Investigating the Coupling Between Metal Oxide Photonic Modes and Noble

Metal Plasmons
Jonah Shoemaker1, Kartik Venkatraman2 and Peter A. 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 electron energy-loss spectroscopy (EELS) can also be employed to
explore the characteristic photonic modes present in dielectric nanoparticles such as thaCeO2t
cerium oxide nanocubes are capable of trapping visible light waves of certain frequencies within
as photonic modes [21]. The electron beam in an aberration-corrected scanning transmission
electron microscope (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 [23]. These photonic modes may be able to couple to
phononic, excitonic ofr plasmonic modes via resonant energy transfer processes. High spatial
resolution, monochromated EELS in a scanning transmission electron microscopeSTEM
provides a convenient way of sensesing mode coupling in nanoparticle systems. Here, we
investigate the coupling between photonic modes in CeO2 with localized surface plasmons
(LSPs) of similar resonant frequency onof supported silver Ag nanoparticles (NPs) through
resonant energy transfer. These excited LSPs have the potential to assist in the catalysis of water
[1]. TheAn initial focus of the project is ion using dielectric theory to simulate the STEM
EELSenergy-loss spectrum for different geometrical configurations of the particles and the
electron probe. To facilitate our understanding of resonant energy and damping on coupling, we
also explore coupling between photonic modes and Drude metals. 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 and supporting supported
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. [34]. Dielectric data for
the silver Ag was obtained from Palik’s Handbook of Optical Constants [ref], and for the ceria
CeO2 from Jarrendahl et al. [45]. Simulations performed for isolated CeO2 cubes showed good
agreement with published experimental data [1]. The inset in Figure 1 shows a typical geometry
for the simulations. The electron beam is positioned 4 nm away from the adjacent face of the
CeO2 ceria cube to avoid signal from the bulk, and the silver Ag nanoparticle is placed on the
opposite side from the beam to minimize its direct contribution to the energy-loss spectra.

Figure 12 shows the energy-loss spectra for a CeO2 ceria cube, aan Ag SILVER NP, and both.
The silver Ag NP had a radius of 75 nm. Numerous peaks are present below the bandgap of the
CeO2 ceria due to the excitation of photonic modes. As can be observed, some interaction
between the CeO2 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 photonic modes and the silver’s plasmonic modes. In particular,
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 2, the size of the Ag hemisphere is varied to examine its effect on the photonic
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 2.8 eV and 3.2 eV shift to slightly higher energy. This evidence of possible coupling
between the photonic modes of the ceria and the plasmons of the silver will should be
detectablebe investigated experimentally with an aberration-corrected STEM and encourage
further investigationand compared to simulation.

References: - suggest you have first initial, last name then et al ….to save space you do not
need the titles of papers

[1] Liu, Qianlang et al. Physical Review B, 99, 16, 2019.

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

[34] Govyadinov, A.lexander 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.
[45] Järrendahl, K., and H. Arwin. et al. Thin Solid Films, vol. 313-314, 1998, pp. 114–118,
1998.., doi:10.1016/s0040-6090(97)00781-5.
[6]5[5]
The support from US National Science Foundation CHE-1508667and U.S. DOE (DE-
SC0004954) is gratefully acknowledged.
 Figure 1.

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 intensity induced by the presence of the
silver can be seen for the modes
Figure 2. at 1.2 eV, 1.5 eV, 1.8
eV, shown in more detail in the inset, in addition to the
modes Simulation results
at 3.1 eV and for the ceria cube with
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
Figure 3
to the increase in NP size.