We explore the potential of Tb- and Yb-doped InVO₄, InTaO₄, and InNbO₄ for applications as phosphors for light-emitting sources. Doping below 0.2% barely change the crystal structure and Raman spectrum but provide optical excitation and emission properties in the visible and near-infrared (NIR) spectral regions. From optical measurements, the energy of the first/second direct band gaps was determined to be 3.7/4.1 eV in InVO₄, 4.7/5.3 in InNbO₄, and 5.6/6.1 eV in InTaO₄. In the last two cases, these band gaps are larger than the fundamental band gap (being indirect gap materials), while for InVO₄, a direct band gap semiconductor, the fundamental band gap is at 3.7 eV. As a consequence, this material shows a strong self-activated photoluminescence centered at 2.2 eV. The other two materials have a weak self-activated signal at 2.2 and 2.9 eV. We provide an explanation for the origin of these signals taking into account the analysis of the polyhedral coordination around the pentavalent cations (V, Nb, and Ta). Finally, the characteristic green (⁵D₄ → ⁷F_J) and NIR (²F_5/2 → ²F_7/2) emissions of Tb³⁺ and Yb³⁺ have been analyzed and explained.

The sensitization of Eu(III) luminescence by the phosphoramide and arylphosphonic diamide ligands OP(NMe₂)₂Ind, OP(NMe₂)₂Cbz, OP(NMe₂)₂Ph, OP(NMe₂)₂(1-Naph) and OP(NMe₂)₂(2-Naph) (Ind = indol-1-yl; Ph = phenyl; Cbz = carbazol-9-yl; 1-Naph = naphtalen-1-yl; 2-Naph = naphtalen-2-yl) was verified by coordination to the [Eu(NO₃)₃] metal fragment. The emission spectra of the corresponding complexes showed only the 5D₀ → 7F_J transitions of the metal centre, with the exception of the carbazolyl derivative. Some of the ligands were also able to sensitize Tb(III) luminescence, in agreement with the triplet state energies estimated from the phosphorescence spectra of the analogous Gd(III) nitrates. On the basis of the photoluminescence results achieved using nitrate as ancillary ligand, heptacoordinate Eu(III) complexes having general formula [Eu(β-dike)₃L] (β-dike = dibenzoylmethanate, tenoyltrifluoroacetonate; L = phosphoramide or arylphosphomic diamide ligand) were prepared and characterized. All the complexes exhibited bright red emission upon excitation with near-UV and violet-blue light, with intrinsic quantum yields ranging between 18 and 36%.

In this paper, the investigation of energy transfer efficiency in Tb³⁺-Yb³⁺ co-doped SiO₂-HfO₂ glass and glass-ceramic waveguides is presented. Cooperative energy transfer between these two ions allows to cut one UV or 488 nm photon in two 980 nm photons and could have important applications in improving the performance of photovoltaic solar cells. Thin films with different molar concentrations of rare earths, up to a total concentration of 21%, were prepared by a sol-gel route, using dip-coating deposition technique on SiO₂ substrates. The ratio between Yb³⁺ and Tb³⁺ ions in all the prepared thin films is constant and equal to 4. The energy transfer between Tb³⁺ and Yb³⁺ ions in glass and glass-ceramic waveguides shows the higher efficiency for glass-ceramic with a maximum quantum transfer efficiency of about 190% for the sample containing 19% of rare earths.

The present work introduces ternary Ln(III) (Ln = Eu, Yb, Lu) complexes with thenoyltriflouro1,3-diketonate (TTA−) and phosphine oxide derivative (PhO) as building blocks for core-shell nanoparticles with both Eu(III)- or Yb(III)-centered luminescence and the dual Eu(III)-Yb(III)-centered luminescence. Solvent-mediated self-assembly of the complexes is presented herein as the procedure for formation of Eu–Lu, Eu–Yb and Yb–Lu heterometallic or homometallic cores coated by hydrophilic polystyrenesulfonate-based shells. Steady state and time resolved Eu-centered luminescence in homolanthanide and heterolanthanide Eu–Lu and Eu–Yb cores is affected by Eu → Eu and Eu → Yb energy transfer due to a close proximity of the lanthanide blocks within the core of nanoparticles. The Eu → Yb energy transfer is highlighted to be the reason for the enhancement of the NIR Yb-centered luminescence. Efficient cellular uptake, low cytotoxicity towards normal and cancer cells, and sensing ability of Eu–Yb nanoparticles on lomefloxacin additives via both red and NIR channels make them promising as cellular imaging agents and sensors.

In order to design and tailor materials for a specific application like gas sensors, the synthesis route is of great importance. Undoped and rhodium-doped barium titanate powders were successfully synthesized by two routes; oxalate route and classic route (a modified conventional route where solid-state reactions and thermal evaporation induced precipitation takes place). Both powders were calcined at different temperatures. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX) and Brunauer-Emmet-Teller (BET) analyses are employed to identify the phases and polymorphs, to determine the morphology, the chemical composition and the specific surface area of the synthesized materials, respectively. The so-called oxalate route yields pure BaTiO₃ phase for undoped samples at 700 °C and 900 °C (containing both cubic and tetragonal structures), while the classic route-synthesized powder contains additional phases such as BaCO₃, TiO₂ and BaTi₂O₅. Samples of both synthesis routes prepared by the addition of Rh contain no metallic or oxide phase of rhodium. Instead, it was observed that Ti was substituted by Rh at temperatures 700 °C and 900 °C and there was some change in the composition of BaTiO₃ polymorph (increase of tetragonal structure). Heat-treatments above these temperatures show that rhodium saturates out of the perovskite lattice at 1000 °C, yielding other secondary phases such as Ba₃RhTi₂O₉ behind. Well-defined and less agglomerated spherical nanoparticles are obtained by the oxalic route, while the classic route yields particles with an undefined morphology forming very large block-like agglomerates. The surface area of the synthesized materials is higher with the oxalate route than with the classic route (4 times at 900 °C). The presence of the oxalate ligand with its steric hindrance that promotes the uniform distribution and the homogeneity of reactants could be responsible for the great difference observed between the powders prepared by two preparation routes.

The Cu(I) coordination polymer [Cu₃(μ³-I)₃(μ-btz^Me)(NCCH₃)]n (btz^Me= 1-methyl-1H-benzotriazole) was prepared and characterized by X-Ray diffraction. The compound showed strong green emission upon excitation with wavelengths below 475 nm, with lifetime of 47 μs. The emission was attributed to ³(X,M)LCT transition on the basis of experimental data and DFT calculations.

Bright and nontoxic quantum dots (QDs) are highly desirable in a variety of applications, from solid-state devices to luminescent probes in assays. However, the processability of these species is often curbed by their surface chemistry, which limits their dispersibility in selected solvents. This renders a surface modification step often mandatory to make the QDs compatible with the solvent of interest. Here, we present a new synthetic approach to produce CuInS₂ QDs compatible with organic polar solvents and readily usable for the preparation of composite materials. 3-Mercaptopropyl trimethoxysilane (MPTS) was used simultaneously as solvent, sulfur source, and capping agent for the QD synthesis. The synthesized QDs possessed a maximum photoluminescence quantum yield around 6%, reaching approximately 55% after growing a ZnS shell. The partial condensation of MPTS molecules on the surface of QDs was probed by solid-state nuclear magnetic resonance, whose results were used to interpret the interaction of the QDs with different solvents. To prove the versatility of the developed QDs, imparted by the thiolated silane molecules, we prepared via straightforward procedures two nanocomposites of practical interest: (i) silica nanoparticles decorated with QDs and (ii) an inexpensive polymeric film with embedded QDs. We further demonstrate the potential of this composite film as a luminescence thermometer operational over a broad temperature interval, with relative thermal sensitivity above 1% K^–1 in the range of biological interest.

Room temperature atmospheric plasma treatments are widely used to activate and control chemical functionalities at surfaces. Here, we investigated the effect of atmospheric pressure plasma jet (APPJ) treatments in reducing atmosphere (Ar/1‰ H2 mixture) on the photoluminescence (PL) properties of single crystal ZnO nanorods (NRs) grown through hydrothermal synthesis on fluorine-doped tin oxide glass substrates. The results were compared with a standard annealing process in air at 300 °C. Steady-state photoluminescence showed strong suppression of the defect emission in ZnO NRs for both plasma and thermal treatments. On the other side, the APPJ process induced an increase in PL quantum efficiency (QE), while the annealing does not show any improvement. The QE in the plasma treated samples was mainly determined by the near band-edge emission, which increased 5–6 fold compared to the as-prepared samples. This behavior suggests that the quenching of the defect emission is related to the substitution of hydrogen probably in zinc vacancies (VZn), while the enhancement of UV emission is due to doping originated by interstitial hydrogen (Hi), which diffuses out during annealing. Our results demonstrate that atmospheric pressure plasma can induce a similar hydrogen doping as ordinarily used vacuum processes and highlight that the APPJ treatments are not limited to the surfaces but can lead to subsurface modifications. APPJ processes at room temperature and under ambient air conditions are stable, convenient, and efficient methods, compared to thermal treatments to improve the optical and surface properties of ZnO NRs, and remarkably increase the efficiency of UV emission.

In this paper we report the study of down-shifting silica-zirconia glass and glass-ceramic films doped by Tb³⁺ ions and Ag nanoaggregates, which combine the typical spectral properties of the rare-earth-ions with the broadband sensitizing effect of the metal nanostructures. Na-Tb co-doped silica-zirconia samples were obtained by a modified sol-gel route. Dip-coating deposition followed by annealing for solvent evaporation and matrix densification were repeated several times, obtaining a homogeneous crack-free film. A final treatment at 700 °C or 1000 °C was performed to control the nanoscale structural properties of the samples, resulting respectively in a glass (G) or a glass-ceramic (GC), where tetragonal zirconia nanocrystals are surrounded by an amorphous silica matrix. Ag introduction was then achieved by ion-exchange in a molten salt bath, followed by annealing in air to control the migration and aggregation of the metal ions. The comparison of the structural, compositional and optical properties are presented for G and GC samples, providing evidence of highly efficient photoluminescence enhancement in both systems, slightly better in G than in GC samples, with a remarkable increase of the green Tb³⁺ PL emission at 330 nm excitation: 12 times for G and 8 times for GC samples. Furthermore, after Ag-exchange, the shape of Tb³⁺ excitation resembles the one of Ag ions/nanoaggregates, with a broad significant absorption in the whole UV-blue spectral region. This broadband enhanced downshifting could find potential applications in lighting devices and in PV solar cells.

Rare earth doped materials play a very important role in the development of many photonic devices, such as optical amplifiers and lasers, frequency converters, solar concentrators, up to quantum information storage devices. Among the rare earth ions, ytterbium is certainly one of the most frequently investigated and employed. The absorption and emission properties of Yb³⁺ ions are related to transitions between the two energy levels ²F_7/2 (ground state) and ²F_5/2 (excited state), involving photon energies around 1.26 eV (980 nm). Therefore, Yb³⁺ cannot directly absorb UV or visible light, and it is often used in combination with other rare earth ions like Pr³⁺, Tm³⁺, and Tb³⁺, which act as energy transfer centres. Nevertheless, even in those co-doped materials, the absorption bandwidth can be limited, and the cross section is small. In this paper, we report a broadband and efficient energy transfer process between Ag dimers/multimers and Yb³⁺ ions, which results in a strong PL emission around 980 nm under UV light excitation. Silica-zirconia (70% SiO₂-30% ZrO₂) glass-ceramic films doped by 4 mol.% Yb³⁺ ions and an additional 5 mol.% of Na₂O were prepared by sol-gel synthesis followed by a thermal annealing at 1000 °C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 430 °C to induce the migration and aggregation of the metal. The structural, compositional, and optical properties were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag dimers/multimers, which could have important applications in different fields, such as PV solar cells and light-emitting near-infrared (NIR) devices.