Optical Properties and Upconversion Luminescence of BaTiO3 Xerogel Structures Doped with Erbium and Ytterbium.

Erbium upconversion (UC) photoluminescence (PL) from sol-gel derived barium titanate (BaTiO3:Er) xerogel structures fabricated on silicon, glass or fused silica substrates has been studied. Under continuous-wave excitation at 980 nm and nanosecond pulsed excitation at 980 and 1540 nm, the fabricated structures demonstrate room temperature PL with several bands at 410, 523, 546, 658, 800 and 830 nm, corresponding to the 2H9/2 → 4I15/2, 2H11/2 → 4I15/2, 4S3/2 → 4I15/2, 4F9/2→ 4I15/2 and 4I9/2→ 4I15/2 transitions of Er3+ ions. The intensity of erbium UC PL increases when an additional macroporous layer of strontium titanate is used beneath the BaTiO3 xerogel layer. It is also enhanced in BaTiO3 xerogel films codoped with erbium and ytterbium (BaTiO3:(Er,Yb)). For the latter, a redistribution of the intensity of the PL bands is observed depending on the excitation conditions. A multilayer BaTiO3:(Er,Yb)/SiO2 microcavity structure was formed on a fused silica substrate with a cavity mode in the range of 650-680 nm corresponding to one of the UC PL bands of Er3+ ions. The obtained cavity structure annealed at 450 °C provides tuning of the cavity mode by 10 nm in the temperature range from 20 °C to 130 °C. Photonic application of BaTiO3 xerogel structures doped with lanthanides is discussed.

Detection of explosives in vapor phase by field asymmetric ion mobility spectrometry with dopant-assisted laser ionization.

Detection of low-volatile explosives in concentrations below 10-14 g/cm3 is a great challenge for portable ion mobility spectrometers (IMS) and field asymmetric IMS (FAIMS). We study the capabilities of FAIMS detector with ultraviolet laser ionization combined with organic additives (dopants) toluene and 1-methylnaphtalene to sense nitro-explosives: trinitrotoluene (TNT) and low-volatile cyclonite (RDX) and nitropentaerythritol (PETN). Differential mobility coefficients were measured for target ion peaks of TNT, RDX and PETN. Presence of dopants in the sample results in multiple growth of ion yield at laser intensities lower than 2 × 107 W/cm2. Limits of detection with dopant-assisted laser ionization were determined: 4.7 × 10-16 g/cm3 for RDX and 9.8 × 10-15 g/cm3 for PETN. Obtained results propose a way to further improve sensitivity of detectors along with improvement of portability of current laser-based FAIMS prototypes by using less powerful and smaller lasers.

Laser-stimulated desorption of organic molecules from surfaces, as a method of increasing the efficiency of ion mobility spectrometry analysis.

Application of laser-induced desorption was investigated as a method of increasing the efficiency of gas phase analyzers on principles of field asymmetric ion mobility spectrometry. Mass spectrometric data of investigations of laser desorption of pentaerythritoltetranitrate molecules and cyclotetramethylenetetranitramine molecules from quartz substrate under vacuum were obtained. Laser sources a Nd3+:YAG with nanosecond pulse duration (λ = 532 nm) and a continuous wave diode laser (λ = 440 nm) were used. It was shown that both laser sources have different desorption abilities. This is expressed in various time of appearance of desorbed products that is caused by different heating mechanisms of surface layer. The desorbed quantity under action of both laser sources exceeds the detection threshold for all modern gas phase analyzers. It should be noted that despite the presence of surface dissociation of explosives under laser radiation, the quantity of nondissociated molecules is large enough for detection by ion mobility and field asymmetric ion mobility spectrometers. The optimal parameters of laser radiation for effective removal (evaporation) molecules of low-volatile compounds from surfaces are defined. The conclusion about preferable use of a Nd3+:YAG laser for increasing the detection ability of detectors based on ion mobility spectrometry was made.

Active sampling system for gas-phase analyzers.

The approaches for increasing a contact-free sampling distance up to 40 cm for a field asymmetric ion mobility spectrometer were investigated and implemented by use both the vortex flow made by a rotating impeller and the laser desorption of traces of low volatile explosives. The sampling device for a laser-based field asymmetric ion mobility spectrometer including a high-speed rotating impeller was designed and built with help of computer simulation of vortex and analytical flows. The dependence of a signal of trinitrotoluene vapors on a rotational speed of an impeller was obtained. The optimization of analytical flow was performed. The effective sampling distance is increased up to 28 cm for trinitrotoulene vapors detection by a field asymmetric ion mobility spectrometer equipped with a rotating impeller. The distance can be increased up to 40 cm using laser irradiation of objects with traces of explosives. It was shown that under ambient conditions the efficient desorption of low-volatile explosives is achieved at laser intensity 107 W/cm2, wavelength λ = 266 nm, pulse energy about 1 mJ and pulse frequency not less than 10 Hz.

Controlled influence of quantum dots on purple membranes at interfaces.

The development of bio-sensitized nanofilms engineered from biomembrane components and inorganic nanoparticles is a promising field of colloid and interface science and technologies. Recent nano-bioengineering approaches employing quantum dots (QDs) permit the enhancement of the purple membrane (PM) "light-harvesting capacity" compared to native PMs. The influence of QDs on the PM properties, especially the bacteriorhodopsin (bR) photocycle, has been found that has both fundamental (mechanisms of photoreception) and applied implications (including the fabrication of hybrid bionanomaterials). Samples of PM-QD complexes capable of energy transfer and characterized by increased rates of M-intermediate formation and decay have been obtained. The modified bR photocycle kinetic parameters may be explained by changes in the PM interface upon QD adsorption. The increase and decrease in absorption at 410 nm (or photopotential) for PM-QD complexes are, on average, several times more rapid than for PM suspensions or PM dry films. These results provide a strong impetus for the development of nanomaterials with advanced properties.

The photophysics of porous silicon: technological and biomedical implications.

Although porous silicon (pSi) was first obtained in the mid-20th century, considerable interest in this material arose much later, due to the discovery of its room-temperature photoluminescence (PL). In the 1990s, most studies on pSi were focused on the analysis and explanation of its photoluminescent and electroluminescent characteristics and their potential practical applications. The latest advances in pSi research are related to its biocompatibility and biomedical applications. The discovery of singlet oxygen generation by pSi through nonradiative transfer of photoexcitation energy has opened new prospects for photodynamic therapy in vivo, and the discovery of laser desorption/ionization on pSi has paved the way for advanced approaches in mass-spectrometry. In this study, the main photophysical properties of pSi are reviewed, and a wide range of photo-processes characteristic of pSi and their practical implications are analyzed in terms of the general principles of energy and charge transfer. Special attention is paid to the possible applications of pSi and pSi-based nanocomposites in photonics, biophysics, medicine, and analytical chemistry.