Chemical Physics 535 (2020) 110785

Contents lists available at ScienceDirect

Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Simulation of light transmission through core-shell heterostructure nano- T

materials
Yunzhen Yina, Yanyan Bub, , Xiangfu Wanga,c,d,
⁎ ⁎

a
College of Electronic and Optical Engineering & College of Microelectronics, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
b
College of Science, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
c
National Electronic Science and Technology Experimental Teaching Demonstrating Center, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
d
National Information and Electronic Technology Virtual Simulation Experiment Teaching Center, Nanjing University of Posts and Telecommunications, Nanjing 210023,
China

ARTICLE INFO ABSTRACT

Keywords: Even though the core–shell nanomaterials were reported as the most efficient up-conversion materials to achieve
Core-shell the energy migration, the light transmission mechanism in core-shell heterostructure and the energy loss induced
Admittance recursive method by multilayer shells have not been studied. In this work, we report the admittance recursive method to simulate
Light transmission the transmission process of TE and TM waves and calculate the light transmission efficiency in core-shell het-
erostructure. The effects of multilayer shell thickness, wavelength of transmitted light, and critical angle on the
light transmittance of core-shell nanoparticles (NPs) are studied. It is found that the TE wave transmission
efficiency from NaYF4@SiO2 core-shell heterostructure can reach more than 96.4%, while the values of trans-
mission efficiency of TE and TM waves are less than 40% in NaYF4@SiO2@Ag core-shell-shell heterostructure.
Only 1540 nm and 980 nm infrared lights transmit from the NaYF4@Ag@SiO2@Ag multilayer shell hetero-
structure.

1. Introduction
Recently, the β-NaYF4 was reported to be one of the most effective
up-conversion host materials due to the low phonon energy of the
crystal lattices [1–5]. In order to enhance the emission efficiency of rare
earth ions doped NaYF4, the core-shell nanostructures based on β-
NaYF4 core [6–12], such as NaYF4@Ag, NaYF4@Au, NaYF4@TiO2,
NaYF4@ SiO2, NaYF4@CaF2, NaYF4@SiO2@Ag, NaYF4@SiO2@Au, and
NaYF4@SiO2@ TiO2, were designed to achieve the energy migration
mediated up-conversion for applications in biomedical [13–15], pho-
tocatalysis [16–19] and solar energy conversion [11,20–22]. Compared
with the bulk materials, the core–shell structure showed intense lumi-
nescence intensity such that the shells protected the active centers in
the core from the annihilation of the surrounding environment [23].
Current researches on the core–shell nanostructures were focused on
up-conversion intensity enhancement [7,24,25], through optimizing
the dopant concentration, controlling the distribution of active ions in
the host material, and modifying the composition, structure and mor-
phology of the upper layer [26,27]. However, few researches have
addressed the transmission process of TE and TM waves, and how much
light lost induced by the shells during the emission process, because
modern measuring instruments can only measure the emission intensity
outside the nanostructures and cannot measure the energy distribution
of the light inside the shells. Thus, the transmission mechanism of TE
and TM waves in core–shell heterostructure is necessary to be explored,
and the energy loss induced by multilayer shells need to be calculated
accurately.
In order to understand the transmission mechanism of light in the
core–shell structure, it is necessary to explore an effective method to
accurately simulate the light transmission process in core–shell nanos-
tructures. When the light propagates in the core–shell nanostructures, it
will reflect and transmit at different interfaces, and also absorbed by the
conductive medium. Reflection and absorption are the major factors for
energy loss. Especially at oblique incidence, when the incident angle
satisfies the condition of total internal reflection (TIR), the loss of light
will be greater. The light transmittance of core–shell nanostructures
was also affected by many factors, such as the number of shell layers,
shell thickness, incident wavelength, and incident angle. Therefore, it is
necessary to systematically study the relationship between the optical
transmission and the shell thickness, the incident wavelength, and the

⁎
Correspondence authors at: College of Electronic and Optical Engineering & College of Microelectronics, Nanjing University of Posts and Telecommunications,
Nanjing 210023, China (X. Wang).
E-mail addresses: buyy@njupt.edu.cn (Y. Bu), xfwang@njupt.edu.cn (X. Wang).

https://doi.org/10.1016/j.chemphys.2020.110785
Received 29 December 2019; Received in revised form 24 March 2020; Accepted 29 March 2020
Available online 02 April 2020
0301-0104/ © 2020 Elsevier B.V. All rights reserved.
Y. Yin, et al. Chemical Physics 535 (2020) 110785

into consideration. Next, the light propagation process between the

shells of nanostructures will be discussed.
In practice, the light transmission process in the core–shell hetero-
structure is very complicated. It is necessary to appropriately simplify
the light transmission process of the core–shell heterostructure. To this
end, the hypotheses are proposed as follows:

(a) The light emitted by the rare earth ions reaches the interface be-
tween the core and the shell-1 without loss, ignoring the absorption
and scattering of light by the core.
(b) The interfaces between layers are smooth, ignoring their rough
microstructures.
(c) Only the first reflection of light at each interface is considered
during light transmission process.

The admittance recursive method is used to study the light trans-

mittance of core–shell nanostructures. It is well known that when a
shell is coated on the outside of the core, the shell and the outer shell
medium can be represented by an equivalent interface. When a multi-
layer shell is applied, it can be recursively calculated from the outer-
most shell to the innermost shell. We assume that the innermost shell is
the first shell and the outermost shell is the kth shell. We can get the
combined admittance of the kth shell and the medium of the outer shell
as [30]:
Fig. 1. Schematic diagram of core–shell nanostructures in simulation process.
Yk + 1cos k + i k sin k
Yk = = yk(1) + iyk(2)
incident angle. In this paper, we develop the admittance recursive cos k + iYk + 1/ k sin k (1)
method to simulate the light transmission process in core–shell nanos- where k and k are the effective phase thickness and the modified
tructures, and study the effects of shell thickness, incident wavelength admittance of the kth shell, and Yk + 1 is numerically equal to the ad-
and incident angle on light transmission. The admittance recursive mittance of the outer shell medium.
method is a recursive method based on Maxwell's equations to deal with Superimposing the shell of the (k-1)th layer on the equivalent in-
multilayer structures without considering the interface effect [28]. terface can still be replaced by a virtual interface with a combined
Some basic optical parameters were accurately calculated by this admittance of Yk - 1. Thus, the recursive calculation to the jth layer shell
method, such as transmittance, absorptivity, and reflectance, through has:
iterating over several variable parameters, such as refractive index,
extinction coefficient, layer thickness, angle and wavelength [29,30]. Yj + 1cos j + i j sin j
Yj = = yj(1) + iyj(2)
Furthermore, we designed the infrared selective filters based on the cos j + iYj + 1/ j sin j (2)
core–shell heterostructure to achieve the monochromatic light output.
After calculating all the shells, the combined admittance of the
entire shell system is obtained as:
2. Model and method
Y1 = y1(1) + iy1(2) (3)
Based on the experimental design of core–shell NPs, the schematic
diagram of core–shell nanostructures used in the simulation process is The amplitude reflection coefficient is:
shown in Fig. 1. The core of radius R is coated with shell-1 of thickness
N0 Y1 (N0 y1(1) )2 iy1(2)
d1 and shell-2 of thickness d2, respectively. The rare earth ions doped in r= =
the core act as illuminating centers, which the direction of the light
N0 + Y1 (N0 + y1(1) )2 + iy1(2) (4)
emitted by is usually random. Therefore, light propagation in the where N0 is the admittance of the core.
core–shell NPs can be broadly classified into three categories, such as The reflection is:
light 1, 2, and 3 in Fig. 1. The simplest case is that the light emitted by
the illuminating center P propagates along the radial direction of the (N0 y1(1) )2 + (y1(2) ) 2
R=
nanostructures to the outside, just like the light 1. In another case, as (N0 + y1(1) )2 + (y1(2) ) 2 (5)
shown by light 2, when light emitted from P is incident to the interface
of the core and the shell-1 with an appropriate angle θ, reflection and In order to obtain the transmittance, we also need to introduce a
refraction occur. When the refracted light continues to propagate, si- physical quantity j , which represents the ratio of the energy flow
milar reflections and refractions occur at other interfaces and the light density of the adjacent interfaces of the jth shell. And j can be written
is eventually emitted to the outside. as [30]:
In both cases above, the light is emitted to the outside. It is assumed yj(1)
+1
that the refractive index of shell-1 is smaller than the core. When the j =
incident angle θ satisfies the TIR condition (θ ≥ θc, θc is the critical yj(1) |cos j + iYj + 1 sin j /Nj |2 (6)
angle of TIR), the light emitted by P will be totally reflected back at the
Therefore, the transmittance of the entire shell system is:
interface between the core and shell-1, as shown by light 3. If shells
with different refractive indices are chosen, TIR will also occur at other k
T = (1 r 2)
interfaces of the core–shell structure, such as the interface between j
j= 1 (7)
shell-1 and shell-2, and the interface between shell-2 and air. If the shell
is the ideal medium, the absorption of the shell can be ignored, but for Generally, incident light can be decomposed into TE waves and TM
the shell of the conductive medium, the absorption loss has to be taken waves. TE waves are called transverse electric waves, which have a

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Y. Yin, et al.
magnetic field component but no electric field component in the di-
rection of propagation [31]. TM waves are called transverse magnetic
waves, which have an electric field component and no magnetic field
component in the propagation direction [31]. When TE and TM waves
propagate in the core–shell heterostructure, they have different trans-
mission mechanisms, mainly due to different field components in the
direction of propagation. Therefore, the transmittances of two kinds of
polarized light (TE waves and TM waves) were studied separately.
For TE waves, the modified admittance of the jth shell is:
= Nj cos
j j
where Nj and j are the admittance and the refraction angle of the jth
shell.
For TM waves, the modified admittance of the jth shell is:
j = Nj /cos j (9)
For single-shell nanostructures, four different structures, such as
NaYF4@Ag, NaYF4@Au, NaYF4@TiO2, and NaYF4@SiO2, were re-
ported as an efficient up-conversion host [6–9], and their schematic
diagrams are shown in Fig. 2. As reported, multicolor up-conversion
emission from visible to infrared, such as blue (470 nm), green
(542 nm), red (654 nm), and infrared light (980 nm and 1540 nm)
[2,32–34], can be observed by the combination of different rare earth
ions and their concentration changes [35]. In addition, it was reported
that many of the prepared single-shell NPs had a diameter of about
20 nm [6,25,36,37] and shells thickness ranging from 2 nm to 100 nm
[6,13,18,26]. Thus, in this paper, light with wavelengths of 470 nm,
542 nm, 654 nm, 980 nm, and 1540 nm is chosen to calculate trans-
mission efficiency in core–shell heterostructures, and the diameter of
core is fixed at 20 nm and the shell thickness is fixed at 2, 5, 10, 15, 20,
30, 50, and 100 nm in simulation process.
The schematic diagram of NaYF4@Ag NPs is shown in Fig. 2(a). The
core radius R1 is 10 nm, and the Ag shell thickness is d. Since the
Fig. 2. Schematic diagrams of (a) NaYF4@Ag NPs, (b) NaYF4@Au NPs, (c) NaYF4@TiO2 NPs, (d) NaYF4@SiO2 NPs in simulation process.
Chemical Physics 535 (2020) 110785
refractive index of Ag (0.208) is smaller than that of NaYF4 (1.466) and
air (1), TIR occurs at the interface between NaYF4 and Ag, and the
critical angle is 8.1°. When light is emitted radially along the NPs (in-
cident angle is 0°), the transmittance of light at different wavelengths as
a function of the Ag shell thickness is shown in Fig. 3(a). One can find
that the transmittance (T) increases with the increase of incident wa-
velength (λ), and the transmittance decays sharply with the increase of
Ag shell thickness. For blue light at 470 nm, the transmittance
T = 10.5% when d = 10 nm, while for 1540 nm infrared light,
T = 57.8%. The wavelength dependent transmittance when the Ag
(8)
shell thickness is fixed at 2, 5, 10, 15, 20, 30, 50, and 100 nm is shown
in Fig. 3(b). It can be found that the transmittance increases with the
increase of wavelength from visible to infrared. For different wave-
lengths of light, the transmittance decreases with the increase of Ag
shell thickness.
The transmittance of TE waves at different wavelengths as a func-
tion of incident angle is shown in Fig. 4, when the Ag shell thickness is
fixed at 5, 10, 20, and 50 nm, respectively. It can be clearly seen from
Fig. 4 that the transmittance increases as the incident angle increases.
Especially in the vicinity of the critical angle, transmittance has a
greater increase. The transmittance of the TM wave is also studied in
Fig. S1. The transmittance of the TM wave in Fig. S1 is basically the
same as that of the TE wave in Fig. 4, since that the critical angle of TIR
at the NaYF4@Ag core–shell interface is small.
It is reported that the NaYF4@Au NPs have been studied for appli-
cations in photovoltaic [21] and photothermal conversion [38], and its
optical properties are also calculated in the paper based on the sche-
matic diagram in Fig. 2(b). The similar optical properties can be ob-
served for the NaYF4@Au NPs, as shown in Figs. S2–S4. The reason is
that Ag and Au have the same effect on achieving up-conversion in
core–shell structures, except for the similar refractive index and ex-
tinction coefficient. In the presence of noble metals shell, such as Au or
Ag shell, the broad absorption of noble metals can increase the power of
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Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 3. For NaYF4@Ag NPs, (a) transmittance as a function of the Ag shell thickness at incident wavelengths of 470, 540, 654, 980, and 1540 nm, and (b)
transmittance as a function of incident wavelength for Ag shells having thicknesses of 2, 5, 10, 15, 20, 30, 50 and 100 nm. Incident angle is 0°.

Fig. 4. For NaYF4@Ag NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and 1540 nm. The
Ag shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

the excitation by local field enhancement, resulted in the increase of
emission intensity of light [39].
For the NaYF4@TiO2 NPs, the schematic diagram used to simulate
light transmission process is shown in Fig. 2(c). Due to the small ex-
tinction coefficient of TiO2 (~10-3 m−1), it can be assumed that TiO2 is
an ideal medium, only considering the reflection and transmission of
different interfaces, regardless of the absorption loss in the medium.
Thus, the light transmission properties of the NaYF4@TiO2 NPs are
different from those of the NaYF4@Ag NPs and the NaYF4@Au NPs. The
refractive index of TiO2 (2.750) is larger than that of NaYF4 and air, so
the TIR occurs at the interface between TiO2 and air, and the critical
angle is approximately 43°. Fig. 5(a) shows the change of transmittance
with the TiO2 shell thickness, when different wavelengths of light are
emitted radially along NPs (incident angle is 0°). It can be seen that the
transmittance of light of different wavelengths periodically oscillates
between 54.4% and 96.5% with the TiO2 shell thickness, and the os-
cillation period increases with the increase of the incident wavelength.
From Fig. 5(b) one can observe that with small thickness of the TiO2
shell, such as 2, 5, 10 nm, the light transmittance in the radial direction
increases rapidly with the wavelength to the maximum value, and then
remains unchanged at the maximum. While, with the increase of TiO2
shell thickness more than 10 nm, the transmittance begins to oscillate
with wavelengths between 54.4% and 96.5%, and the oscillation period
increases as the wavelength increases.
The transmittance of TE wave increases slowly in the incident range
of 0° to 43°, which is shown in Fig. 6. As the TiO2 shell thickness in-
creases, the transmittance of light at different wavelengths decreases.
For example, when the d value is fixed at 5, 10, 20, and 50 nm, the
maximum transmittance of blue light at 470 nm is 94.7%, 90.2%,
77.4%, and 60.2%, respectively. When the TiO2 shell thickness is in-
creased to 50 nm, the anomalous phenomena are observed. In the in-
cident range, the transmittance of blue light is greater than that of
green light, as shown in Fig. 6(d), which is related to the periodic
variation of transmittance with TiO2 shell thickness. However, for TM
wave, the transmittance of each light decreases slowly with the increase
of incident angle, as shown in Fig. 7.

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Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 5. For NaYF4@TiO2 NPs, (a) transmittance as a function of the TiO2 shell thickness at incident wavelengths of 470, 540, 654, 980, and 1540 nm, and (b)
transmittance as a function of incident wavelength for TiO2 shells having thicknesses of 2, 5, 10, 15, 20, 30, 50 and 100 nm. Incident angle is 0°.

The schematic diagram of the NaYF4@SiO2 NPs is shown in
Fig. 2(d). The refractive index of SiO2 (1.451) is slightly smaller than
NaYF4, but larger than air. Therefore, when the light propagates to the
interface between SiO2 and air, TIR occurs, and the critical angle is 43°.
Unlike the above NaYF4@Ag, NaYF4@Au and NaYF4@TiO2 NPs, the
change in transmittance of NPs using SiO2 as a shell is not very obvious
in various aspects. Fig. 8(a) shows the periodic variation of the trans-
mittance with the SiO2 shell thickness in the range of 96.4% to 96.8%
when the light propagates in the radial direction, and the period in-
creases as the wavelength increases. When the thickness of the SiO2
shell is small, the light of different wavelengths always increases with
the increase of the thickness, which is consistent with the experimental
results reported by Wang et al, and the reason for the increase is that
the SiO2 shell can modify the crystal defects [10]. It can be observed
from Fig. 8(b) that the transmittance oscillates with the incident wa-
velength in the short wavelength range. As the incident wavelength
increases, the transmittance eventually approaches a minimum,
meaning that the transmission of infrared light is relatively small.
For NaYF4@SiO2 NPs, the variation of the transmittance of TE wave
and TM wave with the incident angle is completely different from the
above three structures, as shown in Fig. 9 and Fig. 10. Fig. 9 shows the
transmittance of TE wave as a function of the incident angle. The
transmittance of TE wave is always increases first and then decreases
with the incident angle, and the turning point occurs around 30°. As the
TiO2 shell thickness increases, the maximum of transmittance of light at
different wavelengths also increases. For example, for blue light, when
the TiO2 thickness is 5, 10, 20, and 50 nm, the transmittance changes by
0.02%, 0.08%, 0.31%, and 1.63%, respectively. For TM wave, we can
see from Fig. 10 that the transmittance of light of different wavelengths
is substantially the same when the incident angle is within 10° re-
gardless of the thickness of the SiO2 shell. As the incident angle in-
creases to more than 10°, the transmittance of the TM wave begins to
decrease. For TiO2 shells of different thicknesses, the shorter the in-
cident wavelength, the faster the transmittance decreases. By com-
paring the light transmission processes of the four single-shell struc-
tures, it is found that the NaYF4@SiO2 structure has the highest
transmittance for TE waves. There are two main reasons for this phe-
nomenon. On the one hand, the absorption of light by the SiO2 shell is

Fig. 6. For NaYF4@TiO2 NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and 1540 nm.
The TiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

5
Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 7. For NaYF4@ TiO2 NPs, the transmittance of the TM wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and 1540 nm.
The TiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

Fig. 8. For NaYF4@SiO2 NPs, (a) transmittance as a function of the SiO2 shell thickness at incident wavelengths of 470, 540, 654, 980, and 1540 nm, and (b)
transmittance as a function of incident wavelength for SiO2 shells having thicknesses of 2, 5, 10, 15, 20, 30, 50 and 100 nm. Incident angle is 0°.

very weak [11,12,20], which means that SiO2 can be approximated as
an ideal medium. On the other hand, when the NaYF4@SiO2 structure
propagates TE waves, the gradient of the optical admittance is the
smallest [39–41].
In addition to single-shell NPs, double-shell NPs [10–12], such as
NaYF4@SiO2@Ag, NaYF4@SiO2@Au and NaYF4@SiO2@TiO2, are
widely studied for applications in photocatalysis [12] and bioassay
[40]. Double-shell NPs were reported to have a diameter of about 30 to
50 nm [12,39] and an inner shell thickness of about 5 to 20 nm
[11,20,41]. Thus, in this paper, the light transmission properties of
three double-shell structures, NaYF4@SiO2@Ag, NaYF4@SiO2@Au and
NaYF4@SiO2 @TiO2, are also calculated based on the schematic dia-
grams in Fig. 11(a)–(c). For double-shell NPs, the diameter of core and
the thickness of inner shell are fixed at 40 nm and 10 nm, respectively.
It can be found that SiO2 is always used as the inner shell rather than
the outer shell in Fig. 11(a)–(c). What is the effect of the shell dis-
tribution order on the transmittance of the core–shell nanostructures?
In order to better understand the light transmission process of the
double-shell NPs induced by the shell distribution order, the analysis is
also performed on NaYF4@Ag@SiO2, NaYF4@Au@SiO2 and
NaYF4@TiO2@SiO2 NPs, and their schematic diagrams are shown in
Fig. 11(d)–(f).
The schematic diagram of NaYF4@SiO2@Ag NPs is shown in
Fig. 11(a). The NaYF4 core with a radius of R2 = 20 nm is covered with
a SiO2 shell with a thickness of d1 = 10 nm, and then an Ag shell with a
thickness of d2 is coated. TIR will occur first at the interface between
SiO2 and Ag with a critical angle of 8.1°. It is observed that the light
transmission properties of this structure are very similar to those of
NaYF4@Ag NPs, as shown in Figs. S5–S7. The reason is that the SiO2
shell is used to modify crystal defects, which can slightly increase the
transmittance. In addition, SiO2 has a weak effect on reflection and
absorption loss due to its similar refractive index and extinction coef-
ficient to that of NaYF4. Therefore, the SiO2 shell has little effect on
light transmission. It is proved that the Ag shell plays a decisive role in
the transmittance in NaYF4@SiO2@Ag NPs, which is consistent with
the experimental results of Yi Qin et al [39].
By further studying the structure of NaYF4@Ag@SiO2, the re-
lationship between shell distribution order and transmittance was

6
Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 9. For NaYF4@SiO2 NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and 1540 nm.
The SiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

Fig. 10. For NaYF4@SiO2 NPs, the transmittance of the TM wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and 1540 nm.
The SiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

investigated. The schematic diagram of NaYF4@Ag@SiO2 NPs is shown
in Fig. 11(d). TIR occurs at the interface between NaYF4 and Ag, and
the critical angle is still 8.1°. As shown in Fig. 12(a), the transmittance
is periodically oscillated with the SiO2 shell thickness, and the oscilla-
tion period increases as the incident wavelength increases. Differently,
light with different wavelengths oscillates in different ranges. For
example, the transmittance of 1540 nm infrared light oscillates between
57.8% and 79.1%, and the blue light oscillates between 10.0% and
19.8%. The reason for this phenomenon is that Ag can strongly absorb
short-wavelength light, which is shown in Fig. 3(a). Fig. 12(b) shows
the change in light transmittance as a function of incident wavelength.
Transmittance increases with the increase of incident wavelength.

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Y. Yin, et al.
Fig. 11. Schematic diagrams of (a) NaYF4@SiO2@Ag, (b) NaYF4@SiO2@Au, (c) NaYF4@SiO2@TiO2, (d) NaYF4@Ag@SiO2, (e) NaYF4@Au@SiO2 and (f)
NaYF4@TiO2@SiO2 in simulation process.
When the SiO2 shell thickness is small, the transmittance slightly in-
creases as the thickness of the SiO2 shell increases. However, when the
shell thickness reaches 100 nm, the transmittance becomes relatively
small in the range of wavelengths less than 500 nm.
The variation of the transmittance of TE wave with the incident
angle for NaYF4@Ag@SiO2 NPs is shown in Fig. 13. The light trans-
mittance at different wavelengths increases as the incident angle in-
creases. As the SiO2 shell thickness increases, the transmittance will
increase slightly, which corresponds to the change in transmittance in
Fig. 11(a). Because the SiO2 layer can modify crystal defects, which can
only slightly increase the transmittance. The variation of the trans-
mittance of TM wave with the incident angle shown in Fig. S8 is the
same as that of TE wave.
The schematic diagram of NaYF4@SiO2@Au NPs is shown in
Fig. 11(b). Since the Ag shell and the Au shell have the same effect on
the transmittance in the core–shell structure, the optical transmission
properties of NaYF4@SiO2@Au NPs and NaYF4 @SiO2@Ag NPs are also
approximately the same, which are shown in Figs. S9–S11. The
NaYF4@Au@SiO2 structure was also used to study the effect of shell
distribution on transmittance. The schematic diagram of NaYF4@Au@
SiO2 is shown in Fig. 11(e). One can find that the similar optical
transmission properties to NaYF4@Ag@SiO2 NPs are shown in Figs.
S12–S14.
8
Chemical Physics 535 (2020) 110785
Fig. 12. For NaYF4@Ag@SiO2 NPs, (a) transmit-
tance as a function of the SiO2 shell thickness at
incident wavelengths of 470, 540, 654, 980, and
1540 nm, and (b) transmittance as a function of
incident wavelength for SiO2 shells having thick-
nesses of 2, 5, 10, 15, 20, 30, 50 and 100 nm. The Ag
shell thickness is fixed at 10 nm and incident angle
is 0°.
The schematic diagram of NaYF4@SiO2@TiO2 NPs is shown in
Fig. 11(c). TIR occurs at the interface between TiO2 and air with a
critical angle of 43°. As is shown Fig. S15, the variation of the trans-
mittance of NaYF4@SiO2@TiO2 NPs with the TiO2 shell thickness and
incident wavelength is very similar to that of NaYF4@TiO2 NPs. The
reason is that the main role of SiO2 shell is crystal defects modification,
which is the same as those structures analyzed above.
The transmittance of the TE wave increases with the increase of
incident angle, as shown in Fig. 14. When the SiO2 shell thickness is
5 nm, the transmittance of TE waves of different wavelengths is very
close near the critical angle of TIR. As the TiO2 shell thickness increases,
the difference in transmittance near the critical angle becomes larger
and larger. In addition, when d2 = 50 nm, the change in transmittance
shows an anomaly similar to that of NaYF4@TiO2. When the incident
angle is less than 35°, the transmittance of blue light is higher than that
of green light, and even higher than that of red light at a smaller in-
cident angle. For the TM wave, it can be observed from Fig. 15 that the
light transmittance decreases with the increase of incident angle. When
d2 = 50 nm, similar to the TE wave, an anomaly occurs. Differently, the
transmittance of blue light is higher than green light over the entire
incident range, even very close to red light.
We further study the structure of NaYF4@TiO2@SiO2 to investigate
the effect of shell distribution order, and its schematic diagram is shown
Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 13. For NaYF4@Ag@SiO2 NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and
1540 nm. The SiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

in Fig. 11(f). TIR occurs at the interface between SiO2 and air, with a decreases with the increase of incident wavelength. It can be observed
critical angle of 43°. As can be seen from Fig. 16(a), the transmittance from Fig. 16(b) that the transmittance first decreases and then increases
periodically oscillates with the thickness of SiO2 shell. The period in- when d2 = 2, 5, 10, and 15 nm. However, as the thickness increases to
creases with the increase of incident wavelength and the amplitude more than 15 nm, the transmittance begins oscillation. When the

Fig. 14. For NaYF4@SiO2@TiO2 NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and
1540 nm. The TiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

9
Y. Yin, et al.
Fig. 15. For NaYF4@SiO2@TiO2 NPs, the transmittance of the TM wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and
1540 nm. The TiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.
wavelength is greater than 1000 nm, the transmittance no longer os-
cillates with the wavelength. One can find that the transmittance of the
TE wave increases with the increase of the incident angle in Fig. 17. The
shorter the wavelength of the light, the faster the transmittance in-
creases with the incident angle, except for the blue light in Fig. 17(d).
For the TM wave shown in Fig. 18, the transmittance decreases as the
incident angle increases.
By comparison, it is found that the shell distribution has little effect
on the transmittance. In the three structures of NaYF4@SiO2@Ag,
NaYF4@SiO2@Au and NaYF4@SiO2@TiO2, the SiO2 shell plays the
same role. Crystal defect modification by SiO2 shell can result in a slight
increase in transmittance. The effect on the transmittance is determined
by the outer shell, such as the Ag shell, the Au shell, and the TiO2 shell.
Experimentally, researchers often use SiO2 as the inner shell. In addi-
tion to the reason above, it is also possible that the SiO2 shell can make
the NPs surface passivation, isolating the outer shell and the core to
achieve the up-conversion intensity enhancement [39].
According to the light transmission properties of the different
structures analyzed above, if it is assumed that the intensity of light
emitted from the core is the same, there is a significant difference in the
10
Chemical Physics 535 (2020) 110785
Fig. 16. For NaYF4@TiO2@SiO2 NPs, (a) transmit-
tance as a function of the SiO2 shell thickness at
incident wavelengths of 470, 540, 654, 980, and
1540 nm, and (b) transmittance as a function of
incident wavelength for SiO2 shells having thick-
nesses of 2, 5, 10, 15, 20, 30, 50 and 100 nm. The
TiO2 shell thickness is fixed at 10 nm and incident
angle is 0°.
intensity of the emitted light when passing through the shell with
thickness fixed, especially in NaYF4@Ag@SiO2 NPs. For NaYF4@Ag@
SiO2 NPs the longer the wavelength, the greater the light intensity
emitted. In order to obtain only infrared light of 980nn and 1540 nm,
visible light is further absorbed. Therefore, a layer of Ag is coated
outside of the NaYF4@Ag@SiO2 NPs to form a NaYF4@Ag@SiO2@Ag
structure. The schematic diagram of it is shown in Fig. 19(a), where d1,
d2, and d3 are the thicknesses of the inner Ag shell, the SiO2 shell, and
the outer Ag shell, respectively.
In order to achieve filtering, each shell thickness of NaYF4@Ag@
SiO2@Ag NPs is optimized. On the basis of ensuring a transmission
intensity of more than 30%, appropriate thickness combinations have
been determined. When d1 = 50 nm, d2 = 447.5 nm and d3 = 45 nm,
NaYF4@Ag@SiO2@Ag NPs can filter out 1540 nm infrared light.
Fig. 19(b) is a normalized spectrum with a bandwidth of 37 nm. When
d1 = 30 nm, d2 = 284.8 nm and d3 = 30 nm, NaYF4@Ag@SiO2@Ag
NPs can filter out 980 nm infrared light. Fig. 19(c) is its normalized
spectrum with a bandwidth of 24 nm. Comparing Fig. 19(b) with (c), it
is obvious that the 980 nm filter has a narrower bandwidth around the
center wavelength, which means better filtering. However, it is
Y. Yin, et al. Chemical Physics 535 (2020) 110785

Fig. 17. For NaYF4@TiO2@SiO2 NPs, the transmittance of the TE wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and
1540 nm. The SiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

Fig. 18. For NaYF4@TiO2@SiO2 NPs, the transmittance of the TM wave as a function of the incident angle at the incident wavelengths of 470, 540, 654, 980, and
1540 nm. The SiO2 shell thickness was fixed at (a) 5 nm, (b) 10 nm, (c) 20 nm, and (d) 50 nm, respectively.

accompanied by interference of long-wavelength light. In theory, by 3. Conclusions

adjusting the structural parameters, the filtering function can also be
realized for visible light, but the interference of long-wavelength light In summary, we simulated the light transmission process of core–-
will be more serious. shell heterostructure. The effect of shell thickness, incident wavelength

11
Y. Yin, et al.
Fig. 19. (a) Schematic diagram of NaYF4@Ag@SiO2@Ag NPs. Normalized spectrum of the (b) 1540 nm and (c) 980 nm filter.
and incident angle on the light transmission of NPs was systematically
studied by admittance recursive method. It is observed that TE wave
transmission efficiency of the NaYF4@SiO2 core–shell heterostructure is
the highest. Furthermore, the new multilayer shell structure
NaYF4@Ag@SiO2@Ag was designed to achieve selective transmission
of infrared light at 1540 nm and 980 nm on the basis of ensuring their
transmission intensity more than 30%. This work proposes a method for
analyzing the light transmission process of core–shell NPs, which helps
us understand the energy loss of light during transmission in NPs.
CRediT authorship contribution statement
Yunzhen Yin: Methodology, Software, Validation, Investigation,
Data curation, Writing - original draft. Yanyan Bu: Conceptualization,
Methodology, Investigation, Supervision. Xiangfu Wang:
Conceptualization, Methodology, Investigation, Supervision, Project
administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work is supported by the National Natural Science Foundation of
China (11404171), Jiangsu Natural Science Foundation for Excellent
Young Scholar (BK20170101), Scientific Research Foundation of Nanjing
University of Posts and Telecommunications (NY220011, NY220034).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.chemphys.2020.110785.
12
Chemical Physics 535 (2020) 110785
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