(Invited, Digital Presentation) Enhancement of Magnetic Dipole Transition of Molecules By Silicon Nanoparticle Nanoantenna
Authors: Fujii Minoru , Sugimoto Hiroshi 
Published: July 2022

A nanoantenna is a nanodevice that manipulates light propagation and enhances light-matter interaction at the nanoscale. Integration of an emitter into a nanoantenna capable of increasing local density of photonic states at the emission wavelength results in the enhanced spontaneous emission rate (Purcell effect). The most widely studied nanoantennas for the Purcell enhancement are plasmonic nanoantennas made from gold or silver nanostructures supporting surface plasmon resonances. In most cases, nanoantennas have been used for the enhancement of electric dipole-allowed transition of a molecule. In addition, recently, nanoantennas capable of enhancing magnetic dipole transition of a molecule are attracting attention. For the magnetic Purcell enhancement, nanoantennas have to have magnetic resonances at the optical frequency. Although it is possible to achieve magnetic resonances at the optical frequency by plasmonic nanostructures, the inherent absorption loss of noble metals limits the magnetic Purcell enhancement. On the other hand, nanoparticles of high refractive index dielectrics inherently have low-loss magnetic-type Mie resonances at the optical frequency, and thus are potentially more attractive as a material to realize large magnetic Purcell enhancement.
We have developed spherical nanoparticles of crystalline silicon (Si) having the magnetic dipole (MD) and quadrupole (MQ) Mie resonances at the optical frequency [1]. In this work, to demonstrate the potential of a Si nanoparticle as a nanoantenna for the magnetic Purcell enhancement, we develop a composite nanoparticle, that is, a Si nanosphere decorated with europium ion (Eu3+) complexes, in which magnetic dipole emission of Eu3+ is efficiently coupled to the magnetic Mie modes of the nanosphere [2]. We systematically investigate the light scattering and photoluminescence spectra of the coupled system by means of single particle spectroscopy. The results are shown in Figure 1. By tuning the MQ Mie resonance of a Si nanosphere to the 5D0-7F1 magnetic dipole transition of Eu3+, the branching ratio between the magnetic and electric dipole (5D0-7F2) transitions is enhanced up to 7 times. The observed large magnetic Purcell enhancement offers an opportunity to develop novel fluorophores with enhanced magnetic dipole emission. Furthermore, the enhanced magnetic field of dielectric Mie resonators enhances otherwise very weak absorption due to magnetic dipole transition, and makes direct excitation of triplet states of a molecule possible [3]. Direct excitation of triplet states reduces photon energy necessary for energy conversion and chemical reactions utilizing a triplet state compared to a conventional process involving singlet-singlet excitation and singlet-triplet intersystem crossing.
[1] H. Sugimoto, et. al., "Mie Resonator Color Inks of Monodispersed and Perfectly Spherical Crystalline Silicon Nanoparticles" Advanced Optical Materials, 8 (2020) 2000033.
[2] H. Sugimoto, and Minoru Fujii, "Magnetic Purcell Enhancement by Magnetic Quadrupole Resonance of Dielectric Nanosphere Antenna", ACS Photonics, 8 (2021) 1794.
[3] H. Sugimoto, et. al., "Direct Excitation of Triplet State of Molecule by Enhanced Magnetic Field of Dielectric Metasurfaces", Small, 2021, DOI: 10.1002/smll.202104458.
Figure 1: Photoluminescence (red curves) and scattering (black curves) spectra of single Si naosphere-Eu3+ complex composite nanoparticles with different Si nanosphere diameters. The diameters are shown at the right end of the figure.

Figure 1