Truly alloyed PbS(x)Se(1-x) (x = 0-1) nanocrystals (∼5 nm in size) have been prepared, and their resulting optical properties are red-shifted systematically as the sulfur content of the materials increases. Their optical properties are discussed using a modified Vegard's approach and the bowing parameter for these nanoalloys is reported for the first time. The alloyed structure of the nanocrystals is supported by the energy-filtered transmission electron microscope images of the samples, which show a homogeneous distribution of sulfur and selenium within the nanocrystals. X-ray photoelectron spectroscopy studies on ligand-exchanged nanocrystals confirmed the expected stoichiometry and various oxidized species.

The influence of the nanocrystal matrix on the optical properties of lanthanide dopants is investigated with europium ions used as local crystal field probes. The analysis is performed on small NaYF 4 and NaGdF 4 nanocrystals obtained by the thermolysis of the corresponding metal trifluoroacetates. An important role in the synthesis is played by trioctylphosphine oxide which induces the crystallization of nanocrystals with small diameters ($5 to 6 nm). In such small particles, the energy transfer from gadolinium to europium ions is studied with photoluminescence, photoluminescence excitation and time-resolved experiments. We demonstrate that excited gadolinium ions efficiently transfer their energy to europium, and their photoluminescence spectra depend on the nanocrystal size. This is contrary to the direct excitation of Eu 3+ ions, which produces size-dependent emission corresponding to the surface to volume ratio of europium sites. Finally, we propose that Gd 3+ ions transfer their energy mainly to the Eu 3+ in the core of the nanocrystals. These observations provide a base for the optically controlled emission from only the core of the nanocrystals.

Fundamentals of quantum dots (QDs) sensing phenomena show the predominance of these fluorophores over standard organic dyes, mainly because of their unique optical properties such as sharp and tunable emission spectra, high emission quantum yield and broad absorption. Moreover, they also indicate no photo bleaching and can be also grown as no blinking emitters. Due to these properties, QDs may be used e.g., for multiplex testing of the analyte by simultaneously detecting multiple or very weak signals. Physico-chemical mechanisms used for analyte detection, like analyte stimulated QDs aggregation, nonradiative Förster resonance energy transfer (FRET) exhibit a number of QDs, which can be applied in sensors. Quantum dots-based sensors find use in the detection of ions, organic compounds (e.g., proteins, sugars, volatile substances) as well as bacteria and viruses.

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The purely hexagonal phase of ultrasmall (~10 nm) NaYF(4) nanocrystals (NCs), containing different Eu concentrations, has been obtained by a modified co-thermolysis method. Detailed investigations of the excitation and relaxation mechanisms of the Eu ions in such NCs are reported. Based on the photoluminescence excitation, absorbance, photoluminescence and emission decay times measured as a function of the excitation wavelengths, it has been shown that two Eu sites with different excitation and relaxation characteristics are present in the case of ultrasmall NaYF(4) NCs. It has been shown that, when the Eu concentration increases, strong ion-ion interactions influence the relaxation phenomena in Eu ions, changing their optical properties. Moreover, these ion-ion interactions enable connections between the surface ions and the internal ones via energy transfer from the surface to the NCs core. Furthermore, it has been proposed that the different kinetic properties of the surface Eu ions are mainly caused by the formation of a charge transfer state between the ions and ligand groups attached to the NCs surface.

We examined in detail the optical properties of NaYF4:Eu3+ nanocrystals of ~9 nm in diameter. For such small nanocrystals roughly 17 % of Y3+ ions occupy surface sites and can be efficiently substituted by optically active Eu3+ ions. In order to determine the influence of surface Eu3+ on the optical properties of the whole nanocrystal, small β-NaYF4:Eu3+ nanocrystals with homogenous size distribution were prepared using trioctylphosphine oxide as a coordinating solvent. In order to passivate the surface sites, a thin β-NaYF4 shell was further deposited on nanocrystals core and the optical properties were investigated. For this purpose absorption, photoluminescence, photoluminescence excitation, and photoluminescence decays were recorded and analyzed. The optical characteristics of surface Eu3+ significantly diminish for surface passivated nanocrystals. We calculated the increase of quantum yield to the value of 64 % when NaYF4:Eu3+ core was capped by undoped shell. The optical spectroscopy techniques were shown to be sufficient in determination of surface passivation of nanocrystals with high surface to volume ratio.

In this work we report co-thermolysis as a suitable method for nanomaterial synthesis which allows the creation of hexagonal upconverting nanocrystals, NaGdF4:Yb(3+),Er(3+), in a wide range of sizes (20-120 nm). Only a very high Yb(3+) concentration (above 70%) results in pure cubic-phase nanocrystals with irregular shape. Additionally, we showed that the impact of Yb(3+), Er(3+) and Gd(3+) ions on the size and optical properties of nanocrystals is significant. We found that the main changes in optical properties do not depend on the nanocrystal size mostly, but are determined by the ion-ion interactions which include both Er(3+)-Er(3+) and Er(3+)-Yb(3+) cross relaxation.

Multicolor emission is reported from ultrasmall (<10 nm) b-NaYF4:Eu,Tb nanocrystals depending on the excitation wavelengths or emission detection delay time. Detailed optical investigations of three samples (NaYF4:Eu, NaYF4:Tb and NaYF4:Eu,Tb) obtained by a co-thermolysis method have been carried out. Photoluminescence, photoluminescence excitation and emission decay time obtained at different excitation wavelengths have been measured. Excitation mechanisms of Eu and Tb ions have been explained based on the experimental results and calculations using Judd-Ofelt theory. It has been shown that efficient energy transfer from Tb to Eu ions accounts for the efficient red emission of NaYF4:Tb,Eu nanocrystals. Experimental detailsSodium trifluoroacetate Na(CF 3 COO) (98%), yttrium(III) trifluoroacetate hydrate Y(CF 3 COO) 3 $xH 2 O (99%), europium(III)