.15,
the λR is below 400 nm in the visible region and sensitivity is
found to gradually increase. However, the DA decreased pro-
gressively. A maximum sensitivity of 3050 nm/RIU at nS =
463
1.399 is achieved. Beyond this, the transmission curve is ob-
served to spread out largely that prevents the detection of λR.
For an Al thickness of 40 nm, sensing is possible up to a
maximum nS value of 1.41; beyond which, the λR shifts to
the IR range. The observed sensitivity that is very low for
small values of nS is found to increase monotonously above
nS = 1.33. Also, it is found that the dip of the transmission
curve increases with increase in nS (not shown). The DA is
found to increase with increase in nS up to about 1.33 where
the sensitivity is low and decreases thereafter. The sensitivity
improves rapidly at the higher region of the sensing range and
a very high sensitivity of 14,550 nm/RIU is observed for nS =
1.41. Analysis with a 60-nm Al film shows that up to nS =
1.29, no noticeable output could be observed, but beyond nS =
1.37, a reasonable sensitivity is observed. In this range, the
sensitivity is found to vary similar to the sensor with 40-nm-
thick Al. The sensing is found to be possible for a maximum
nS of 1.41. The DA of the curves is too small for the entire
possible sensing range of nS = 1.37–1.41. For an Al thickness
greater than 60 nm, sensing is found to be impossible.
Therefore, again, it is observed that 40 nm is the optimal
thickness of the metal layer. Figure 5d shows the variation
of sensitivity and DA with number of graphene layers, for
different thicknesses of Ti3C2Tx. It is seen that sensitivity in-
creases while DA decreases progressively, with the addition of
graphene and Ti3C2Tx layers. Even in the absence of graphene
layers, a sensitivity of 2450 nm/RIU is observed with a single
layer of Ti3C2Tx. It is observed (not shown here) that γR ex-
periences a bathochromic shift while the magnitude of SPR
dip decreases with the increase in number of layers of
graphene and Ti3C2Tx.
In addition to the benchmark levels mentioned, to identify
the best suitable configuration of nanostructured materials for
the detection of VOCs relevant to medical diagnosis and food
processing, we need to consider the amount of surface adsorp-
tion of VOCs by the sensor which is crucial in establishing
proper value of nS corresponding to the specific VOC to which
the sensor is exposed. The presence of graphene and MXene
layers over the metal ensures excellent adsorption of VOCs.
This prevents any possible oxidation of the metal layers, es-
pecially for Ag- and Al-based sensors. However, increasing
the thickness of these layers is seen to result in a decrease in
DA of the sensors, though the sensitivity is greatly enhanced.
Hence, if attaining higher DA is the design goal, our studies
suggest that it would be prudent to develop metal/graphene/
MXene fiber-optic SPR sensors with minimal layers of
graphene and MXene. For higher sensitivity for the detection
of acetone in the visible region, within the benchmark levels
of DA, the ideal combinations are listed in Table 2. The
highest sensitivity of 5150 nm/RIU is obtained for the sensor
having 40 nm of Au, 10 layers of graphene, and 3 layers of
Ti3C2Tx. The difference in number of optimal layers of
graphene and Ti3C2Tx for maximum sensitivity is due to the
464 Plasmonics (2020) 15:457–466

1.0 3000 32
(b)
Normalised Transmitted Power

Detection Accuracy (nm )

-1
0.8

Sensitivity (nm/RIU)
(a)
2000 24
0.6
Al-10 nm
0.4 Al-20 nm
Al-30 nm 1000 16
Al-40 nm
0.2 Al-50 nm
Al-60 nm
0.0 0 8
200 400 600 800 10 20 30 40 50 60 70
Wavelength (nm) Thickness of Al (nm)
16000
(c) Al- 10 nm (d) Ti3C2Tx-0 Layer
100
14000 Ti3C2Tx-1 Layer

Detection Accuracy (nm )

Detection Accuracy (nm )
Al- 40 nm

-1
-1
30 4000 Ti3C2Tx-2 Layers

Sensitivity (nm/RIU)
Sensitivity (nm/RIU)

Al- 60 nm
12000 Ti3C2Tx-3 Layers 80
10000
3500 60
8000 20

6000 40
3000
4000
10 20
2000 2500
0 0
1.0 1.1 1.2 1.3 1.4 1.5 0 5 10 15 20 25
Refractive Index, ns Number of Graphene Layers
Fig. 5 a Wavelength dependence of transmitted power as a function of single layer of Ti3C2Tx, and nS = 1.358. c Dependence of sensitivity and
varying thickness of Al as the metallic layer, for a sensor having four DA on nS for sensors having four layers of graphene and a single layer of
layers of graphene and a single layer of Ti3C2Tx, for an analyte having Ti3C2Tx, for three different thicknesses of Al. d Sensitivity and DA as a
refractive index of nS = 1.358. b Variation of sensitivity and DA as a function of number of layers of graphene, for different layers of Ti3C2Tx,
function of thickness of Al for sensors having four layers of graphene, a keeping thickness of Al as 40 nm and nS as 1.358

fact that the effective refractive index of the metal/graphene reasonable to expect variations of RI of these 2D materials,
layers drives the excitation of surface plasmons at the and hence deviations from the considered dispersion relations.
Ti3C2Tx/sensing medium interface. Since the permittivity of This would alter the optimal thickness of the layers for max-
the considered metals is all different, the phase matching con- imum sensitivity at reasonable DA. Therefore, only practical
ditions for excitation of the surface plasmons can be achieved measurements can validate the findings reported herein.
only for different thicknesses of graphene and Ti3C2Tx.
Finally, we would like to discuss the practical implementa-
tion of the proposed sensors and associated challenges. We Conclusion
have used dispersion relations of graphene and MXene obtain-
ed from the literature for simulations of transmitted power In the present study, we have proposed and analyzed three
through the optic fiber. Depending on the mode of synthesis different configurations of metal/graphene/Ti3C2Tx fiber-
and accuracy of the characterization tools, it would be optic SPR sensors on PCS fiber, with Au, Ag, and Al as the

Table 2 Optimized thickness of

layers for maximum sensitivity in Metal Thickness of metal Number of layers of Number of layers of Sensitivity (nm/
the visible range, for detection of (nm) graphene Ti3C2Tx RIU)
acetone
Au 40 10 3 5150
Ag 40 24 1 4500
Al 40 20 3 4200
Plasmonics (2020) 15:457–466
metals. A thickness of 40 nm for the metal layer was found to
be optimal for high sensitivity. The presence of graphene and
Ti3C2TxMXene layers was found to enhance the sensitivity;
the higher the number of layers, the better was the sensitivity,
but at the expense of DA. Effective sensing could be achieved
with select combinations of metal and different numbers of
layers of graphene and Ti3C2TxMXene in order to span sens-
ing medium refractive index of 1.34–1.45 corresponding to a
variety of VOCs such as acetone, ethanol, and glycerol. The
results indicate that Ti3C2TxMXene with its strong physical
adsorption capabilities for VOCs together with graphene hav-
ing excellent conductivity and carrier mobility matching with
those of metals can be tailored to optimize optical sensing
probes for rapid screening of medical conditions and quality
of food products.
Acknowledgments The authors are thankful to Dr. K. V. Dominic,
Professor of English (retired) and Editor-in-Chief, Writers Editors
Critics (WEC), Prof. B. Hariharan, Institute of English, University of
Kerala, and Thomas Nedumpara, North Cumbria University Hospitals
NHS Trust, Carlisle, UK, for the support given in English language
editing. Sudheer VR acknowledges the Co-Operative Academy of
Professional Education for providing fellowship under the Faculty
Development Program
Compliance with Ethical Standards
Conflict of Interest The authors declare that they have no conflict of
interest.
References
1. Dong D, Jiao L, Li C, Zhao C (2019) Rapid and real-time analysis
of volatile compounds released from food using infrared and laser
spectroscopy. TrAC Trends Anal Chem 110:410–416
2. Popov TA (2011) Human exhaled breath analysis. Ann Allergy
Asthma Immunol 106:451–456
3. Galassetti PR, Novak B, Nemet D, Rose-Gottron C, Cooper DM,
Meinardi S, Newcomb R, Zaldivar F, Blake DR (2005) Breath
ethanol and acetone as indicators of serum glucose levels: an initial
report. Diabetes Technol Ther 7:115–123
4. Ruzsányi V, Péter Kalapos M (2017) Breath acetone as a potential
marker in clinical practice. J Breath Res 11:024002
5. Nardi-Agmon I, Peled N (2017) Exhaled breath analysis for the
early detection of lung cancer: recent developments and future pros-
pects. Lung Cancer (Auckland, NZ) 8:31–38
6. Gruber B, Keller S, Groeger T, Matuschek G, Szymczak W,
Zimmermann R (2016) Breath gas monitoring during a glucose
challenge by a combined PTR-QMS/GC×GC-TOFMS approach
for the verification of potential volatile biomarkers. J Breath Res
10:036003
7. Tanda N, Hinokio Y, Washio J, Takahashi N, Koseki T (2014)
Analysis of ketone bodies in exhaled breath and blood of ten
healthy Japanese at OGTT using a portable gas chromatograph. J
Breath Res 8:046008
8. Righettoni M, Schmid A, Amann A, Pratsinis SE (2013)
Correlations between blood glucose and breath components from
portable gas sensors and PTR-TOF-MS. J Breath Res 7:037110
465
9. Phan N-T, Kim K-H, Jeon E-C, Kim U-H, Sohn JR, Pandey SK
(2012) Analysis of volatile organic compounds released during
food decaying processes. Environ Monit Assess 184:1683–1692
10. Jiao L, Guo Y, Chen J, Zhao X, Dong D (2019) Detecting volatile
compounds in food by open-path Fourier-transform infrared spec-
troscopy. Food Res Int 119:968–973
11. Kim SJ, Koh H-J, Ren CE, Kwon O, Maleski K, Cho S-Y, Anasori
B, Kim C-K, Choi Y-K, Kim J, Gogotsi Y, Jung H-T (2018)
Metallic Ti3C2Tx MXene gas sensors with ultrahigh signal-to-
noise ratio. ACS Nano 12:986–993
12. Andre RS, Sanfelice RC, Pavinatto A, Mattoso LHC, Correa DS
(2018) Hybrid nanomaterials designed for volatile organic com-
pounds sensors: a review. Mater Des 156:154–166
13. Pang J, Mendes RG, Bachmatiuk A, Zhao L, Ta HQ, Gemming T,
Liu H, Liu Z, Rummeli MH (2019) Applications of 2D MXenes in
energy conversion and storage systems. Chem Soc Rev 48:72–133
14. Anasori B, Lukatskaya MR, Gogotsi Y (2017) 2D metal carbides
and nitrides (MXenes) for energy storage. Nat Rev Mater 2:16098
15. Tang H, Hu Q, Zheng M, Chi Y, Qin X, Pang H, Xu Q (2018)
MXene–2D layered electrode materials for energy storage. Prog
Nat Sci Mater Int 28:133–147
16. Hantanasirisakul K, Zhao M-Q, Urbankowski P, Halim J, Anasori
B, Kota S, Ren CE, Barsoum MW, Gogotsi Y (2016) Fabrication of
Ti3C2Tx MXene transparent thin films with tunable optoelectronic
properties. Adv Electron Mater 2:1600050
17. Khazaei M, Ranjbar A, Arai M, Sasaki T, Yunoki S (2017)
Electronic properties and applications of MXenes: a theoretical
review. J Mater Chem C 5:2488–2503
18. Wu L, You Q, Shan Y, Gan S, Zhao Y, Dai X, Xiang Y (2018) Few-
layer Ti3C2Tx MXene: a promising surface plasmon resonance
biosensing material to enhance the sensitivity. Sensors Actuators
B Chem 277:210–215
19. Sinha A, Dhanjai H, Zhao Y, Huang XL, Chen J, Jain R (2018)
MXene: an emerging material for sensing and biosensing. TrAC
Trends Anal Chem 105:424–435
20. Kumar S, Lei Y, Alshareef NH, Quevedo-Lopez MA, Salama KN
(2018) Biofunctionalized two-dimensional Ti3C2 MXenes for ul-
trasensitive detection of cancer biomarker. Biosens Bioelectron
121:243–249
21. Bai X, Ling C, Shi L, Ouyang Y, Li Q, Wang J (2018) Insight into
the catalytic activity of MXenes for hydrogen evolution reaction.
Sci Bull 63:1397–1403
22. Li Z, Wu Y 2D early transition metal carbides (MXenes) for catal-
ysis. Small 0:1804736
23. Maleski K, Ren CE, Zhao M-Q, Anasori B, Gogotsi Y (2018) Size-
dependent physical and electrochemical properties of two-
dimensional MXene flakes. ACS Appl Mater Interfaces 10:
24491–24498
24. Zheng J, Diao J, Jin Y, Ding A, Wang B, Wu L, Weng B, Chen J
(2018) An inkjet printed Ti3C2-GO electrode for the electrochem-
ical sensing of hydrogen peroxide. J Electrochem Soc 165:B227–
B231
25. Wang F, Yang C, Duan M, Tang Y, Zhu J (2015) TiO2 nanoparticle
modified organ-like Ti3C2 MXene nanocomposite encapsulating
hemoglobin for a mediator-free biosensor with excellent perfor-
mances. Biosens Bioelectron 74:1022–1028
26. Liu F, Zhou A, Chen J, Jia J, Zhou W, Wang L, Hu Q (2017)
Preparation of Ti3C2 and Ti2C MXenes by fluoride salts etching
and methane adsorptive properties. Appl Surf Sci 416:781–789
27. Justino CIL, Gomes AR, Freitas AC, Duarte AC, Rocha-Santos
TAP (2017) Graphene based sensors and biosensors. TrAC
Trends Anal Chem 91:53–66
28. Nag A, Mitra A, Mukhopadhyay SC (2018) Graphene and its
sensor-based applications: a review. Sensors Actuators A Phys
270:177–194
466
29. Liu N, Chortos A, Lei T, Jin L, Kim TR, Bae W-G, Zhu C, Wang S,
Pfattner R, Chen X, Sinclair R, Bao Z (2017) Ultratransparent and
stretchable graphene electrodes. Sci Adv 3:e1700159
30. Xiao S, Wang T, Liu T, Yan X, Li Z, Xu C (2018) Active modula-
tion of electromagnetically induced transparency analogue in
terahertz hybrid metal-graphene metamaterials. Carbon 126:271–
278
31. Liu T, Wang H, Liu Y, Xiao L, Zhou C, Liu Y, Xu C, Xiao S (2018)
Independently tunable dual-spectral electromagnetically induced
transparency in a terahertz metal–graphene metamaterial. J Phys
D Appl Phys 51:415105
32. Xiao S, Wang T, Jiang X, Yan X, Cheng L, Wang B, Xu C (2017)
Strong interaction between graphene layer and Fano resonance in
terahertz metamaterials. J Phys D Appl Phys 50:195101
33. Xiao S, Liu T, Zhou C, Jiang X, Cheng L, Xu C (2019) Tailoring
slow light with a metal–graphene hybrid metasurface in
the terahertz regime. J Opt Soc Am B 36:E48–E54
34. Sharma AK, Jha R, Gupta BD (2007) Fiber-optic sensors based on
surface plasmon resonance: a comprehensive review. IEEE Sensors
J 7:1118–1129
35. Jorgenson RC, Yee SS (1993) A fiber-optic chemical sensor based
on surface plasmon resonance. Sensors Actuators B Chem 12:213–
220
36. Gupta G, Kumar A, Boopathi M, Thavaselvam D, Singh B,
Vijayaraghavan R (2011) Rapid and quantitative determination of
biological warfare agent Brucella abortus CSP-31 using surface
plasmon resonance
37. Ghosh N, Gupta G, Boopathi M, Pal V, Singh AK, Gopalan N, Goel
AK (2013) Surface plasmon resonance biosensor for detection of
bacillus anthracis, the causative agent of anthrax from soil samples
targeting protective antigen. Indian J Microbiol 53:48–55
38. Villuendas F, Pelayo J (1990) Optical fibre device for chemical
seming based on surface plasmon excitridon. Sensors Actuators A
Phys 23:1142–1145
39. Yuan H, Ji W, Chu S, Qian S, Wang F, Masson J-F, Han X, Peng W
(2018) Fiber-optic surface plasmon resonance glucose sensor en-
hanced with phenylboronic acid modified au nanoparticles. Biosens
Bioelectron 117:637–643
40. Semwal V, Gupta BD (2019) Highly sensitive surface plasmon
resonance based fiber optic pH sensor utilizing rGO-Pani nanocom-
posite prepared by in situ method. Sensors Actuators B Chem 283:
632–642
41. Homola J (1997) On the sensitivity of surface plasmon resonance
sensors with spectral interrogation. Sensors Actuators B Chem 41:
207–211
Plasmonics (2020) 15:457–466
42. Ghatak AK, Thyagarajan K (2006) Introduction to fiber optics.
Cambridge University Press, Cambridge
43. Sharma AK, Gupta BD (2007) On the performance of different
bimetallic combinations in surface plasmon resonance based fiber
optic sensors. J Appl Phys 101:093111
44. Ordal MA, Long LL, Bell RJ, Bell SE, Bell RR, Alexander RW,
Ward CA (1983) Optical properties of the metals Al, Co, Cu, Au,
Fe, Pb, Ni, Pd, Pt, Ag, Ti, and W in the infrared and far infrared.
Appl Opt 22:1099–1119
45. Lambrecht A, Reynaud S (2000) Casimir force between metallic
mirrors. Eur Phys J D 8:309–318
46. Bruna M, Borini S (2009) Optical constants of graphene layers in
the visible range. Appl Phys Lett 94:031901
47. Miranda A, Halim J, Lorke A, Barsoum MW (2017) Rendering
Ti3C2Tx (MXene) monolayers visible. Mater Res Lett 5:322–328
48. Sarika S, Gupta BD (2010) Simulation of a surface plasmon
resonance-based fiber-optic sensor for gas sensing in visible range
using films of nanocomposites. Meas Sci Technol 21:115202
49. Hansen WN (1968) Electric fields produced by the propagation of
plane coherent electromagnetic radiation in a stratified medium. J
Opt Soc Am 58:380–390
50. Downes F, Taylor CM (2015) Optical fibre surface plasmon reso-
nance sensor based on a palladium-yttrium alloy. Procedia Eng 120:
602–605
51. Mohammadi MD, Hamzehloo M (2019) Densities, viscosities, and
refractive indices of binary and ternary mixtures of methanol, ace-
tone, and chloroform at temperatures from (298.15–318.15) K and
ambient pressure. Fluid Phase Equilib 483:14–30
52. Mishra AK, Mishra SK, Verma RK (2016) Graphene and beyond
graphene MoS2: a new window in surface-plasmon-resonance-
based fiber optic sensing. J Phys Chem C 120:2893–2900
53. Luo J, Zhang W, Yuan H, Jin C, Zhang L, Huang H, Liang C, Xia Y,
Zhang J, Gan Y, Tao X (2017) Pillared structure design of MXene
with ultralarge interlayer spacing for high-performance lithium-ion
capacitors. ACS Nano 11:2459–2469
54. Chen H, Kou X, Yang Z, Ni W, Wang J (2008) Shape- and size-
dependent refractive index sensitivity of gold nanoparticles.
Langmuir 24:5233–5237
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