ABSTRACT
Here we report on the non-hydrothermal aqueous synthesis and characterization of nanocrystalline lithium aluminum iodate, LiAl(IO3)4. Morphological and compositional analyses were carried out by using scanning electron microscopy (SEM) and energy-dispersive X-ray measurements (EDX). The optical and vibrational properties of LiAl(IO3)4 have been studied by UV-Vis and IR spectroscopy. LiAl(IO3)4 is found to crystallize in the non-centrosymmetric, monoclinic P21 space group, contrary to what was reported previously. Theoretical simulations and Rietveld refinements of crystal structure support this finding, together with the relatively high Second Harmonic Generation (SGH) response that was observed. Electronic band structure calculations show that LiAl(IO3)4 crystal has an indirect band gap Egap=3.68 eV, in agreement with the experimental optical band gap Egap=3.433 eV. The complex relative permittivity and the refraction index of LiAl(IO3)4 have also been calculated as a function of energy, as well as its elastic constants and mechanical parameters. LiAl(IO3)4 is found to be a very compressible and ductile material. Our findings imply that LiAl(IO3)4 is a promising material for optoelectronic and non -linear optical applications.
ABSTRACT
Phase-pure, highly crystalline sub-50 nm LiNbO3 nanocrystals were prepared from a non-aqueous solvothermal process for 72 h at 230 °C and a commercial precursor solution of mixed lithium niobium ethoxide in its parent alcohol. A systematic variation of the reaction medium composition with the addition of different amounts of co-solvent including butanol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol resulted in the formation of nanocrystals of adjustable mean size and shape anisotropy, as demonstrated from XRD measurements and TEM imaging. Colloidal stability of ethanol- and water-based suspensions was evaluated from dynamic light scattering (DLS)/zeta potential studies and correlated with FTIR data. Thanks to the evolution in the nanocrystal size and shape distribution we observed, as well as to the available literature on the alkoxide chemistry, the reaction pathways and growth mechanisms were finally discussed with a special attention on the monomer formation rate, leading to the nucleation step. The polar, non-perovskite crystalline structure of LiNbO3 was also evidenced to play a major role in the nanocrystal shape anisotropy.
ABSTRACT
BACKGROUND: Harmonic Nanoparticles are a new family of exogenous markers for multiphoton imaging exerting optical contrast by second harmonic (SH) generation. In this tutorial, we present the application of Hyper-Rayleigh Scattering (HRS) for a quantitative assessment of the nonlinear optical properties of these particles and discuss the underlying theory and some crucial experimental aspects. METHODS: The second harmonic properties of BaTiO3, KNbO3, KiTiOPO4 (KTP), LiNbO3 and ZnO nanocrystals (NCs) are investigated by HRS measurements after careful preparation and characterization of colloidal suspensions. RESULTS: A detailed analysis of the experimental results is presented with emphasis on the theoretical background and on the influence of some experimental parameters including the accurate determination of the nanocrystal size and concentration. The SH generation efficiency and averaged nonlinear optical coefficients are then derived and compared for six different types of NCs. CONCLUSIONS: After preparation of colloidal NC suspensions and careful examination of their size, concentration and possible aggregation state, HRS appears as a valuable tool to quantitatively assess the SH efficiency of noncentrosymmetric NCs. All the investigated nanomaterials show high SH conversion efficiencies, demonstrating a good potential for bio-labelling applications.
