ABSTRACT
Using first-principles calculations and La3Te4 as an example of an n-type gapped metal, we demonstrate that gapped metals can develop spontaneous defect formation resulting in off-stoichiometric compounds. Importantly, these compounds have different free carrier concentrations and can be realized by optimizing the synthesis conditions. The ability to tune the free carrier concentration allows the tailoring of the intraband and interband transitions, thus controlling the optoelectronic properties of materials in general. Specifically, by realizing different off-stoichiometric La3-xTe4 compounds, it is possible to reach specific crossings of the real part of the dielectric function with the zero line, reduce the plasma frequency contribution to the absorption spectra, or, more generally, induce metal-to-insulator transition. This is particularly important in the context of optoelectronic, plasmonic, and epsilon-near-zero materials, as it enables materials design with a target functionality. While this work is limited to the specific gapped metal, we demonstrate that the fundamental physics is transferable to other gapped metals and can be generally used to design a wide class of new optoelectronic/plasmonic materials.
ABSTRACT
Doping glass with semiconductors, particularly with nanostructured semiconductors, has attracted attention due to the large optical absorption cross-sections of the latter. Based on this property, Ni[Formula: see text] (5 wt%) doped phosphate glass and Zn[Formula: see text]Ni[Formula: see text]Te (x = 0.5, 1.0, 5.0 and 10.0 wt% of Ni[Formula: see text]) nanocrystals (NCs) doped phosphate glasses (GCs) were prepared by fusion method and subsequent heat treatment. Influence of Ni[Formula: see text] on structural, thermo-optical and third-order nonlinear optical properties have been analysed through various spectroscopic characterizations. The XRD pattern of the glass (G) exhibits the amorphous nature of the host material while GCs exhibit not only amorphous halo but also the presence of quantum dots (QDs) or nanocrystals (NCs) phases. TEM analysis of the studied GCs samples confirm the presence of quantum dots (QDs) and bulk NCs with an average diameter of approximately 4.2 [Formula: see text] 0.3 nm and 13.4 [Formula: see text] 0.2 nm, respectively. Several phosphate groups were observed and reported from Raman and FTIR-ATR spectra. The absorption band positions confirmed that Ni[Formula: see text] ions resemble to the octahedral symmetry. The intensity of absorption band around 1352 nm ([Formula: see text]T[Formula: see text](F) [Formula: see text] [Formula: see text]A[Formula: see text](F)) increased with the increase of Ni[Formula: see text] in GCs which is an indicative of the [Formula: see text]Ni[Formula: see text] coordination. The emission properties such as emission cross-sections ([Formula: see text]) full width at half maxima (FWHM) for the [Formula: see text]T[Formula: see text](D) [Formula: see text] [Formula: see text]T[Formula: see text](F) (visible) and [Formula: see text]A[Formula: see text](F) [Formula: see text] [Formula: see text]T[Formula: see text](F) (near-infrared) emission transitions were reported. Among the glass-containing semiconductor nanocrystals (GCs), the emission cross-sections in GC4 sample (x = 10% of Ni[Formula: see text]) are the largest for both the visible (11.88 [Formula: see text] 10[Formula: see text] cm[Formula: see text]) and infrared (0.98 [Formula: see text] 10[Formula: see text] cm[Formula: see text]) transitions. Thermal diffusivity (D), thermal conductivity (K) and temperature dependent optical path length change (ds/dT) were obtained through time-resolved thermal lens (TL) and thermal relaxation (TR) methods. The D and K parameters do not change significantly with increase of Ni[Formula: see text] ions (0.5-5%) in GCs. Nonlinear-refractive index and nonlinear absorption of the studied samples were also obtained using femtosecond Z-scan technique. The increase of nonlinear absorption coefficient ([Formula: see text]) is observed from GC2 (2.53 [Formula: see text] 10[Formula: see text] cm/W) to GC4 (7.98 [Formula: see text] 10[Formula: see text] cm/W). The GC4, sample with 10 wt% of Ni[Formula: see text], showed the lowest ds/dT (1.22 [Formula: see text] 10[Formula: see text] K[Formula: see text]) with good lasing (FOM and emission cross-sections) and nonlinear absorption properties suggesting that it can be a good candidate for visible-red emission light conversion in LED technology.
