Structural Stability, Vibrational Properties, and Photoluminescence in CsSnI3 Perovskite upon the Addition of SnF2.

The CsSnI3 perovskite and the corresponding SnF2-containing material with nominal composition CsSnI2.95F0.05 were synthesized by solid-state reactions and structurally characterized by powder X-ray diffraction. Both materials undergo rapid phase transformation upon exposure to air from the black orthorhombic phase (B-γ-CsSnI3) to the yellow orthorhombic phase (Y-CsSnI3), followed by irreversible oxidation into Cs2SnI6 within several hours. The phase transition occurs at a significantly lower rate in the SnF2-containing material rather than in the pure perovskite. The high hole-carrier concentration of the materials prohibits the detection of Raman signals for B-γ-CsSnI3 and induces a very strong plasmonic reflectance in the far-IR. In contrast, far-IR phonon bands and a rich Raman spectrum are observed for the Y-CsSnI3 modification below 140 cm-1 with weak frequency shift gradients versus temperatures between -95 and +170 °C. Above 170 °C, the signal is lost due to B-α-CsSnI3 re-formation. The photoluminescence spectra exhibit residual blue shifts and broadening as a sign of structural transformation initiation.

Calcium-modified clinoptilolite as a recovery medium of phosphate and potassium from anaerobically digested olive mill wastewater.

Olive mill wastewater (OMW) is characterized as a high-strength effluent due to the high organic load, low biodegradability, and presence of phytotoxic compounds. Most of the OMW treatment methods proposed, including adsorption, focus mainly on the reduction of chemical oxygen demand and recovery of polyphenols. Adsorption studies aiming at nutrient removal from OMW are very limited. In the present work, Ca(OH)2-treated zeolite (CaT-Z) in a granular form was used for simultaneous recovery of phosphate (PO43-) and potassium (K+) ions from two samples of anaerobically digested OMW. Nutrient adsorption was investigated as a function of contact time, pH and dilution of OMW with deionized water. The lower removal efficiency of phosphorus (P) by CaT-Z was observed at higher dilution ratios consisted of 3.125-6.25% OMW-1 and 5% OMW-2. The maximum P removal was 73.9% in 25% OMW-1 and 85.9% in 10% OMW-2. Potassium removal, as the predominant cation of OMW samples, increased from 17.3 to 46.1% in OMW-1 and from 15.1 to 57.7% in OMW-2 with increasing dilution. The maximum experimental adsorption capacities were 15.8 mg K and 2.14 mg P per gram of CaT-Z. Five sequential treatments of 50% OMW-2 with fresh CaT-Z at each stage ensured a cumulative removal of 87.5% for P and 74.9% for K. Adsorption kinetics were faster for K than for P. The plant-available P was found to be the predominant fraction on the loaded CaT-Z. Electron Probe Micro-analysis confirmed the enhanced content of K and P on the loaded CaT-Z, whereas X-ray mapping revealed the co-distribution of Ca and P. This study demonstrates the potential usage of CaT-Z as an immobilization medium of P and K from anaerobically treated OMW.

Nanographene oxide-TiO2 photonic films as plasmon-free substrates for surface-enhanced Raman scattering.

The development of nanostructured semiconductors with tailored morphology and electronic properties for surface-enhanced Raman scattering (SERS) has been attracting significant attention as a promising alternative to conventional coinage metal SERS substrates. In this work, functionalized TiO2 photonic crystals by graphene oxide nanocolloids (nanoGO) are demonstrated as highly sensitive, recyclable, plasmon-free SERS substrates that combine slow-photon amplification effects with the high adsorption capacity and surface reactivity of GO nanosheets. Comparative evaluation of photonic band gap engineered nanoGO-TiO2 inverse opal films was performed on methylene blue SERS detection under different laser excitations in combination with rigorous theoretical simulations of the photonic band structure. A very low detection limit of 6 × 10-7 M and an enhancement factor of 5 × 104 along with excellent self-cleaning performance and reusability could be achieved by the interplay of slow-photon effects assisted by interfacial charge transfer between the analyte and the nanoGO-TiO2 semiconducting substrate. Slow-photon management in combination with judicious engineering of chemical enhancement in photonic nanostructures is accordingly proposed as an advanced approach for the design of efficient dielectric SERS substrates.

Structure and properties of orthoborate glasses in the Eu2O3-(Sr,Eu)O-B2O3 quaternary.

The structure and properties of melt-quenched glasses and partially crystallized samples from the borate series (1-2x)Eu2O3-x((Eu,Sr)O-B2O3) were investigated in the supermodified regime of x < 0.5, using Raman, infrared (IR), electron spin resonance (ESR), and UV-vis absorption and fluorescence spectroscopic techniques. ESR and optical spectroscopy showed that, despite the strongly reducing synthesis conditions, the Eu(2+)/Eu(3+) equilibrium remained shifted to the side of trivalent Eu(3+). Stable and transparent overmodified borate glasses were produced for compositions with x ≥ 0.36. Higher europium oxide concentrations resulted in precipitation of crystalline Eu2Sr3(BO3)4 and EuBO3 phases, as traced by X-ray diffraction. Raman and IR spectroscopy showed that the metaborate configuration which is present at x = 0.46 transforms gradually, with increasing Eu2O3 levels, into orthoborate [BO3](3-) triangular units. At higher europium oxide content (x ≤ 0.36), the presence of Eu(3+) supports the formation of orthoborate [BØ2O2](3-) tetrahedral species. These units organize into [B3O9](9-) rings, which exist in equilibrium with [BO3](3-) triangles. As a consequence, distinct variations can be observed also in the macroscopic properties such as density, glass transition temperature, refractive index, optical basicity, and oxygen polarizability. This observation confirms previous findings on manganese-strontium borates with high modification levels.

Charge transport mechanisms and memory effects in amorphous TaNx thin films.

Amorphous semiconducting materials have unique electrical properties that may be beneficial in nanoelectronics, such as low leakage current, charge memory effects, and hysteresis functionality. However, electrical characteristics between different or neighboring regions in the same amorphous nanostructure may differ greatly. In this work, the bulk and surface local charge carrier transport properties of a-TaNx amorphous thin films deposited in two different substrates are investigated by conductive atomic force microscopy. The nitride films are grown either on Au (100) or Si [100] substrates by pulsed laser deposition at 157 nm in nitrogen environment. For the a-TaNx films deposited on Au, it is found that they display a negligible leakage current until a high bias voltage is reached. On the contrary, a much lower threshold voltage for the leakage current and a lower total resistance is observed for the a-TaNx film deposited on the Si substrate. Furthermore, I-V characteristics of the a-TaNx film deposited on Au show significant hysteresis effects for both polarities of bias voltage, while for the film deposited on Si hysteresis, effects appear only for positive bias voltage, suggesting that with the usage of the appropriate substrate, the a-TaNx nanodomains may have potential use as charge memory devices.