Magnetic functionalization of ZnO nanoparticles surfaces via optically generated methyl radicals.

The combination of nuclear and electron magnetic resonance techniques, in pulse and continuous wave regimes, is used to unravel the nature and features of the light-induced magnetic state arising at the surface of chemically prepared zinc oxide nanoparticles (NPs) occurring under 120 K when subjected to a sub-bandgap (405 nm) laser excitation. It is shown that the four-line structure observed around g ∼ 2.00 in the as-grown samples (beside the usual core-defect signal at g ∼ 1.96) arises from surface-located methyl radicals (•CH3), originating from the acetate capped ZnO molecules. By functionalizing the as-grown zinc oxide NPs with deuterated sodium acetate, the •CH3 electron paramagnetic resonance (EPR) signal is replaced by trideuteromethyl (•CD3). For •CH3, •CD3, and core-defect signals, an electron spin echo is detected below ∼100 K, allowing for the spin-lattice and spin-spin relaxation-time measurements for each of them. Advanced pulse-EPR techniques reveal the proton or deuteron spin-echo modulation for both radicals and give access to small unresolved superhyperfine couplings between adjacent •CH3. In addition, electron double resonance techniques show that some correlations exist between the different EPR transitions of •CH3. These correlations are discussed as possibly arising from cross-relaxation phenomena between different rotational states of radicals.

Design of infrared optical absorber using silver nanorings array made by a top-down process.

This paper presents the numerical simulation and fabrication of a metasurface composed of silver nanorings with a split-ring gap. These nanostructures can exhibit optically-induced magnetic responses with unique possibilities to control absorption at optical frequencies. The absorption coefficient of the silver nanoring was optimized by performing a parametric study with Finite Difference Time Domain (FDTD) simulations. The absorption and scattering cross sections of the nanostructures are numerically calculated to assess the impact of the inner and outer radii, the thickness and the split-ring gap of one nanoring, as well as the periodicity factor for a group of four nanorings. This showed full control on resonance peaks and absorption enhancement in the near infrared spectral range. The experimental fabrication of this metasurface made of an array of silver nanorings is achieved by e-beam lithography and metallization. Optical characterizations are then carried out and compared to the numerical simulations. In contrast to usual microwave split-ring resonator metasurfaces reported in literature, the present study shows both the realization by a top-down process and modelling performed in the infrared frequency range.

Light-induced high-spin state in ZnO nanoparticles.

The effects of white-light irradiation on ∼15 nm diameter ZnO nanoparticles are investigated by means of electron paramagnetic resonance, near liquid-nitrogen and liquid-helium temperatures. Under dark conditions, usual core- and surface-defects are detected, respectively, at g = 1.960 and g = 2.003. Under white-light illumination, the core-defect signal intensity is strongly increased, which is to be correlated to the light-induced conductivity's augmentation. Beside, a four-lines structure appears, with the same gravity center as that of the surface defects. Simulations and intensity power-dependence measurements show that this four-line-structure is very likely to arise from a localized high spin S = 2, induced by light irradiation, and subjected to a weak axial anisotropy. At 85 K, this high-spin state can last several hours after the light-irradiation removal, probably due to highly spin-forbidden recombination process. The possible excited resonant complexes at the origin of this signal are discussed. Other light-induced S = 1/2-like centers are detected as well, which depend on the nanoparticles growth conditions.