Titanium Dioxide, Black Phosphorus and Bimetallic Layer-Based Surface Plasmon Biosensor For Formalin Detection: Numerical Analysis
Titanium Dioxide, Black Phosphorus and Bimetallic Layer-Based Surface Plasmon Biosensor For Formalin Detection: Numerical Analysis
Titanium Dioxide, Black Phosphorus and Bimetallic Layer-Based Surface Plasmon Biosensor For Formalin Detection: Numerical Analysis
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Abstract
Formalin detection is a deep concern in food items as its recurring consumption causes
some life-taking diseases like chronic cancer. This article proposes a biosensor based on
surface plasmon resonance (SPR) that uses this resonance-based concept for formalin
detection. Our proposed hybrid design consists of two metallic layers of gold (Au), black
phosphorus (BP) as a basic recognition element (BRE), and a single titanium dioxide layer
(TiO2) film. The performance parameters were being calculated. The highest sensitivity
achieved is 327.6 deg∕RIU for Bi-films of TiO2 and one BP film. By using attenuated total
reflection (ATR), the formalin detection using biosensor with the help of reflectance and
incident angle plot for various formalin concentrations. Finally, the previous and this com-
parative research analysis is being studied. The analysis of the proposed sensor has been
carried out using COMSOL Multiphysics.
* Bhishma Karki
magnum.photon@gmail.com
1
Department of Physics, Tri-Chandra Multiple Campus, Tribhuvan University, Kathmandu 44600,
Nepal
2
National Research Council Nepal, New Baneshwor‑10, Kathmandu 44600, Nepal
3
Department of EEE, Sri Krishna College of Engineering and Technology, Coimbatore,
Tamil Nadu, India
4
Department of EEE, Kumaraguru College of Technology, Coimbatore, Tamil Nadu, India
5
Department of Mechanical Engineering, ABES Engineering College, Ghaziabad, UP 201009,
India
6
Department of ECE, DIT University, Dehradun 248009, India
13
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451 Page 2 of 15 B. Karki et al.
1 Introduction
The surface plasmon-based biosensor has been extensively used in biochemical sensing
for a few decades. Their exclusive properties like reliability, label-free detection, greater
sensitivity, and real-time detection capacity (Homola et al. 1999; Borisov and Wolfbeis
2008; Fan et al. 2008; Wijaya et al. 2011; Kaminski et al. 2017) make them appropriate for
sensing-based applications. Different configurations of SPR based sensors were designed
for sensing purposes based on optical fiber, prism, grating, and coupled waveguide. Here,
Kretschmann configuration-based biosensor (prism-based) has been analyzed, in which a
metal film is placed on a prism base (Kretschmann and Raether 1968). The prism-based
biosensor follows the attenuated total reflection (ATR) phenomenon (Karki et al. 2022a).
The transverse magnetic (TM) polarized input wave generates evanescent waves with
exponential attenuation penetrating the thin metal layer at the prism-metal interface (Wang
et al. 2022). Finally, it generates surface plasmon at the metal-sensing layer interface. The
change in the analyte’s refractive index (RI) varies the resonance angle (Xu et al. 2019;
Bhatia and Gupta 2011). The optical properties of 2-D material have made Black phos-
phorus (BP) widely used in the SPR sensor design over the last decade (Churchill and
Jarillo-Herrero 2014). Black phosphorus has a high surface-to-volume ratio, high mobil-
ity, direct bandgap, and greater bio-molecule absorption (Rouf and Haque 2018; Li et al.
2014; Cho et al. 2016). The main shortcoming of using BP is it frequently oxidizes (Su
et al. 2020), which can further be decreased with the inclusion of some other material or
using the hybrid layer-based using different combinations of 2-D materials (Jia et al. 2020;
Xiang et al. 2018; Vahedi and Kouhi 2020; AlaguVibisha, et al. 2020; Lin et al. 2020;
Saifur Rahman et al. 2018). Some research shows work on SPR sensor design based on
graphene, BP, transition metal dichalcogenides (TMDCs) materials has been carried out.
Shrivastava and Jha proposed an SPR biosensor to achieve the sensitivity of 110 deg/RIU
as BP-MoS2 materials are used as core plasmonic 2D material (Srivastava and Jha 2018).
A gas detection-based SPR sensor is proposed by Singh and Raghuvanshi with dual Au
layer and bi-BP layers, achieving sensitivity to 245.5 deg∕RIU (Singh and Raghuwanshi
2019). Wu. et al. (Wu et al. 2017) proposed the biosensor based on surface plasmon mech-
anism using graphene, BP, and Au as a metal layer, giving 279 deg/RIU sensitivity. Pal and
Jha theoretically demonstrated an SPR biosensor with BaTiO3 and achieved a sensitivity
of 294 deg∕RIU (Pal and Jha 2021). Bijalwan et al. designed an SPR biosensor using gra-
phene and metal layers of gold and aluminum, giving a 160 deg/RIU sensitivity. In another
design with W Se2-Au-Al, the sensitivity of 163 deg∕RIU was achieved (Bijalwan et al.
2020). Karki et al. proposed that an SPR biosensor with a sensitivity of 352 deg/RIU is
achieved with bi-metallic nickel and silver nanofilms with a franckeite layer in between
(Karki et al. 2021a). Liu et al. designed an SPR biosensor based on tilted fiber Bragg grat-
ing (TFBG) for the detection of environmental estrogens (EEs) (Liu, et al. 2021). Yang and
colleagues investigated the nonlinear response of a Fano resonant Silicon relied on a meta-
surface driven by a strong laser field. They observed improved high-harmonic emission and
differential frequency production (Yang et al. 2021). Sun et al. proposed a pressure sensor.
Their main findings include the device’s 45 ms response time and 14,000 cycles of impres-
sive cyclic repeatability (Sun et al. 2021). Du et al. proposed a robust optical fiber-based
photodetector based on vertical ZnO-P3HT heterostructure to get self-powered and ultrafast
UV sensing. They achieved tunable photo response and very fast response and recovery
time less than 40 ms (Du et al. 2022). Liu et al. proposed a gas sensor based upon the ZnO-
Bi2O3 structure which can diagnose the diabetes in initial stages (Liu et al. 2021). Olyaee
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The biosensor based on the Kretschmann configuration is shown in Fig. 1. The sen-
sor design is composed of Ag-TiO2-Au-BP layers are stacked on a prism base. This
layer composition is made to contact a sensing medium in which Phosphate buffer saline
(PBS) solution is present. This PBS layer has the target analytes which is used for sens-
ing. From the constructional point of view, initially BK7 prism with RI, np = 1.55 is pre-
sent. The next layer is of silver (Ag) metal film of an optimized thickness (t1 = 50 nm and
n1 = 0.1350 + 4*i*3I9850) is placed over the prism; in continuation, the third film is of
TiO2 with the thickness (t2 = T*2 nm and n2 = 2.5837) with the gold (Au) layer deposited
above it with an optimized thickness ( t3 = 5nm and n 3 = 0.181 + i*3.068), the fourth layer
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where np , ns represents the RI of BK7 prism (1.515) and RI of sensing medium (PBS solu-
tion) equals 1.34, respectively. The nc is the equivalent RI of
√ Ag-TiO2-Au-BP materials.
The expression for the composite layer’s RI, defined by nc = 4 (n1 n2 n3 n4 ) . When a mono-
adhesive polymer called chitosan, after combining with the Formalin and flowing on the
sensor surface, changes the RI of the sensing layer because of a biochemical reaction
between the two. This change in RI mathematically be expressed as (Theisen et al. 1999):
𝛿n
Δns = n2s − n1s = C (2)
𝛿c
where n2s = n1s + C 𝛿n
𝛿c
where C denotes the concentration of biomolecules adsorbed.
The change in the refractive index of formalin is given by Eq. (2). RI of sensing media
before formaldehyde molecule adsorption n2s and n1s is the RI of PBS without dielectric
existence inside the sensing layer. The formaldehyde molecular concentration is 1000 nM,
with the sensing layer considered C = 1000 nM. The fraction 𝛿n 𝛿c
indicates the RI value
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Titanium dioxide, black phosphorus and bimetallic layer‑based… Page 5 of 15 451
incrementor. This RI variation occurs after the formaldehyde molecule is dissolved in the
PBS solution consisting of sensing layer. The fraction 𝛿n
𝛿c
= 0.182 cm3 ∕g for PBS (Hos-
sain et al. 2019). This PBS is a composition of monosodium phosphate (NaH2 PO4 ) con-
sisting of 0.0003 mol, disodium phosphate Na2 HPO4 with 0.0016 mol, sodium chloride
( )
(NaCl) with 0.022 mol, and potassium chloride (KCl) of 0.00054 mol mixed in m Q water
(Shushama et al. 2017).
The surface plasmon wave (SPW) propagation constant is given by Eq. (3). It varies
with variations in SPR angle (Ngamchana and Surareungchai 2004).
2Π
kS = n sin 𝜃SPR (3)
𝜆 p
After this change in kS , i.e., SPW propagation constant the surface resonance frequency
also varies given by the mathematical relation (Rahman et al. 2017):
ks C
ΔSRF = ∗ 0 (4)
2Π nc
Here, n 0 is the SPW propagation velocity (Jorgenson and Yee 1993). The SPR sensor
C
c
performance parameters are sensitivity (S), full width half maximum (FWHM), detection
accuracy (DA) or signal to noise ratio (SNR), and figure of merit (FOM). The sensitivity
calculation in the angle interrogation method is the change in SPR angle with the change in
sensing layer RI, i.e., S = 𝛿𝜃SPR ∕𝛿nsm . The FWHM (𝜃SPR = 0.5), or spectral width is defined
as the span of the SPR curve at 50% of maximum reflected light intensity (Karki et al.
2021a). The Detection accuracy (DA) and FWHM are inverse of each other, i.e.,
FWHM = 1/DA. With the multiplication of sensitivity and DA, the figure of merit is being
calculated, i.e., FOM = S*DA. The output values for these parameters (S, DA, FOM)
should be high, and the value of FWHM should be minimum for better performance of bio-
sensors. These parameters are being summarized here in Table 1:
2.1 Experimental feasibility
The experimental setup bench used for our proposed formalin detection SPR sensor has
been shown in Fig. 2. The proposed optical system uses Krestchmann’s configuration fol-
lowing the ATR principle. The prism here made up of BK7 glass with RI 1.55. The input
source of light was He–Ne laser. This input wave was p-polarized after passing through
polarizer. The output device (photo detector) used to measure the intensity of the reflected
wave w.r.t the angle of incidence.
The fabrication process has been explained with the help of Fig. 3. The fabrication of
Ag, TiO2, Au, and BP layers, which are being utilized to make SPR chips, was first done.
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451 Page 6 of 15 B. Karki et al.
Soak the BK7 prism in acetone vapor, methanol, and de-ionized water. After that, it is
being connected to the Ag layer. The thermal evaporator system performs physical vapor
deposition of metal layers on the BK7 prism (Luna-Moreno et al. 2020). BP layer can be
made using a well-known chemical vapor deposition (CVD) procedure (Smith et al. 2016),
which can then be chemically transferred over a TiO2 nanosheet. After being manufactured,
these chips are placed on top of BK7 glass, and experimental findings are determined using
a sensor setup. For sensing, de-ionized water with bacteria and viruses as organic pollut-
ants is used. This mixture is also poured over an SPR sensor chip for biomolecule and
analyte detection. Now, to set the resonance angle, place the whole thing on the goniometer
with the rotary base. The input wave from a 633 nm He–Ne laser source is coupled to a
BK7 prism after passing through lens, polarizer, and collimator stages. The optical photo
detector detects the reflected light on the prism and outputs a signal proportional to the
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Titanium dioxide, black phosphorus and bimetallic layer‑based… Page 7 of 15 451
reflected light intensity. Computer software controls the input laser light with an angle of
incidence (θ) that focuses on the sensor’s surface. Finally, a reflectance curve graph can be
generated, allowing for comparison and analysis of experimental and simulation data.
This article gives information about simulated results observed during SPR sensor
designing to detect Formalin.
3.1 Detection of formalin
We used a chitosan probe to detect Formalin in the sensing media aqueous solution with
a sensing medium. The absorption of Formalin with chitosan is quite efficient (Jorgenson
and Yee 1993). In many research articles (Moznuzzaman et al. 2021; Nuasaen et al. 2013),
chitosan as a probe has been used. Its main features are biocompatibility, non-toxicity and
biodegradability, and high Formalin selectivity (Fen and Yunus 2011).
Table 2 indicates detection attributes after the inclusion of Formalin. The sensing layer’s
variation in concentration due to restraining chitosan, the sensing layer RI varies following
Eq. 2. Earlier, Eqs. 1 and 3 indicate a change in SPR angle with a change in ns and finally,
changing the value of kS.
Figure 4 gives a plot for reflectance and incidence angle for various detectionable tar-
gets for formalin detection. Initially, for 1000 nM concentration without Formalin and after
that for different concentrations of formalin due to chemical bonding reaction of the probe
with sensing target, the different
) SPR curves were obtained. The number of variations in
the parameters Rmin and 𝜃SPR after the inclusion of Formalin is given in Table 2. The data
(
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451 Page 8 of 15 B. Karki et al.
Fig. 5 Variation in reflectance with respect to incidence angle for different SPR sensor designs: a Ag-Au;
Δ𝜃 = 0.646, b Ag-Au-BP; Δ𝜃 = 0.748, c Ag-TiO2-Au; Δ𝜃 = 0.69, d Ag-TiO2-Au-BP; Δ𝜃 = 0.69
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Titanium dioxide, black phosphorus and bimetallic layer‑based… Page 9 of 15 451
Fig. 6 Optimized metal layers a for Ag, Minimum reflectance variations with incident angle, and b for Au,
Minimum reflectance variations with incident angle
Fig. 7 Reflectance as an incident angle function for BP and TiO2 based SPR biosensor with a single layer
of BP and variable layers of TiO2 b single layer of TiO2 and variable layers of BP
in the is inserted bi-metallic layer. With the thickness of T iO2 as T*2 nm, the sensitivity
goes down to 138 deg∕RIU . Finally, in Fig. 5d, for a single layer of TiO2 (T*2 nm) and BP
(B*1.8 nm), the sensitivity significantly ascends to 165.4 deg∕RIU . This study indicates
the impact of the addition of T iO2 and BP layer on the sensitivity of the proposed sen-
sor. The thickness of the TiO2 and BP are taken as zero. The Ag and Au layer’s optimized
thickness is 50 nm, and 5 nm is considered.
Figure 6a and b indicate the minimum reflectance values for different input incident
angles (55 to 90 degrees) for Ag thickness varying from (30 to 50 nm) as in Fig. 6a. In
the same manner, Fig. 6b shows the minimum reflectance and incident angle curves for
Au layer thickness varying from (1 to 5 nm). The next plots in Fig. 7 give different SPR
curves at variable RI for sensing medium from 1.34 to 1.36 with an alteration of 0.05. Two
different cases are considered during the analysis, firstly considering a single BP layer and
correspondingly varying the number of TiO2 layers (1 to 4); its impact on the minimum
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451 Page 10 of 15 B. Karki et al.
reflectance is observed for different incidence angles as in Fig. 7a. Next, Fig. 7b gives SPR
curves for a single TiO2 layer with variation in BP layers, and its impact is observed in the
same fashion as earlier on the minimum reflectance.
In Fig. 8, the sensitivity variation with the RI change of sensing medium. The RI of the
sensing medium varies from 1.33 to 1.35, with an increasing factor of 0.005. The curve
for single TiO2 and single BP layer (T = 1, B = 1) shows maximum sensitivity as 198.2
deg∕RIU compared to the conventional design curve (T = 0, B = 0) as 143.2 deg∕RIU.
The sensitivity parameter increases with the increase in RI of the sensing layer. The other
cases (T = 1, B = 0) and (T = 0, B = 1) show the sensitivity of 155.4 deg∕RIU and 171.8
deg∕RIU.
The sensitivity also depends on the number of the TiO2 and BP layers. When two lay-
ers of TiO2 and one layer of BP are considered, the maximum sensitivity of the sensor
327.6 deg/RIU is achieved (shown in the analysis of the current work with the earlier
works reported has been discussed with the help of Table 3.
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Titanium dioxide, black phosphorus and bimetallic layer‑based… Page 11 of 15 451
We find the sensitivity for the different combinations of layers for TiO2 and BP in Fig. 9.
We further investigated the sensitivity and FOM parameters alteration w.r.t the sensing
medium’s RI (with ΔRI = 0.005) shown in Fig. 10. As shown in this plot, the values of
FOM are very close to each other. The sensitivity values vary as 227.4, 249.6, 281.2, and
327.6 (in deg/RIU) for RI of 1.34 to 1.36, respectively.
Figure 11 shows the electric field distribution for a bimetallic layer of the BP layer. The
contact between BP and the sensing medium is a critical point where the level of electric
field intensity is maximum. Light intensity is the bare minimum at the interface between
BP and sensing media, and energy is converted from photonic to electromagnetic waves
(Chen and Lin 2019).
The table below, Table 3, motivates our research work as the sensitivity we achieve is
higher than the previous works reported. This SPR based Biosensor is highly sensitive
for analysis of formalin detection, diagnosis based on medical, chemical, and bio-mass
detection.
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4 Conclusion
A highly sensitive SPR based biosensor is proposed giving a sensitivity of 327.6 deg∕RIU .
This heterogeneous layered structure consists of a single Au and Ag layer with two lay-
iO2 and a BP layer. The Ag and Au layer’s thickness was first optimized, and the
ers of T
impact of layers of T iO2 and BP on the sensitivity was observed. The Ag and Au layers’
optimized thickness is 50 nm, and 5 nm has been considered. The proposed SPR sensor
design detects the presence of Formalin in the food preservatives, as it is very hazardous to
human health.
Authors’ contributions BK formulated the problem statement, giving the theoretical background and math-
ematical modeling for the SPR biosensor. He also helped in drafting and finalizing the manuscript. RKC
provided the theoretical background to biosensing and the importance of Optical Biosensing. He also helped
in finalizing the design of the proposed sensor. SDRS worked towards the complete manuscript, formatting,
and finalizing the manuscript. VS provided statistical analysis for the results. He provided the theoretical
background to SPR biosensors. He also helped in formatting the manuscript. AP worked towards revising
the manuscript and formatting design and finalization towards developing this work.
Declarations
Conflict of interest The author declares no conflict of interest.
Ethics approval Not applicable. The work presented in this manuscript is mathematical modeling only for
the proposed biosensor. No experiment was performed on the human body and living organism/ animal. So,
ethical approval from an ethical committee is not required.
Consent for publication The author has given their consent to publish this work.
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