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A task-specific ionic liquid (IL) is employed as a structure directing agent for the synthesis of quantum cutting BaGdF5:Eu3+ nanophosphors. Herein, IL and temperature dependent quantum cutting is observed. Maximum (160%) and minimum (123%) quantum cutting efficiencies (QCEs) are obtained in the presence and absence of IL, respectively, at room temperature (295 K). However, at low temperature (10 K), the emission spectrum is dominated by Eu2+ 5d–4f emission which is further confirmed by X-ray excited luminescence study. It is also observed that decay kinetics recorded for Eu2+ 5d–4f emission demonstrate longer (with lifetime from 580 ns to 1.5 μs) and faster (with lifetime from 35 to 50 ns) decay components related to normal and surface quenched emission, respectively. In addition, maximum quantum yield (η = 73.5%) is obtained for the sample prepared in the presence of IL compared to that for the sample prepared without IL (η = 65%). The easy yet highly phase selective green synthesis of the materials is promising for large scale industrial application in nanothermometry as well as in environmentally benign energy efficient lighting. [ABSTRACT FROM AUTHOR]

An ionic liquid (IL)‐based solvothermal method is employed to prepare single‐phase, luminescent, cubic rare‐earth doped and silica‐coated BaF2 nanomaterials. High energy transfer efficiency (∼60%) from Ce3+ to Tb3+ for BaF2:Ce3+/Tb3+ nanoparticles dispersed in DMSO solution is observed. Furthermore, for the first time to the best of our knowledge, as‐prepared RE ion/s doped and silica‐coated BaF2 nanoparticles are used for the toxicological assessment on live zebrafish larvae. Interestingly, static exposure of these nanoparticles from 6 hpf till 96 hpf period at high concentration (70 mg/L) do not show any developmental anomalies as judged by bright‐field and birefringence optical imaging method which promises its large‐scale applications in imaging and other biological purposes.However, as a positive control, cypermethrin‐based pesticide could induce developmental defects at 0.1 mg/L concentration. It is worth mentioning that the concentration of BaF2 nanoparticles chosen in present study is much higher than the other nanoparticles reported so far. [ABSTRACT FROM AUTHOR]

Phase pure BaF2 doped with Ce3+ (0.1%) nanocrystals are synthesized using an ionic liquid (IL) ([C4mim][BF4]) assisted solvothermal method where the IL is not only used as a reaction medium and a capping agent, but also as a reaction partner. Subsequently, upon calcining the as-prepared nanocrystals at various temperatures (200, 400, 600 and 800 °C), athough the crystal phase remains the same, however, a significant change in the lattice strain and morphology is observed. Tensile strain appears in the nanocrystals calcined at temperatures up to 400 °C, but a reversal of the strain, i.e. compressive strain, takes place when calcination is performed at 600 °C and onwards. Nanoflakes are obtained until calcination at 400 °C. However on calcination at 600 °C and beyond, a drastic modification in the morphology is observed. Layer or step-like structures appear due to secondary nucleation of nanoparticles. Meanwhile, the photoluminescence (PL) intensity of Ce3+ ions gradually decreases with the calcination temperature and finally vanishes at 600 °C/800 °C. To investigate the reasons for the quenching of the PL intensity, thermally stimulated luminescence (TSL) and thermally stimulated exoelectron emission (TSEE) measurements are performed. The TSL and TSEE results indicate that in addition to the domination of deeper electron traps that appear as a high-temperature shift of TSEE glow peaks for both 600 °C and 800 °C, some new types of defects like F vacancies (F-centers) can be present, especially in the 800 °C calcined sample. The conditions leading to the quenching of Ce3+ luminescence in the nanoparticles are analyzed and discussed. [ABSTRACT FROM AUTHOR]

Phase pure BaF2 doped with Ce3+ (0.1%) nanocrystals are synthesized using an ionic liquid (IL) ([C4mim][BF4]) assisted solvothermal method where the IL is not only used as a reaction medium and a capping agent, but also as a reaction partner. Subsequently, upon calcining the as-prepared nanocrystals at various temperatures (200, 400, 600 and 800 °C), athough the crystal phase remains the same, however, a significant change in the lattice strain and morphology is observed. Tensile strain appears in the nanocrystals calcined at temperatures up to 400 °C, but a reversal of the strain, i.e. compressive strain, takes place when calcination is performed at 600 °C and onwards. Nanoflakes are obtained until calcination at 400 °C. However on calcination at 600 °C and beyond, a drastic modification in the morphology is observed. Layer or step-like structures appear due to secondary nucleation of nanoparticles. Meanwhile, the photoluminescence (PL) intensity of Ce3+ ions gradually decreases with the calcination temperature and finally vanishes at 600 °C/800 °C. To investigate the reasons for the quenching of the PL intensity, thermally stimulated luminescence (TSL) and thermally stimulated exoelectron emission (TSEE) measurements are performed. The TSL and TSEE results indicate that in addition to the domination of deeper electron traps that appear as a high-temperature shift of TSEE glow peaks for both 600 °C and 800 °C, some new types of defects like F vacancies (F-centers) can be present, especially in the 800 °C calcined sample. The conditions leading to the quenching of Ce3+ luminescence in the nanoparticles are analyzed and discussed. [ABSTRACT FROM AUTHOR]

Highly crystalline, phase pure Cu3P nanocrystals (NCs) have been successfully synthesized using ionic liquid-assisted solvothermal method at relatively low temperature (200 °C). Herein, ionic liquids (ILs) are used as a structure directing/templating agent. Effect of ILs and precursor concentration on crystal phase, crystallite size, lattice strain, morphology and grain size of Cu3P NCs is studied. In the presence of IL, crystallite size and lattice strain significantly change with changing the concentration of red phosphorus. For example, smaller crystallite size (38.5 nm) and compressive lattice strain are obtained when 10 times of red phosphorous is used. However, bigger size (41.9 nm) and tensile lattice strains are obtained for the lower concentration of phosphorous (5 times). At higher phosphorus concentration, hexagonal shaped micro-crystals with prominent grain are observed. HRTEM images reveal that spherical-shaped particles on further agglomeration through Ostwald ripening process form hexagonal-shaped bigger microstructures. However, on doping the rare-earth ions (RE3+ = Ce3+/Tb3+) in the Cu3P NCs show the green luminescence (at 542 nm) which is attributed to the emission of Tb3+ ions. To the best of our knowledge, this is the first report on rare-earth doped Cu3P nanoparticles and shows promise on the luminescence aspect of Cu3P nanomaterials along with its already existing plasmonic and semiconducting properties. [ABSTRACT FROM AUTHOR]

Nanoparticles with biomedical applications should be evaluated for their biocompatibility. Rare-earth doped nanoparticles with unique spectral properties are superior in vivo optical probes in comparison with quantum dots and organic dyes, however, studies describing their nano-bio interactions are still limited. Here, we have evaluated the nano-bio interactions of green-synthesized, phase-pure BaF 2 nanoparticles doped with rare-earth (RE 3+ = Ce 3+ /Tb 3+ ) ions using larval zebrafish. We found that zebrafish can tolerate a wide concentration range of these nanoparticles, as the maximal lethality was observed at very high concentrations (more than 200 mg L -1 ) upon five days of continuous exposure. At a concentration of 10 mg L -1 , at which Zn 2+ , Ti 4+ and Ag + nanoparticles are reported to be lethal to developing zebrafish, continuous exposure to our nanoparticles for four days produced no developmental anomalies, craniofacial defects, cardiac toxicity or behavioural abnormalities in the developing zebrafish larvae. We have also found that the doping of rare-earth ions has no major effect on these biomarkers. Interestingly, the function of acetylcholinesterase (AChE) and the cellular metabolic activity of whole zebrafish larvae remained unchanged, even during continuous exposure to these nanoparticles at 150 mg L -1 for four days; however, severe developmental toxicities were evident at this high concentration. Based on these results, we can conclude that the biocompatibility of rare-earth doped nanoparticles is concentration dependent. Not all biomarkers are sensitive to these nanoparticles. The high concentration-dependent toxicity occurs through a mechanism distinct from changes in the metabolic or AChE activity. The significance of these findings lies in using these nanoparticles for bioimaging applications and biomarker studies, especially for prolonged exposure times.

Phase tuned quantum confined In 2 S 3 nanocrystals are accessible solvothermally using task-specific ionic liquids (ILs) as structure directing agents. Selective tuning of size, shape, morphology, and, most importantly, crystal phase of In 2 S 3 is achieved by changing the alkyl side chain length, the H-bonding, and aromatic π-stacking ability of the 1-alkyl-3- methylimidazolium bromide ILs, [C n mim]Br (n = 2, 4, 6, 8, and 10). It is observed that crystallite size is significantly less when ILs are used compared to the synthesis without ILs keeping the other reaction parameters the same. At 150 °C, when no IL is used, pure tetragonal form of β-In 2 S 3 appears however in the presence of [C n mim]Br [n = 2,4], at the same reaction condition, a pure cubic phase crystallizes. However, in case of methylimidazolium bromides with longer pendant alkyl chains such as hexyl (C 6 ), octyl (C 8 ) or decyl (C 10 ), nanoparticles of the tetragonal polymorph form. Likewise, judicious choice of reaction temperature and precursors has a profound effect to obtain phase pure and morphology controlled nanocrystals. Furthermore, the adsorption driven catalytic and photocatalytic activity of as-prepared nanosized indium sulfide is confirmed by studying the degradation of crystal violet (CV) dye in the presence of dark and visible light. A maximum of 94.8% catalytic efficiency is obtained for the In 2 S 3 nanocrystals using tetramethylammonium bromide (TMAB) ionic liquid.