Investigating the Coupling Between Metal Oxide Photonic Modes and Noble

Metal Plasmons
Jonah Shoemaker1, Peter Crozier2
1.
Department of Physics, Arizona State University, Tempe, Arizona 85287-6106, USA.
2.
School for the Engineering of Matter, Transport and Energy, Arizona State University, Tempe,
Arizona 85287-6106, USA.

It has been demonstrated that cerium oxide nanocubes are capable of trapping visible light waves
of certain frequencies within as photonic modes [2]. These photonic modes may be able to
couple to localized surface plasmons (LSPs) of similar resonant frequency on supported silver
nanoparticles (NPs) through resonant energy transfer. These excited LSPs have the potential to
assist in the catalysis of water [1]. The electron beam in an aberration-corrected STEM can be
used as both a source of supercontinuum light that simultaneously excites all photonic modes
present within the ceria cube and a means of detecting the excitations through EELS [3]. Given
the presence of silver NPs of the right size and shape supported on the ceria cubes, it will be
possible to record any induced changes in the energy-loss spectra. In this study, we seek to
understand the nature of this coupling between the ceria’s photonic modes and the silver’s
plasmons through theoretical analysis.

Aloof-beam EELS simulations were conducted in COMSOL Multiphysics ® to test for resonant
coupling between a ceria nanocube with side length 250 nm supporting hemispherical silver NPs
of various sizes. All simulations were performed with a beam energy of 60 kV using the EELS
simulation methods detailed in Govyadinov et al [4]. Dielectric data for the silver was obtained
from Palik’s Handbook of Optical Constants, and for the ceria from Jarrendal et al [5]. Figure 1
shows a typical geometry for the simulations. The electron beam is positioned 4 nm away from
the adjacent face of the ceria cube to avoid signal from the bulk, and the silver nanoparticle is
placed on the opposite side from the beam to minimize its direct contribution to the energy-loss
spectra.

Figure 2 shows the energy-loss spectra for a ceria cube, a silver NP, and both. The silver NP had
a radius of 75 nm. Numerous peaks are present below the bandgap of the ceria due to the
excitation of photonic modes. As can be observed, some interaction between the ceria cube and
the Ag hemisphere induces shifting in the photonic mode peaks that cannot be accounted for by
either on their own. It is hypothesized that these shifts are due to resonance between the ceria’s
cavity modes and the silver’s plasmonic modes. The inset in Figure 2 shows the region between
1 and 2 eV in more detail. Significant changes in the relative intensities of the peaks at 1.2 eV,
1.5 eV, and 1.8 eV can be seen. In Figure 3, the size of the Ag hemisphere is varied to examine
its effect on the cavity mode peaks between 2.5 and 3.5 eV. It can be seen that as the size of the
Ag NP increases, the peaks at 2.8eV and 3.2eV shift to slightly higher energy. This evidence of
possible coupling between the cavity modes of the ceria and the plasmons of the silver should be
detectable with an aberration-corrected STEM and encourage further investigation.
[1] Yang, Wei-Chang D., et al. “Site-Selective CO Disproportionation Mediated by Localized Surface Plasmon Resonance
Excited by Electron Beam.” Nature Materials, vol. 18, no. 6, 2019, pp. 614–619., doi:10.1038/s41563-019-0342-3.

[2] Liu, Qianlang, et al. “Nanoscale Probing of Resonant Photonic Modes in Dielectric Nanoparticles with Focused Electron
Beams.” Physical Review B, vol. 99, no. 16, Mar. 2019, doi:10.1103/physrevb.99.165102.

[3] Abajo, F. J. García De. “Optical Excitations in Electron Microscopy.” Reviews of Modern Physics, vol. 82, no. 1, Mar. 2010,
pp. 209–275., doi:10.1103/revmodphys.82.209.

[4] Govyadinov, Alexander A., et al. “Probing Low-Energy Hyperbolic Polaritons in Van Der Waals Crystals with an Electron
Microscope.” Nature Communications, vol. 8, no. 1, 2017, doi:10.1038/s41467-017-00056-y.

[5] Järrendahl, K., and H. Arwin. “Multiple Sample Analysis of Spectroscopic Ellipsometry Data of Semi-Transparent Films.”
Thin Solid Films, vol. 313-314, 1998, pp. 114–118., doi:10.1016/s0040-6090(97)00781-5.

[6]
 Figure 1
Geometry Setup for the simulations.
The ceria cube has side length 250 nm
for all tests.
Figure 2
Simulation results for CeO2 cube by itself (red), silver NP with radius 75 nm by itself
(blue), and both (purple). Hybridized photonic modes are visible for the ceria below
its bandgap in the 2.5 – 3.5 eV range. The peaks at 2.78 eV and 3.20 eV for the ceria
cube shift to 2.80 eV and 3.22 eV in the presence of the silver NP. Changes in
Figure 3
intensity induced by the presence of the silver can be seen for the modes at 1.2 eV,
1.5 eV, 1.8 eV, shown in more detailSimulation
in the inset,results
in addition to the
for the modes
ceria cubeatwith
3.1 eV
and 3.3 eV. silver hemispheres with radii of 50 nm
(cornflower blue), 75 nm (blue), and 100 nm
(navy). The peak on the left shifts from 2.80
eV to 2.84 eV with increasing radius. The
peak on the right shifts from 3.22 eV to 3.24
eV. In addition, the modes at 2.94 eV and
3.30 eV see changes in relative intensity due
to the increase in NP size.
Figure 3