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Abstract— Surface plasmon resonance (SPR) based fluoride Ethanol and methanol are two important organic compounds
fiber-optic sensor with graphene and sodium fluoride layers is used for different purposes and their detection has been an
simulated and analyzed in near infrared (NIR) for detection of area of considerable interest for applications in several fields,
alcohols. Through this paper, the fluoride fiber has been employed
for the first time in SPR sensing application. The proposed fiber ranging from environment to food to chemical industries [4].
optic sensor is analyzed under angular interrogation method, The detection of organic compounds (e.g., methanol and
which is based on on-axis launching of monochromatic light ethanol) should be carried out in infrared (IR) because they
into the fiber core at varying angle followed by measuring the have their characteristic absorption bands in IR enabling a
power transmitted through the SPR probe region. The sensor’s label-free and real time sensing procedure [6]. In addition,
specificity towards alcohols plus a significantly increased sensi-
tivity and accuracy are ensured by a polythiophene layer. The several other key benefits are achievable in IR such as
results indicate that longer NIR wavelength (λ) provides superior enhanced sensitivity [7], lower power requirement [8], and
sensing performance. Further, the proposed sensor’s performance deeper penetration depth [7] etc.
can be significantly enhanced by tuning the chemical potential For designing an SPR-based sensor probe in near-IR (NIR),
(μ) of graphene monolayer. In summary, monochromatic light appropriate materials (i.e., glass substrate, metal, and dielectric
of λ = 1550 nm and 0.65 eV < μ < 0.70 eV provides
substantially high performance in terms of sensitivity, accuracy, layers) need to be selected for optimal and stable sensing per-
and figure of merit. The proposed sensor has the capability to formance. Taking this into consideration, heavy metal fluoride
provide significantly better performance than previously-reported glasses have been recognized to provide better performance
SPR sensors. in NIR due to their excellent optical properties such as low
Index Terms— Infrared sensors, optical fiber sensors, organic mean dispersion [9], low Rayleigh scattering [9], smaller
compounds, plasmons, sensitivity and specificity. birefringence [10], lesser thermal dependence of optical prop-
erties [10], low optical non-linearity, and broad transmission
I. I NTRODUCTION window [9]–[11]. It is worth-mentioning that in NIR wave-
length region, fiber materials other than silica are yet to
T HE surface plasmon resonance (SPR) sensing technique,
wherein the manipulation of electromagnetic (EM) radi-
ation for the excitation of plasmons and confinement of the
be explored in detail. In particular, fluoride fibers, in view
of above-mentioned exceptional optical properties, should be
field generated to regions below diffraction limit have been exploited in SPR-based chemical- and bio-sensing. However,
utilized for extensive applications in several chemical and the reliability of the fiber chosen also depends on protecting
environmental processes [1], [2] due to its advantage of better it against moisture and reducing the surface crystallization
selectivity, non invasiveness, and higher sensitivity compared effects of the fluoride glass [11]. The solution to these prob-
to other existing techniques such as infrared spectroscopy lems is to select a fluoride glass with high crystallization
etc. [3]. Interestingly, it can be noted that fiber optic sensors stability [9], e.g., ZBLAN glass, as the material for the fiber
provide several features, such as passivity and immunity to EM core and coat it with protective layers to prevent corrosion.
interferences [4], remote sensing applications, multiplexing Further, fluoride fibers exhibit slightly higher thermal expan-
abilities, low-cost probe design, and portability [5] etc. sion characteristics compared to conventional silica fibers [9].
The above-mentioned features of fiber-optic sensor probe However, this issue can be negated by keeping the temperature
are hugely advantageous while sensing different chemical unchanged (preferably near room temperature).
compounds with minimal interference with the environment. Further, among the generally used noble metals, silver (Ag)
exhibits a better performance owing to its superior detection
Manuscript received February 17, 2018; accepted March 14, 2018. Date of accuracy in terms of SPR-based detection. However, Ag gets
publication March 22, 2018; date of current version April 23, 2018. The work
of A. Dominic was supported by MHRD (India) in the form of assistantship. oxidized very rapidly, and therefore, causes chemical instabil-
The associate editor coordinating the review of this paper and approv- ity [12]. So, a due protection is required in order to use Ag
ing it for publication was Prof. Bhaskar Choubey. (Corresponding author: in SPR-based detection of organic compounds.
Anuj K. Sharma.)
A. K. Sharma is with the Department of Applied Sciences, Physics A recent attraction among researchers has been the use
Division, National Institute of Technology Delhi, Delhi 110040, India (e-mail: of graphene in design of various electronic and photonic
anujsharma@nitdelhi.ac.in). devices [13]. Graphene, with its phenomenal optical and chem-
A. Dominic is with the Department of Electronics and Communication
Engineering, National Institute of Technology Delhi, Delhi 110040, India. ical properties such as impermeability, chemical stability, and
Digital Object Identifier 10.1109/JSEN.2018.2818197 compatibility [14], [15], possesses an immense capability to
1558-1748 © 2018 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
4054 IEEE SENSORS JOURNAL, VOL. 18, NO. 10, MAY 15, 2018
Fig. 3. Simulated variation of FOM with wavelength of light source. The Fig. 4. Simulated variation of FOM with chemical potential (μ) of graphene
points (+) indicate the wavelength of some commercially available laser monolayer (0.34 nm thick) at λ = 1550 nm. The right inset shows the
diodes. The inset shows the corresponding variations of detection sensitivity corresponding simulated variation of sensitivity and accuracy with chemical
and detection accuracy with wavelength. potential at λ = 1550 nm. The left inset shows the simulated variation of
FOM with chemical potential at λ = 1550 nm for ZBLAN prism based
sensor probe.
However, the above analysis is carried out only for a single
NIR wavelength (λ = 785 nm), and it is imperative to analyze
between SD and AD , it may not be possible to clearly get
the influence of NIR wavelength on the sensor’s performance.
an optimized value of wavelength. Nevertheless, a practical
solution can be found by setting a performance criterion
B. Effect of NIR Wavelength related to minimum requisite values of SD and AD leading
to an appropriate selection of wavelength. In this context,
Figure 3 represents the variation of proposed sensor’s FOM
it is important to mention that in addition to significantly
with λ corresponding to the NIR spectral range in which
better overall sensing performance (i.e., FOM), longer NIR
a number of monochromatic laser diodes are commercially
wavelength also provides superior suitability for biosample
available.
detection due to much smaller photodamage [7], [31] and
The above plot shows that the FOM improves signifi-
reduced Rayleigh scattering (∝ 1/λ4 ). Thus, it can be con-
cantly with an increase in wavelength. Numerically, the FOM
cluded that longer NIR wavelength source should be used in
improves from 144.310 RIU−1 to 325.011 RIU−1 when λ
the proposed fiber optic SPR sensor probe for detection of
is increased from 780 nm to 980 nm. It indicates towards
organic compounds. Here, it should also be noted that above
nearly 125% enhancement in FOM for a corresponding
spectral variation of FOM (as shown in figure 3) has been
increase of 200 nm in light wavelength. The above out-
simulated without PT layer (due to lack of dispersion data
come corroborates another previously reported work regard-
for PT at several wavelengths). However, it is expected from
ing enhanced plasmonic sensing performance at longer NIR
figure 2 and the related discussion that employing the PT will
wavelength [30].
further increase the FOM at longer wavelengths.
At this point, it is important to analyze how the light
wavelength individually affects the sensitivity and accuracy
of the proposed sensor. The above variation of SD and AD C. Effect of Graphene’s Chemical Potential at Longer
with λ is shown in the inset of figure 3, which clearly NIR Wavelength
indicates a trade-off between SD and AD . The sensitivity Following the above observation regarding using longer NIR
decreases whereas accuracy increases for longer wavelength. wavelength, the proposed fiber optic SPR sensor is further
Numerically, SD decays from 130.6010/RIU for λ = 780 nm simulated at λ = 1550 nm and the corresponding FOM is
to 113.6440/RIU for λ = 980 nm, which amounts to nearly obtained as 443.163 RIU−1 . It means that there is nearly 240%
13% decrease in SD for a corresponding change of 200 nm increase in FOM at λ = 1550 nm compared with the FOM at
in λ. On the other hand, AD increases from 1.105/0 for λ = 780 nm. However, the wavelength cannot be increased
λ = 780 nm to 2.786/0 for λ = 980 nm, i.e., nearly 152% beyond a certain level because of corresponding decay in
increase in AD for a corresponding change of 200 nm in sensitivity (as discussed in previous section). At this point, it
λ. Main reason behind this effect is that at shorter wave- becomes essential to explore the role of graphene properties in
lengths, the multilayered plasmonic structure becomes highly order to further enhance the sensor’s performance. Variation
lossy (due to much greater imaginary part of its effective in graphene’s chemical potential (μ) is a crucial parameter
index) mainly owing to increased lossy behavior of metal that affects its complex RI due to corresponding variations in
layer [30]. Since, the magnitude of increase in AD is much charge career concentrations [32]. Recently, the influence of
larger than the decay in SD , therefore, the combined effect of graphene’s chemical potential on fluoride prism-based SPR
the above opposite spectral variations of SD and AD results sensor probe’s performance has been studied in NIR [16].
in nearly 125% increase in FOM within the above λ-range Fig. 4 depicts the variation of FOM of proposed fiber-optic
(i.e., 780-980 nm). SPR sensor probe with μ at λ = 1550 nm.
In above context, it is worth-mentioning that even though It is clear from Fig. 4 that the sensor’s FOM varies signif-
shorter wavelength provides larger sensitivity of a plasmonic icantly with chemical potential. FOM is 443.163 RIU−1 at
sensor, it is equally important to ensure greater accuracy μ = 0 eV and it increases steadily until it becomes
(i.e., as small measurement error as possible) that is achievable 470.345 RIU−1 at μ = 0.41 eV. Thereafter, it decreases
with longer wavelength (as discussed above). Due to trade-off sharply until it encounters a minimum value of 345.460 RIU−1
SHARMA AND DOMINIC: FLUORIDE FIBER-OPTIC SPR SENSOR WITH GRAPHENE AND NaF LAYERS 4057
at μ = 0.49 eV. For μ > 0.49 eV, the FOM keeps on TABLE I
increasing until it reaches its peak value of 510.994 RIU−1 C OMPARISON OF SPR S ENSING P ERFORMANCE
at μ = 1.0 eV. It clearly indicates that tuning the chemical
potential to adequate levels can bring desirable enhancement
in the sensor’s FOM. The chemical potential of graphene can
be tuned mainly either by external gate voltage or by chemical
doping methods [33]. For the present study, we consider
that the chemical potential of graphene layer is not being
actively tuned. Since, chemical doping can permanently tune
graphene for long-term device application assuming that once
graphene is chemically prepared and doped (typical value of μ
around 0.6 eV), it is isolated from the environment [22], [23],
therefore, we have considered that different chemically doped
graphene monolayers are being individually used for sensor
simulation. However, it becomes more complicated to achieve
greater values of μ (e.g., 1 eV). This difficulty may be
significantly avoided by choosing the value of μ around
0.65 - 0.70 eV that provides a significantly large FOM of
nearly 500 - 504 RIU−1 , which is extremely close to the
peak FOM (i.e., 510.994 RIU−1 corresponding to μ = 1 eV)
at λ = 1550 nm. In view of above discussion about the
permanent tuning of μ through chemical doping, it is expected
that the above range of μ (i.e., 0.65 - 0.70 eV) may be achieved
by chemical doping. Nevertheless, as suggested by a previous
study that if graphene is sufficiently doped to support SPW
near λ = 1550 nm, the external electric and magnetic fields
can still be used for dynamic (active) tuning [24], which is
an important point if further higher values of μ are required.
Combining two or more doping methods (e.g., external gate
voltage and chemical/molecular doping) may also be explored, and, therefore, greater FOM than prism-based probe. The
if needed. above comparison further strengthens the utility of proposed
The right inset of figure 4 shows the corresponding variation fiber-optic SPR sensor probe over the prism-based one.
of SD and AD with μ at λ = 1550 nm. As is visible, there Going further, the following table I shows the comparison
is hardly any variation in SD with μ but the AD component of the proposed sensor’s FOM with a few important works on
shows a significant variation, which effectively commands the SPR sensor [35]–[41].
whole variation of FOM with μ. It signifies that the above The above table indicates that the proposed fiber optic SPR
range of μ (i.e., 0.65 - 0.70 eV) is able to provide nearly sensor for alcohol detection has the capability of providing
constant sensitivity (around 1000/RIU, which is sufficiently greater FOM compared with other plasmonic sensor designs.
large in view of the angular resolution of 0.0010 available
with present instruments [34]), high accuracy (around 5 /0 ), IV. C ONCLUSION
as well as large FOM (around 500 RIU−1 ) extremely close to ZBLAN fluoride fiber optic SPR sensor with graphene
maximum possible FOM. and NaF layers has been studied in NIR for detection of
alcohols. The simulation results indicate that the fiber-optic
probe provides much better sensing performance compared
D. Sensing Performance Comparison with its prism-based counterpart. The introduction of alcohol-
The left inset of figure 4 shows the simulated variation specific PT layer leads not only to enhanced sensing perfor-
of FOM with μ at λ = 1550 nm for ZBLAN prism based mance but also adds to the specificity of the sensor. It is
SPR sensor probe with Ag layer (45 nm) and graphene found that laser sources of longer NIR wavelength should be
monolayer (0.34 nm). The corresponding SPR curve consists used as they lead to greater FOM of the sensor. However,
of the variation of reflection coefficient (R) with θ , while the sensitivity may be slightly smaller for longer wavelength
FOM is defined as same as in Eq. (6). The objective of but the same can be compensated with much greater accuracy.
showing this variation is to appreciate the comparison between The chemical potential (μ) of graphene can be exploited as
prism-based and the proposed fiber-optic SPR sensor probes. a crucial parameter to improve the sensor’s performance at
Clearly, the FOM achievable with the fiber-optic probe is longer NIR wavelength. At λ = 1550 nm, an exceptionally
much better (nearly 2.5 times greater) compared with the balanced set of performance parameters (sensitivity, accuracy,
prism-based probe. The main reason is that due to multiple and FOM) can be achieved for 0.65 eV < μ < 0.7 eV.
reflections, the fiber-optic probe is able to cause more change The proposed sensor has the capability to provide significantly
in output signal (i.e., power loss) leading to smaller FWHM better performance than previously-reported SPR sensors.
4058 IEEE SENSORS JOURNAL, VOL. 18, NO. 10, MAY 15, 2018