ABSTRACT
The electromagnetic field enhancement mechanisms leading to surface-enhanced Raman scattering (SERS) of R6G molecules near Ti3C2TxMXene flakes of different shapes and sizes are analyzed theoretically in this paper. In COMSOL simulations for the enhancement factor (EF) of SERS, the dye molecule is modeled as a small sphere with polarizability spectrum based on experimental data. It is demonstrated, for the first time, that in the wavelength range of500 nm-1000 nm, the enhancement of Raman signals is largely conditioned by quadrupole surface plasmon (QSP) oscillations that induce a strong polarization of the MXene substrate. We show that the vis-NIR spectral range quadrupole SP resonances are strengthened due to interband transitions (IBTs), which provide EF values of the order of 105-107in agreement with experimental data. The weak sensitivity of the EF to the shape and size of MXene nanoparticles (NPs) is interpreted as a consequence of the low dependence of the absorption cross-section of QSP oscillations and IBT on the geometry of the flakes. This reveals a new feature: the independence of EF on the geometry of MXene substrates, which allows to avoid the monitoring of the shape and size of flakes during their synthesis. Thus, MXene flakes can be advantageous for the easy manufacturing of universal substrates for SERS applications. The electromagnetic SERS enhancement is determined by the 'lightning rod' and 'hot-spot' effects due to the partial overlapping of the absorption spectrum of the R6G molecule with these MXene resonances.
ABSTRACT
Superparamagnetic iron oxide nanoparticles can be assembled to form anisotropic microrod supraparticles with the assistance of a magnetic field during synthesis. Optionally, these iron oxide microrods can furthermore be coated with a thin silica shell. Due to their anisotropic structure, both microrod types can be aligned in a magnetic field while being dispersed in a matrix material which can be cured during the alignment of the microrods. In this way, an anisotropic magnetic composite is obtained. Interestingly, it was observed that the optical extinction properties for visible light in such a composite are direction dependent, which can be explained by using appropriate models based on Maxwell equations. Based on the understanding of this principle, a clever approach for a hidden code could be proposed which is obtained from mixing pure iron oxide and silica coated microrod supraparticles in such an anisotropic composite. The hidden code, which comes down to obtaining a single value eventually, can only be revealed when knowing that the system needs to be measured with a certain "twist".
