Results in Physics 13 (2019) 102320

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Sensitivity enhancement of surface plasmon resonance sensors with 2D T

franckeite nanosheets
⁎
Shuaiwen Gan, Yuting Zhao, Xiaoyu Dai , Yuanjiang Xiang
International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology of Ministry of Education, Key Laboratory of Optoelectronic Devices and
Systems of Ministry of Education and Guangdong Province, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China

A R T I C LE I N FO A B S T R A C T

Keywords: As a latest novel two-dimensional (2D) material with naturally occurring van der Waals heterostructure,
Franckeite franckeite has the unique advantages compared with the artificial stacking heterostructures. Herein, we propose
van der Waals heterostructure a surface plasmon resonance (SPR) sensor with 2D franckeite nanosheets to improve the sensitivity. In this
Sensor structure, franckeite is covered on the surface of 50 nm silver film, so that the SPR sensitivity is related to the
Surface plasmon resonance
thickness of the franckeite overlayer. The sensitivity as high as 188 °/RIU in theory has been obtained, which is a
62% increasing compared with the conventional SPR biosensor. Moreover, an additional film of graphene is
considered for the virtue of bio-compatible, and the sensitivity of the franckeite-graphene heterostructures is
furthermore improved. As an air-stable 2D material, we believe that 2D franckeite nanosheets could have po-
tential applications in the field of chemical and biological sensors in the future.

Introduction biosensors have been actively explored in recent years [14–16].

Surface plasmon refers to the electron-dense wave that propagates
along the metal surface by the interaction of freely vibrating electrons
and photons on the metal surface [1,2]. Surface plasmon waves (SPW)
are generally stimulated through prism coupler in the Otto geometry or
Kretschmann geometry [3,4]. When the wave vector of SPW well-
matches with the evanescent wave vector, the phenomenon of surface
plasmon resonance (SPR) occurs [5]. SPR may exist on the interface of
two kinds of media with dielectric constants of opposite signs, such as
the dielectric and metal. Moreover, SPW is the transverse magnetically
(TM) polarization wave (the magnetic vector is perpendicular to the
propagation direction of the wave and parallel to the interface plane)
[5,6]. Since most of the field of the SPW is focused on the dielectric, the
SPW propagation constant is very sensitive to changes in the refractive
index (RI) of the surrounding environment [7]. Based on this, the SPR
sensor, a combination of modern physics, biology, and sensing tech-
nology, has achieved a series of developments [8,9]. SPR sensor is an
effective means to study the interaction of biological macromolecules,
nowadays, it has brought forward widespread applications in chemical,
environmental monitoring, food safety, biological analysis [10–13] and
other fields because of its outstanding advantages, such as real-time
analysis, high reliability, and high sensitivity. In order to achieve higher
sensitivity and lower limit of detection, different designs of SPR
Wide applications of two-dimensional (2D) materials have brought
great convenience to many complex devices [17–21]. Furthermore,
researchers have begun to study sensors based on the van der Waals
(VDW) heterostructures [22], which are formed by artificially stacking
different 2D materials in selected order. Such as, Wu et al. proposed a
SPR biosensor by using few-layer black phosphorus-graphene/TMDCs
heterostructure with sensitivity as high as 217∘/RIU [23]. Qin et al.
designed a highly sensitivity sensor based on magneto-optical SPR in
Ag/CeYIG heterostructure [24]. But actually, the VDW heterostructures
is difficult to control the lattice orientations and may have unwanted
atmospheric adsorbates between the layers [25]. Unlike this, franckeite
is a 2D material and from the sulfosalt family with spontaneously oc-
curring VDW heterostructure, incommensurately stacked PbS-like and
SnS2-like layers separated by van der Waals gaps (PbS-SnS2) [26–28]. In
recently, Velický et al. obtained the single layer heterostructure
(thickness about 1.8 nm) by mechanical and liquid-phase exfoliation of
franckeite [29], which facilitates our theoretical analysis. Franckeite is
a p-type doping material, which is a very rare feature in 2D semi-
conductors. Moreover, franckeite is air-stable and has a below 0.7 eV
narrow band gap. These characteristics make franckeite a great alter-
native to black phosphorus, although there are little studies on
franckeite, it is considered to have great potential in optoelectronic
devices [30–32].

⁎
Corresponding author.
E-mail address: xiaoyudai@126.com (X. Dai).

https://doi.org/10.1016/j.rinp.2019.102320
Received 18 April 2019; Received in revised form 28 April 2019; Accepted 29 April 2019
Available online 08 May 2019
2211-3797/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
S. Gan, et al. Results in Physics 13 (2019) 102320

Fig. 1. The proposed SPR sensor for (a) by using a natural VDW heterostructure of franckeite to enhance the sensitivity; (b) measured refractive index of franckeite (n
is the real part and k is the imaginary part) with wavelength from 450 nm to 750 nm [27].

In this paper, we demonstrate that the franckeite cover on the sur- where rp represents the reflection coefficient, and:
face of Ag film can improve the sensitivity, and we also discussed in
(M11 + M12 qN )q1 − (M21 + M22 qN )
detail the influence of franckeite film with different layers on the re- rP = ,
(M11 + M11 qN )qN + (M21 + M22 qN ) (4)
fractive index of sensing medium. We obtain the highest sensitivity
with188°/RIU, which means an increase of 62% in sensitivity compared N
M M12 ⎤
to the conventional SPR sensor. Besides, we have discussed the per- M= ∏ Mj = ⎡ M11 M22 ⎦
.
formance of the proposed biosensor, including the sensitivity and figure j=2 ⎣ 21
(5)
of merit (FOM). We have also analyzed the origin for the increasing
Here Mj is given by
sensitivity by analyzing the electric field distributions.
⎡ cosβj − isinβj/qj ⎤
Design consideration and theoretical model Mj = ⎢ ,
− iqjsinβj cosβj ⎥ (6)
⎣ ⎦
The proposed SPR sensor was shown in Fig. 1(a). Obviously, it’s a with
typical Kretschmann configuration. In this structure, the wavelength of
the incident TM polarized light is 633 nm. Chalcogenide (2S2G), BK7, 2π dj
βj = (εj − n12sin2θ1)1/2 ,
or SF10 can be chosen as the coupling prism, in this article, BK7 glass is λ (7)
chosen, the refractive index can be computed by the following formula and
[33]:
(εj − n12sin2θ1)1/2
nBK 7 qj = .
εj (8)
1.03961212λ2 0.231792344λ2 1.01046945λ2
= 1+ + + where θ1 is the angle of incidence at the base of BK7 glass, j represents
λ2 − 0.00600069867 λ2 − 0.0200179144 λ2 − 103.560653
the j th layer of the N-layer model, dj, nj and εjare defined as the
(1)
thickness, refractive index and dielectric constant of each layer, re-
The wavelength (λ ) in the relation is measured in micron ( μm) , and spectively. In the curve of angle-dependent reflectivity, the resonance
we can easily calculated that nBK7 = 1.5151at λ = 633 nm. angle, corresponding to the minimum reflection intensity, will change a
Silver (Ag) is coated on the surface of glass, the refractive index is little (Δθ) due to the minor changes of refractive index of sensing region
[23]: (Δn) . SPR sensors have two main performance parameters: sensitivity
(S) and figure of merit (FOM), which are defined as S = Δθ /Δn (°/RIU)
λ c λ2
nm = 1− and FOM = S/FWHM (1/RIU) , where FWHM is the full width of the
λ p2 (λ c + iλ ) (2) reflectivity graph corresponding to the half maxima [31].
where wavelength (λ ) is also measured in micron, λ c = 17.614μm and
λ p = 0.14541μm is the collision wavelength and the wavelength for the Results and discussions
bulk plasma frequency, respectively.
Then, a natural VDW heterostructure of franckeite is covered on the BK7 as the coupling prism with low refractive index can provide a
surface of Ag film to improve the sensitivity. Franckeite is very stable in relatively high sensitivity [34]. Ag film with thickness of 50 nm is
its natural condition, which is a very rare feature in 2D semiconductors. coated on the surface of prism, for this thickness we can get a deep SPR
Fig. 1(b) shows the refractive index (real part n and imaginary part k) of curve, which usually means a higher FOM. We choose 5.4 nm (3 layers)
franckeite with 1.8 nm thickness in the visible range from the experi- of franckeite to cover on the Ag film and Fig. 2(a) has shown the SPR
mental measurement [27], and the refractive index 3.53 + 0.39i for curve of the structure when ns = 1.33 and ns = 1.335. From the result,
λ = 633nm can be obtained. The refractive index of sensing medium we can find that the resonance angle is shifted about 0.94°, compared
can be given as ns = 1.330 + Δn , where Δn is assumed to be a change with the traditional structures as shown in Fig. 2(b), the shifted re-
of refractive index in the solution caused by biological or chemical sonance angle Δθ is increased by 62%, this also means a 62% increase in
reactions. sensitivity. The FWHM are 5.01° in Fig. 2(a) and 1.28° in Fig. 2(b) at
For calculating the reflection intensity of the TM-polarized light of ns = 1.330.
the configuration, we employ the N-layer transfer matrix method [34], Then, we analyzed the effect of franckeite thickness (d = 1.8nm × L ,
the reflectivity can be expressed as: where L is the layers of franckeite, d is the thickness) on sensitivity and
FOM. Fig. 3(a) has shown the changing of sensitivity and FOM with the
R = |rp|2 (3) number of franckeite layers, where the first coordinate point means a

2
S. Gan, et al. Results in Physics 13 (2019) 102320

Fig. 2. The curve of reflectivity with incident angle for (a) the sensitivity-enhanced structure by using 3 layers (about 5.4 nm) of franckeite, S = 188° /RIU and (b)
the conventional configuration biosensor based on single Ag film with S = 116° /RIU .

Fig. 3. (a) Sensitivity is proportional to the layers of franckeite and FOM decreases gradually when the number of layers changes from 0 to 3. (b)The changing of
reflectance with incident angle in different layers of franckeite (from 1 to 4) as the ns = 1.33.

Fig. 4. (a-b) The diagrammatic model for analysis the enhancement of the sensitivity. (c) The changing of reflectance with incident angle for different refractive
index of sensing medium and (d) the corresponding electric-field distribution (E0 is the electric field of incident light).

conventional configuration, the corresponding sensitivity
S = 116°/RIUandFOM = 90.3/RIU . As we can see, when use three
layers (about 5.4 nm) franckeite, the sensitivity as high as188°/RIU ,
and the corresponding FOM is37.6/RIU . Fig. 3(b) has shown the var-
iation of reflectivity with respect to the angle of incidence in different
thickness of franckeite when ns = 1.330. We can found that the
minimum reflectivity corresponding to the resonance angle is gradually
increased with the thickness of franckeite. The figures may lead us to
the conclusion that the minimum reflectivity will be over than 0.5 while
the refractive index of the surrounding medium is greater than 1.330
for L = 4 or more.
In order to analyze the enhancement of the sensitivity, we use a
diagrammatic model as shown in Fig. 4. In Fig. 4(a), the angle of in-
cident light in the prism (np ) is θp , and in an additional dielectric
medium (n1), the refraction angle is θ1, then we obtain npsinθp = n1sinθ1
according to Snell’s law. Then in Fig. 4(b), we find that a high refractive
index dielectric (n2 ) is clamped between the glass (np ) and dielectric
medium (n1), here n1 < n eff < n2 with n eff = n1 + Δn . The incident
angle is θp + Δθ , then we have npsin(θp+Δθ)=n eff sinθ1=(n1+Δn)sinθ1,
hence the increase of Δn will cause a change of Δθ , this means an extra
film with relatively high refractive index may enhance the sensitivity.
In addition, we have also analyzed the electric field distribution.

3
S. Gan, et al.
Fig. 5. (a) The changing of reflectance with incident angle in different layer of graphene. (b) The reflectance curve of the structure by use 2 layers of graphene in
different refractive index of sensing medium.
Fig. 6. (a) The changing of sensitivity with the different layer of graphene. (b) The reflectance curve of the structure by use 2 layers of graphene and (c) the changing
of sensitivity with the different refracture index of surrounding medium.
Fig. 4(c) has shown the changing of reflectance for ns = 1.33,
ns = 1.34, ns = 1.35 and ns = 1.36 respectively, from it we can find
that the resonance angle are 75.585°, 77.515°, 79.675° and 82.025°,
respectively. A narrow band gap will enhance the electric field and
result a high sensitivity [35], as shown in Fig. 4(d). It is found that in
the interface of franckeite/sensing medium, the electric intensity
reached the maximum for 20.73, 23.01, 25.97 and 29.28 corresponding
to a small change of ns from 1.33 to 1.36. This means an electric field
enhancement more than 20 times on the interface of franckeite and
semsing medium.
Graphene is a 2D carbon nanomaterial with the virtue of bio-com-
patible and other outstanding performance, which has potential fields
of use in energy, biomedicine, materials science and micro-nano pro-
cessing, etc [36]. We have also considered the heterostructure by cov-
ering graphene on the surface of franckeite (5.4 nm thickness). The
refractive index of graphene is ng = 3.0 + 1.149i and the single layer
thickness is 0.34 nm [37]. Fig. 5(a) has shown the variation of re-
flectivity with respect to the angle of incidence for the different layers
of grapheme (N). From the figure, we can found that the reflectivity
corresponding to the resonance angle is gradually increased with the
increasing layers of graphene from N = 1 to N = 5 due to the increasing
absorption. Fig. 5(b) has shown the changing of reflectance for
ns = 1.33, ns = 1.34, ns = 1.35 and ns = 1.36 for two layers of gra-
phene, and the resonance angles are 76.845°, 78.84°, 80.94° and
82.815° respectively. Fig. 6(a) has illustrated the changing of sensitivity
with the different layer of graphene, we can see that the sensitivity can
reach the highest (196°/RIU ) when use two layers of graphene. In
Fig. 6(b) we have shown the reflectance curve of the structure by using
two layers of graphene for ns = 1.33 and ns = 1.335. From it, we can
obtain that Δθ = 0.98°, S = 196°/RIU and FOM = 40.29/RIU . Then in
Fig. 6(c) we have shown the sensitivity at different refractive index of
surrounding medium by using two layers of graphene, we can find that
the sensitivity has over 126°/RIU when n s in the range of 1.33–1.36.
4
Results in Physics 13 (2019) 102320
Conclusions
A SPR sensor by using a natural VDW heterostructure of franckeite
to improve the sensitivity is put forward. In the configuration, franck-
eite is covered on a surface of Ag layer with 50 nm thickness. We
considered the effect of thickness of franckeite on sensitivity, and the
result shows that the sensitivity as high as188°/RIU with 5.4 nm
thickness (about 3 layers) can be obtained, which also means a 62%
increase compared with the conventional SPR biosensor in theoretical
simulations. Moreover, an additional film of graphene is coated on the
surface of franckeite for considering the virtue of bio-compatible, the
sensitivity can be slightly enhanced with196°/RIU and FOM with
40.29/RIU have been obtained for two layers of graphene. As an air-
stable 2D material, we believe that the SPR sensor with franckeite could
have potential applications in the field of chemical and biological
sensors in the future.
Acknowledgements
This work is partially supported by the National Natural Science
Foundation of China (Grant Nos. 61875133 and 11874269), the China
Postdoctoral Science Foundation (Grant Nos. 2017M622746 and
2018M633129), and the Guangdong Natural Science Foundation (Grant
No. 2018A030313198).
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