Plasmonics

https://doi.org/10.1007/s11468-024-02432-z

RESEARCH

Sensitivity Enhancement of Franckeite‑Based Surface Plasmon

Resonance Sensors Using A Bimetallic Structure
Rajeev Kumar1 · Shivam Singh2 · Partha Sarkar3 · Lalit Garia4 · Varun Kumar Kakar4 · Abdullah Saad Alsubaie5 ·
Amrindra Pal6

Received: 25 May 2024 / Accepted: 15 July 2024

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2024

Abstract
This study proposes the franckeite layer onto a bimetallic (Au–Cu) based sensor. The proposed sensors use C­ aF2 prism, Au
(39 nm), Cu (5 nm), with/without franckeite, and adsorption layer (sensing medium (SM). All the performance analysis is
carried out at 633 nm wavelength. At optimized, the bimetallic layer, the remarkable sensitivity, DA, and FoM of 350.76°/
RIU, 0.144/°, and 50.50/RIU are achieved, respectively. The proposed sensor’s computed electric field (EF) intensity and
penetration depth (PD) are 2.11 × 105 V/m and 204.28 nm at an RI of 1.330 SM. With a quick response indicated by a
significant shift in resonance angle, the suggested structure would help detect the RI between 1.33 and 1.335. A detailed
comparison with the most recent publications in biomedical applications confirms the outstanding performance of the
proposed SPR sensors. This comparison highlights the significant potential of the sensors in biosensing and biomedicine.

Keywords Surface plasmon resonance · Sensitivity · Detection accuracy · Franckeite · Penetration depth

Introduction various applications, such as biological research, food safety,

environmental monitoring, gas detection, and biochemical
The remarkable sensitivity, quick response time, and real-time analysis [2, 4–8]. Other applications have been used for various
improvements in biosensor technology, particularly in surface disease detection by the demultiplexer, interferometer, coupler,
plasmon resonance (SPR)-based sensing, have increased and photonics [9–11]. SPR depends on optical stimulation to
biosensing applications’ popularity [1–3]. High sensitivity excite surface plasmon waves (SPW) at the metal-dielectric
and label-free detection make this method unique for interface. The interaction of photons and electrons on the

2
* Amrindra Pal Department of Electronics and Communication
[email protected] Engineering, ABES Engineering College, Ghaziabad,
Uttar Pradesh 201009, India
Rajeev Kumar
3
[email protected] Department of Electronics and Communication Engineering,
National Institute of Technology, Mahatma Gandhi Road,
Shivam Singh
Durgapur Pin 713209, West Bengal, India
[email protected]
4
Department of Electronics & Communication Engineering,
Partha Sarkar
B. T. Kumaon Institute of Technology, Dwarahat,
[email protected]
Uttarakhand 263653, India
Lalit Garia 5
Department of Physics, College of Khurma University
[email protected]
College, Taif University, Taif 21944, Saudi Arabia
Varun Kumar Kakar 6
Department of ECE, University Centre for Research
[email protected]
and Development, Chandigarh University,
Abdullah Saad Alsubaie Gharuan, Mohali 140413, India
[email protected]
1
Department of Electronics and Communication Engineering,
Graphic Era Deemed to be University, Dehradun,
Uttarakhand 248001, India

Vol.:(0123456789)
Plasmonics

metal surface drives this process, which creates an electric 0.7 eV. Gan et al. [34] designed an SPR sensor based on
field (EF) that decays exponentially in both the metal and franckeite by combining graphene and Ag layers. Maximum
the dielectric medium. Binding events can be precisely sensitivity, up to 188°/RIU, has been obtained with the
detected to the sensitivity of SPR sensors with variations proposed structure. Karki et al. [28] proposed the malaria
in the refractive index (RI) of sensing mediums (SM). The detection-based SPR sensor, which exhibits a maximum
p-polarized light incident on the prism and a metallic layer sensitivity of 227.9°/RIU. Yesudasu et al. [35] presented an
generates surface plasmon waves (SPW), also known as SPR sensor using franckeite, barium titanium ­(BaTiO3), and
surface plasmon polaritons (SPP) or surface plasmons (SP). BP with a significant sensitivity increase. The maximum
The SPWs propagate along the metal-dielectric interface. In sensitivity of 331.54°/RIU is attained at an optimized metal
addition to incident light at the SPR angle, the surface plasmon layer thickness. Kumar et al. [36] discussed the leptospirosis
wave vector and evanescent wave vector must match to observe bacteria detection-based SPR sensor with the highest
the SPR condition [12, 13]. Prism-based and optical fiber- sensitivity of 214.51°/RIU.
based SPR sensors are frequently employed; however, due to
their practicality, prism-based designs such as Kretschmann
geometry are recommended [14–16]. The selection of metal, Device Modeling, Refractive Index,
like Au or Ag, affects the sensor’s performance; Au offers and Performance Evaluation Parameter
lower oxidation but lower sensitivity than Ag, which is more
sensitive but more oxidation-prone [17–20]. Bimetallic The proposed SPR sensor includes ­CaF2/Au/Cu/Franckeite/
coatings can increase the stability of metal. To improve sensor SM in a Kretschmann configuration, as shown in Fig. 1.
performance, recent developments in biosensor technology Prism coupling is the base in the Kretschmann configura-
have used graphene and transition metal dichalcogenides tion-based proposed structure, which operates through an
(TMDCs) as biorecognition elements [21]. With its high angular interrogation method. This method analyzes the
surface-to-volume ratio and tunable characteristics, graphene reflectance (R) of the incident angle at a fixed wavelength
shows promise for biosensing applications [14, 15, 22–25]. of 633 nm. The performance parameter values calculated
Graphene and TMDC-based heterostructures can be highly by the SPR sensor that has been described are a multilayer
sensitive [26, 27]. Still, naturally occurring layered minerals stacking ­CaF2 prism and a monochromatic laser source (He-
such as franckeite offer Vander Waal (VDW) superlattices Ne laser), as illustrated in Fig. 1.
free of surface impurities, which makes them appealing for The reflectance can be calculated with the N-layer model
sensor development [28–31]. With its narrow energy band gap for the p-polarized light is expressed as follows [37–39]:
and stable crystalline structure, franckeite exhibits promise
as a graphene [26, 32], MXene [33], and black phosphorus | |2
R = |rp | (1)
| |
substitute material in optoelectronic devices. A franckeite-
based surface plasmon resonance sensor with high sensitivity The reflection coefficient rp is expressed as
has been obtained. The two-dimensional p-type property of ( ) ( )
franckeite allows it to be mechanically exfoliated into layers. m11 + m12 qn q1 − m21 + m22 qn
rp = ( ) ( ) (2)
Franckeite is a promising substitute for graphene and black m11 + m12 qn q1 + m21 + m22 qn
phosphorus, with a similarly narrow band gap of less than

Fig. 1  Proposed sensor Display

Sensing medium
Reflectance (a.u.)

Molecules
Franckeite layer
Copper (Cu) layer Angle ()
Gold (Au) layer
Laser P1 CaF2 prism
Source L1 L4 Detector
L2 P2

L3

Rotary

L1, L2, L3, L4 -Lens P1, P2 - Polarizer

Plasmonics

with The detection accuracy (DA) depends on the full width at

[ ] half maximum (FWHM) because they are inversely propor-
+ ∏N−1 m11 m12
M= m = (3) tional to each other. The FWHM depends on the width reflec-
k=2 k m21 m22 tance curve. The reflectance width is measured at 50% of the
reflection intensity. The DA is expressed as Eq. (8).
where,
[ ( ) ] 1
cos βk ) −i sin βk ∕qk DA = (∕◦ ) (8)
mk = (
−iqk sin βk cos βk (4) FWHM
Moreover, the product of sensitivity and DA is known as
here, the figure of merit (FoM) and is expressed as Eq. (9).
√
√ εk − n21 sin2 𝜃1 FoM = DA ∗ S(∕RIU) (9)
μk (5)
qk = cos θk =
εk εk All performance parameters are determined by the MAT-
LAB and COMSOL software.
and
( ) 2πdk √
2π
βk = nk cos θk zk − zk−1 = εk − n21 sin2 𝜃1 (6) Result Analysis
λ λ
Here, k varies from 2 to N-1, and nk is the RI of the kth First, a study has been single (structure: ­CaF2/Au/SM) and
layer, while dk is the layer’s thickness. The first and Nth lay- bimetal (structure: ­CaF2/Au/Cu/SM) layer is optimized to get
ers are layered with C ­ aF2 prisms and the SM, which meas- the minimum reflectance (Rmin) value, which maximizes the
ures the RI between 1.33 and 1.335 SM. The incident angle structure’s SPs excitation, was necessary to achieve this. For
is indicated by θ1, while the wavelength of light excitation the single metal layer, Fig. 2a shows the sensitivity and Rmin
is indicated by λ. variation regarding the optimal thickness of the Au layer. The
We have utilized the ­CaF2 prism with low RI for the coupling minimum reflectance is displayed at both RI of 1.33 and 1.335
device. The RI of the ­CaF2 prism is 1.4329 [40]. Next, the Au SM. The sensitivity variation from 61.42°/RIU to 365.05°/
layer generates the plasmon with an optimized 20–60 nm thick- RIU at a particular thickness decreases to 330.25°/RIU. The
ness and RI of 0.1378 + 3.6196i [41]. Next, the Cu layer is uti- highest sensitivity of 365.20/°/RIU is attained at a remarkable
lized to enhance the sensitivity with a thickness of 1 to 5 nm and minimum reflectance (i.e., Rmin = 0.25 a.u. at 1.335 SM). The
having RI of 0.0369 + 4.5393i [41]. Next, the franckeite layer is minimum reflectance is firstly decreased at a particular thick-
used to the prone to oxidation from the Cu layer with a thickness ness and then increased for both SM, as shown in Fig. 2a. The
of 1.8 nm and having RI of 3.53 + 0.39i [34, 35]. For the detec- reflectance curve is plotted at the lowest Rmin value as shown in
tion of molecules, we have used the RI of SM 1.33–1.335 [41]. Fig. 2b. The resonance angle of 82.53° to 84.22° is shifted. The
The sensitivity (S) is needed for the best performance change in resonance angle of 1.695° is achieved. At the same
of an SPR sensor. The change in resonance angle (Δθres) to resonance angle, the sensitivity, DA, and FoM of 339.19°/RIU,
the change in RI of SM (Δns) is known as sensitivity and is 0.154/°, and 52.23/RIU are attained, respectively.
defined as Eq. (7): Further, the bimetallic structure shows the sensitivity and
Δθres ◦ Rmin regarding the optimal thickness Au (25–60 nm) layer at
S= ( ∕RIU) (7) a fixed thickness of Cu (5 nm) layer as depicted in Fig. 3(a).
Δns

Fig. 2  Structure: ­CaF2/Au/SM

SPR sensor a sensitivity and
Rmin vs variation in Au thick-
ness and b reflectance curve at
maximum sensitivity at below
0.1 (a.u.) Rmin value
Plasmonics

Fig. 3  Structure: ­CaF2/Au/Cu/

SM SPR sensor a sensitivity
and Rmin vs variation in Au
thickness and b reflectance
curve at maximum sensitivity at
below 0.1 (a.u.) Rmin value

Show the Rmin at both RI of 1.33 and 1.335 SM. The change 59.70°/RIU to 321°/RIU (after that decrease up to 23.83°/
in sensitivity from 178.99°/RIU to 293.46°/RIU is achieved. RIU at 42 nm thickness of Au layer), 60.50°/RIU to 337.70°/
The Rmin value decreases first and then increases. The low- RIU (after that decrease up to 25.43°/RIU at 50 nm thick-
est Rmin is at 45 nm of Au layer with 5 nm thickness of Cu ness of Au layer), and 183.46°/RIU to 350.76°/RIU(after
layer. At remarkable Rmin, the reflectance curve is shown in that decrease up to 252.10°/RIU at 50 nm thickness of Au
Fig. 3b. The resonance angle is shifted from 79.59° (at RI layer) with 0 nm, 1 nm, 3 nm and 5 nm thickness of Cu layer,
1.33) to 80.90° (at RI 1.335). The difference between two respectively shown in Fig. 4a. The maximum sensitivity is
resonance angles of 1.40° is obtained. At the same resonance achieved at 5 nm Cu thickness at optimum Au thickness,
angle, the sensitivity, DA, and FoM of 261.26°/RIU, 0.277/°, and next, the Rmin is plotted at an optimum thickness of the
and 72.36/RIU are attained, respectively. Au layer with both RI of SM (1.33 and 1.335) as depicted in
Due to oxidation problems, the franckeite layer is utilized Fig. 4b and c. The Rmin first decreases at a particular thick-
onto a bimetal layer, affecting the sensor’s sensitivity. At ness and then increases. The lowest Rmin was obtained at
optimal thickness (25–50 nm) of the Au layer, the variation 35 nm, 35 nm, 36 nm, and 36 nm thickness of the Au layer
in sensitivity from 59.47°/RIU to 310.54°/RIU (after that and 0 nm, 1 nm, 3 nm, and 5 nm thickness of the Cu layer
decrease up to 36.55°/RIU at 39 nm thickness of Au layer), with franckeite layer.

Fig. 4  Proposed (structure:

­CaF2/Au/Cu/Franckeite/SM)
SPR sensor a sensitivity vs Au
thickness, b Rmin (at ns = 1.330)
vs variation in Au thickness,
and c Rmin (at ns = 1.335) vs
variation in Au thickness at
various thickness of Cu layer

0.8
(c)
Rmin at ns = 1.335
0.7
Min. reflectance, Rmin (a.u.)

Cu thickness
0.6 0nm
1nm
0.5 3nm
5nm
0.4
0.3
0.2
0.1
0.0
20 25 30 35 40 45 50
Au thickness (nm)
Plasmonics

Fig. 5  Reflectance curve vs

incident angle at maximum
sensitivity below 0.1 (a.u.) Rmin
value of a structure: ­CaF2/Au/
Franckeite/SM, b structure:
­CaF2/Au/Cu(1 nm)/Franckeite/
SM, c structure: ­CaF2/Au/
Cu(3 nm)/Franckeite/SM, and
d structure: C
­ aF2/Au/Cu(5 nm)/
Franckeite/SM

Furthermore, Fig. 5 shows the reflectance curve at vary- Au(39 nm)/Cu (5 nm)/Franckeite/SM, respectively. It is
ing layers of 0 nm, 1 nm, 3 nm, and 5 nm Cu thickness observed that the sensitivity increases then increases the RI
at an optimum Au layer thickness with franckeite layer for of SM. The Rmin is displayed in graphical representation as
the change RI of SM 1.33 and 1.335. Figure 5a shows the depicted in Fig. 6b. The Rmin is also increased then increased
sensitivity, DA, and FoM of 310.54°/RIU,0.313/°, and FoM RI of SM. Figure 6c shows the DA value with various struc-
35.09/RIU w/o Cu layer. The change in resonance angle tures. The DA also decreases and then increases the RI of SM.
(Δθres) is 1.552°. Next, the sensitivity is improved using The maximum FoM is achieved using this structure C ­ aF2/Au
the Cu layer between the Au and franckeite layer, as shown (46 nm)/Cu (5 nm)/SM, as shown in Fig. 6d. It is noted that
in Fig. 5b. The sensitivity, DA, and FoM of 321.54°/RIU, as the RI of SM, the FoM increases for all structures.
0.116/° and FoM 37.29/RIU with 1 nm Cu thickness. The Perform the numerical analysis of the proposed structure
Δθres is 1.72° with remarkable Rmin. Figure 5c shows the using the finite element method (FEM) based on COM-
reflectance curve at 3 nm thickness of the Cu layer. Simi- SOL Multiphysics. Figure 7a shows the normalized elec-
larly, Fig. 5d shows the sensitivity, DA, and FoM of 337.70°/ tric field (EF) of the proposed sensor. The EF is increased
RIU,0.121/°, and FoM 40.86/RIU 3-nm Cu layer with from the Au layer to the franckeite layer after that decay in
franckeite layer. The Δθres is 1.688°. Furthermore, the reflec- exponential nature. The maximum field is obtained from
tance curve at maximum sensitivity with 5 nm Cu thick- the interface between the franckeite and the SM layer. The
ness is depicted in Fig. 5d. The sensitivity, DA, and FoM of normalized EF (i.e., 1D plot) is plotted at RI of SM 1.330.
350.76°/RIU, 0.0.144/° and FoM 50.50/RIU 5 nm Cu layer The maximum field of 2.11 × ­105 V/m is achieved. The dis-
with franckeite layer. The Δθres is 1.75°. It is observed that tance between the metal surfaces where surface plasmons
by increasing the Cu thickness, the Δθres is increased. are excited to the region where the evanescent field decays to
Figure 6 depicts the performance parameters like sensitiv- about 1/e (approximately 37%) of its maximum EF intensity
ity, Rmin, DA, and FoM about SM’s RI changes with vari- is known as the PD in an SPR sensor. The PD of 204.28 nm
ous structures. In Fig. 6a, the sensitivity variation is from is achieved. The enlarged picture in Fig. 7a clearly illustrates
307.67°/RIU to 339.19°/RIU, 242.93°/RIU to 261.26°/RIU the normalized EF inside the Cu-franckeite and SM layers of
and 330.02°/RIU to 350.76°/RIU with structure of ­CaF2/ the proposed sensor. The excited SPWs are shown in Fig. 7b
Au(45 nm)/SM, ­CaF2/Au(46 nm)/Cu (5 nm)/SM and ­CaF2/ (2D plot) and c (3D plot) at an angle of θ = 83.48°.
Plasmonics

Fig. 6  Performance parameters (a) 0.10

vs change RI of SM at various (b)
structures: a sensitivity, b Rmin, 350 Proposed structure
c DA, and d FoM CaF2/Au(46nm)/Cu(5nm)/SM

Sensitivity (/RIU)
CaF2/Au(45nm)/SM

Rmin (a.u.)
300 Proposed structure
0.05
CaF2/Au(46nm)/Cu(5nm)/SM
CaF2/Au(45nm)/SM

250

0.00
1.33 1.331 1.332 1.333 1.334 1.335 1.33 1.331 1.332 1.333 1.334 1.335
Change RI of SM Change RI of SM

Fabrication Process thin layer of Cu is deposited on top of the Au layer using the
PVD technique. This method ensures a high-purity and uni-
The fabrication process of the proposed sensor is shown in form Cu layer. The deposition parameters are carefully con-
Fig. 8. The ­CaF2 prism serves as the substrate for the sensor trolled to achieve the desired thickness. Next, the complex
to provide the best possible light transmission. Before being layered mineral franckeite is prepared through mechanical
rinsed with deionized water and dried under nitrogen gas, the exfoliation. Using adhesive tape, a bulk franckeite sample
substrate is meticulously cleaned using a piranha solution, a is transformed into small flakes, which are placed on the Cu
mixture of sulfuric acid and hydrogen peroxide, to remove layer using the chemical vapor deposition (CVD) technique.
any organic contaminants. A thin layer of Au is deposited Therefore, we choose an operating wavelength of 633 nm,
onto the cleaned ­CaF2 prism substrate using a sputtering considering all refractive index (RI) values for each material
technique or physical vapor deposition (PVD). Sputtering is at this wavelength. The changes in RI that occur when the
chosen for its ability to produce a uniform and smooth layer sensor is exposed to a sample that contains the analyte of
of Au. The thickness of the Au layer is precisely controlled various molecules are detected by either intensity shifts or
by adjusting the deposition time and power settings. Next, a resonance angles.

Fig. 7  a Normalized electric

field inside layers, b 2D SPP
mode, and c 3D SPP mode
Plasmonics

Cu layer Author Contribution Rajeev Kumar: Conceptualization, Simulation,

Au layer
CaF2 prism Writing – original draft, Shivam Singh: Formal analysis, Writing –
original draft Partha Sarkar: Design, Modeling, Formal analysis, response
PVD PVD to reviewer comments Lalit Garia: Formal analysis, Writing – original
draft, Varun Kumar Kakar: Formal analysis, Writing – original draft,
(i) (ii) (iii) Abdullah Saad Alsubaie: Formal analysis, Writing – original draft,
Sensing medium CVD response to reviewer comments Amrindra Pal: Supervision, Formal
Analysis.
Sensor Chip
Franckeite layer
Funding This research was funded by Taif University, Saudi Arabia,
Project No. (TU-DSPP-2024-106).

Availability of Data and Material No datasets were generated or ana-

(vi) (v) (iv) lysed during the current study.

Declarations
Fig. 8  Fabrication process
Consent for Publication The authors of this draft express their consent
to publish this theoretical research.
Table 1  Comparison of the proposed work with existing published
papers based on SPR sensor Consent to Participate No consent is required.

Structure S (°/RIU) Year Competing Interests The authors declare no competing interests.

Gan et al. [34] 188 2019

Disclaimer This manuscript has yet to be published and is not even
Karki et al. [28] 227.9 2024
under consideration for publication elsewhere.
Yesudasu et al. [35] 331.54 2024
Kumar et al. [36] 214.51 2024
Present work 350.76 2024
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