Luiz G. Jacobsohn

Preparation and Characterization of Rare Earth Doped Fluoride Nanoparticles

This paper reviews the synthesis, structure and applications of metal fluoride nanoparticles, with particular focus on rare earth (RE) doped fluoride nanoparticles obtained by our research group. Nanoparticles were produced by precipitation methods using the ligand ammonium di-n-octadecyldithiophosphate (ADDP) that allows the growth of shells around a core particle while simultaneously avoiding particle aggregation. Nanoparticles were characterized on their structure, morphology, and luminescent properties. We discuss the synthesis, properties, and application of heavy metal fluorides; specifically LaF3:RE and PbF2, and group IIA fluorides. Particular attention is given to the synthesis of core/shell nanoparticles, including selectively RE-doped LaF3/LaF3, and CaF2/CaF2 core/(multi-)shell nanoparticles, and the CaF2-LaF3 system.

Fluoride nanoscintillators

A preliminary investigation of the scintillation response of rare earth-doped fluoride nanoparticles is reported. Nanoparticles of CaF2 : Eu, BaF2 : Ce, and LaF3 : Eu were produced by precipitation methods using ammonium di-n-octadecyldithiophosphate (ADDP) as a ligand that controls growth and lessens agglomeration. The structure and morphology were characterized by means of X-ray diffraction and transmission electron microscopy, while the scintillation properties of the nanoparticles were determined by means of X-ray and 241 Am irradiation. The unique aspect of scintillation of nanoparticles is related to the migration of carriers in the nanoscintillator. Our results showed that even nanoparticles as small as ∼4nm in size effectively scintillate, despite the diffusion length of e-h pairs being considerably larger than the nanoparticles themselves, and suggest that nanoparticles can be used for radiation detection.

Structural and optical properties of rare earth–doped (Ba0.77Ca0.23)1−x(Sm, Nd, Pr, Yb)xTiO3

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba0.77Ca0.23TiO3 (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 °C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO6 octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of...

Stability of Grafted Polymer Nanoscale Films toward Gamma Irradiation

The present article focuses on the influence of gamma irradiation on nanoscale polymer grafted films and explores avenues for improvements in their stability toward the ionizing radiation. In terms of applications, we concentrate on enrichment polymer layers (EPLs), which are polymer thin films employed in sensor devices for the detection of chemical and biological substances. Specifically, we have studied the influence of gamma irradiation on nanoscale poly(glycidyl methacrylate) (PGMA) grafted EPL films. First, it was determined that a significant level of cross-linking was caused by irradiation in pure PGMA films. The cross-linking is accompanied by the formation of conjugated ester, carbon double bonds, hydroxyl groups, ketone carbonyls, and the elimination of epoxy groups as determined by FTIR. Polystyrene, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, dimethylphenylsilanol, BaF2, and gold nanoparticles were incorporated into the films and were found to mitigate different aspects of the radiation damage.

Scintillation of rare earth doped fluoride nanoparticles

The scintillation response of rare earth (RE) doped core/undoped (multi-)shell fluoride nanoparticles was investigated under x-ray and alpha particle irradiation. A significant enhancement of the scintillation response was observed with increasing shells due: (i) to the passivation of surface quenching defects together with the activation of the REs on the surface of the core nanoparticle after the growth of a shell, and (ii) to the increase of the volume of the nanoparticles. These results are expected to reflect a general aspect of the scintillation process in nanoparticles, and to impact radiation sensing technologies that make use of nanoparticles.

Spectral engineering of LaF3:Ce3+ nanoparticles: The role of Ce3+ in surface sites

Due to the high surface-to-volume ratio, luminescence centers on the surface have relative dominance in the overall spectral response of nanoparticles. The luminescence of LaF3:Ce3+ nanoparticles was investigated in the spectral and temporal domains with a particular focus on the role of Ce3+ on the surface. These nanoparticles present two luminescence bands at 4.10 eV and 4.37 eV attributed to Ce3+ transitions from the 5d level to the spin-orbit split 4f ground levels 2F5/2 and 2F7/2, in addition to a low-energy band at 3.62 eV that has been attributed to Ce3+ ions residing in perturbed sites. The growth of up to three undoped shells, ca. 0.9 nm thick each, around the core promoted a progressive enhancement of luminescence output, concomitant with an increase in the fluorescence lifetime due to the weakening of energy transfer through multipolar interaction between Ce3+ in the core and quenching defects on the surface. Also, the growth of the first shell led to a decrease in the relative intensity of the...

Synthesis, structure, and scintillation of Ce-doped gadolinium oxyorthosilicate nanoparticles prepared by solution combustion synthesis

The synthesis of Ce-doped Gd oxyorthosilicate nanoparticles using the solution combustion synthesis (SCS) method was investigated as a function of the amount of SiO2 in the precursor mixture. The SCS product consists of mixtures of Ce-doped Gd2SiO5, Gd4.67(SiO4)3O, and Gd2O3, whose relative concentrations depend on the amount of SiO2 in the precursor mixture; the synthesis of GSO:Ce was obtained with a reduction by 30% of the SiO2 content. Accordingly, this is the brightest material produced, with a photoluminescence signal that is comparable to that obtained from the bulk sample. Thermoluminescence (TL) results showed a considerably lower concentration of trapping defects in the nanoparticles than in the bulk sample. A previous study [E. G. Yukihara, L. G. Jacobsohn, M. W. Blair, B. L. Bennett, S. C. Tornga, and R. E. Muenchausen, J. Lumin. 130, 2309-2316 (2010)] reporting a comparison between photoluminescence and scintillation measurements, coupled to the TL characterization, suggests that surfaces pla...

Investigation on the color center distribution in LiF thin films

The F2 center depth distribution in LiF thin films irradiated by 15 and 30 keV electron beams was obtained experimentally by means of optical absorption measurements of multilayered LiF/KBr films. Monte Carlo simulations of the incidence of electron beams in LiF were also carried out to provide the dissipated energy and the fluor ionization depth profiles for comparison with the experimental data. The ionization and the dissipated energy profiles have essentially the same shape, with their maxima at a depth of 41±5% of the electron range. The F2 distributions could be described by Gaussian distributions centered at depths of 1.5 and 1.6 μm for 15 and 30 keV irradiation, respectively.The F2 center depth distribution in LiF thin films irradiated by 15 and 30 keV electron beams was obtained experimentally by means of optical absorption measurements of multilayered LiF/KBr films. Monte Carlo simulations of the incidence of electron beams in LiF were also carried out to provide the dissipated energy and the fluor ionization depth profiles for comparison with the experimental data. The ionization and the dissipated energy profiles have essentially the same shape, with their maxima at a depth of 41±5% of the electron range. The F2 distributions could be described by Gaussian distributions centered at depths of 1.5 and 1.6 μm for 15 and 30 keV irradiation, respectively.

Permeation and optical properties of YAG:Er3+ fiber membrane scintillators prepared by novel sol–gel/electrospinning method

An electrospinning method for fabrication of the YAG:Er3+ fibrous membrane is developed and the scintillation properties of the obtained membranes were examined. A homogeneous precursor YAG sol was synthesized allowing to control the sol–gel transition. The synthesized precursor allows one to achieve the 5 wt.% level of fiber doping with Er without formation of any undesired crystalline phases. It was found that the relative humidity had a strong impact on the fiber microstructure. The fibers obtained at the low relative humidity level (~30%) had almost straight cylindrical shape with an average diameter of ~590 nm, their surface was smooth. The shape of fibers obtained at the high relative humidity level (~50%) deviated from the straight cylindrical shape and the average diameter was larger, ~1.12 µm. The fluid permeability of membranes, K, obtained at the low relative humidity level was measured using an upward wicking experiment to give K~10−13 m2. The YAG:Er membrane presented a strong green photoluminescence under ultraviolet excitation and intense radioluminescence dominated by emission lines at 398 and 467 nm under the X-ray excitation. The properties of these materials make them promising candidates as porous scintillators for the detection of ionizing radiation of flowing fluids.Graphical Abstract

Scintillation of nanoparticles: Case study of rare earth doped fluorides

An investigation of the scintillation response of rare earth doped fluoride nanoparticles was carried out taking advantage of core/multi-shell structures. A significant enhancement of the scintillation response was observed and attributed to the increase of the volume of the nanoparticles. Larger nanoparticles contain larger fractions of the irradiation cascade, their dimensions approach the electron-hole mean recombination length increasing the probability of radiative recombination, and separates the luminescence centers in the core from quenching defects on the surface of the nanoparticles.