Krisjanis Smits

Advanced nanocrystalline ZrO 2 for optical oxygen sensors

It was shown that ZrO2 nanopowders and nanoceramics can be used as an optical oxygen sensor, where the luminescence signal is proportional to the partial oxygen pressure in gases. The nanopowders were obtained in a hydrothermal microwave driven process followed by annealing at 750°C. Nanoceramics were obtained by sintering at pressures up to 6 GPa and at 250°C so that grain growth did not occur. Luminescence of both materials depends linearly on the oxygen content in nitrogen-oxygen mixtures for 2.1% - 25 vol% oxygen content. For luminescence excitation using an electron beam, the luminescence intensity decreases as oxygen pressure increases. For excitation with a laser beam, the opposite effect is observed - the lower the oxygen pressure, the lower the luminescence signal. The experimental results are explained in terms of luminescence centers being distorted lattice sites close to vacancies.

Radiative Decay of Electronic Excitations in ZrO

The time-resolved luminescence was studied for ZrO2:Y single crystal and nanocrystals. The similar recombination centres were found in both single crystal and nanocrystals. Luminescence decay is within 200 ns in nanocrystals, whereas it extends to the microseconds in single crystal. It was shown that the defects responsible for transient absorption were not involved directly in radiative recombination process.

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Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+ doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions.

Nanocrystals and Macroscopic Single Crystals

Pure and Al3+ doped ZnO nanopowders were studied by means of time-resolved luminescence spectroscopy. The powders were synthesized by hydrothermal and plasma methods. These powders were used as a raw material for vaporization-condensation process inside the Solar reactor. The commercially available ZnO nanopowder was studied for a comparison. Exciton to defect band luminescence intensity ratio was estimated in different types of ZnO nanopowders. It was found that nanopowders with whiskers morphology show superlinear luminescence intensity depending on excitation density. The observed effect depends on the average nanoparticle size and on the powder morphology.

Doped zirconia phase and luminescence dependence on the nature of charge compensation

This study reports on the synthesis and characterisation of two- and three-component visible light active photocatalytic nanoparticle heterostructures, based on TiO2 and NiFe2O4 and sensitized with Ag. We observe that a Ag content as small as 1 at% in the TiO2/NiFe2O4 heterostructure increases by more than an order of magnitude the rate constant for the visible light photocatalytic process. We rationalise this in terms of the measured structure and electronic structure data of the binary and ternary combinations of the component materials and focus on details, which show that an optimised deposition sequence is vital for attaining high values of photocatalytic efficiency, because the charge transfer across the interfaces appears to be sensitive to where the Ag is loaded in the heterostructure. The overall higher visible light photocatalytic activity of the TiO2/Ag/NiFe2O4 heterostructure was observed and is attributed to enhanced charge carrier separation efficiency and migration via vectorial electron transfer.

The Luminescence Properties of ZnO nanopowders

Nowadays a large variety of applications are based on solid nanoparticles dispersed in liquids-so called nanofluids. The interaction between the fluid and the nanoparticles plays a decisive role in the physical properties of the nanofluid. A novel approach based on the nonradiative energy transfer between two small luminescent nanocrystals (GdVO4 :Nd3+ and GdVO4 :Yb3+ ) dispersed in water is used in this work to investigate how temperature affects both the processes of interaction between nanoparticles and the effect of the fluid on the nanoparticles. From a systematic analysis of the effect of temperature on the GdVO4 :Nd3+ → GdVO4 :Yb3+ interparticle energy transfer, it can be concluded that a dramatic increase in the energy transfer efficiency occurs for temperatures above 45 °C. This change is properly explained by taking into account a crossover existing in diverse water properties that occurs at about this temperature. The obtained results allow elucidation on the molecular arrangement of water molecules below and above this crossover temperature. In addition, it is observed that an energy transfer process is produced as a result of interparticle collisions that induce irreversible ion exchange between the interacting nanoparticles.

Ag sensitized TiO2 and NiFe2O4 three-component nanoheterostructures: synthesis, electronic structure and strongly enhanced visible light photocatalytic activity

Colorimetric gas sensing is demonstrated by thin films based on ultrasmall TiO2 nanoparticles (NPs) on Si substrates. The NPs are bound into the film by p-toluenesulfonic acid (PTSA) and the film is made to absorb volatile organic compounds (VOCs). Since the color of the sensing element depends on the interference of reflected light from the surface of the film and from the film/silicon substrate interface, colorimetric detection is possible by the varying thickness of the NP-based film. Indeed, VOC absorption causes significant swelling of the film. Thus, the optical path length is increased, interference wavelengths are shifted and the refractive index of the film is decreased. This causes a change of color of the sensor element visible by the naked eye. The color response is rapid and changes reversibly within seconds of exposure. The sensing element is extremely simple and cheap, and can be fabricated by common coating processes.

Unveiling Molecular Changes in Water by Small Luminescent Nanoparticles.

Nanomanipulation experiments were carried out on nanodumbbells (NDs) to study their kinetic behavior and tribological properties. Ag, Au and Cu NDs were produced by laser-induced melting of corresponding nanowires (NWs). NDs were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Manipulation experiments were performed first with atomic force microscope (AFM) at ambient conditions, and then inside SEM at high vacuum conditions. Different regimes of motion were observed. In-plane and out-of-substrate-plane rotation were identified as the most preferred motion types of NDs.

Colorimetric gas detection by the varying thickness of a thin film of ultrasmall PTSA-coated TiO2 nanoparticles on a Si substrate

The characteristics and sinterability of the Al2O3-ZrO2(Y2O3) nanoparticles produced by simple and effective microwave and molten salts methods and processed by using spark plasma sintering were studied and compared. The crystalline powders with the specific surface area in the range of 72–108 m2/g and crystallite size of 5–13 nm were obtained by calcination of samples prepared by both methods at 800 °C. The content of t-ZrO2 phase depends on concentration of Al2O3, Y2O3 and on calcination temperature but the impact of the preparation method is insignificant. The phase transition of tetragonal ZrO2 to monoclinic for the samples without Y2O3 started at 1000 °C though it was incomplete in the case of high content of Al2O3. The bulk materials with relative density of 86.1–98.7% were fabricated by the spark plasma sintering method at 1500–1600 °C depending on the content of Al2O3 and Y2O3.