Zr and Ba edge phenomena in the scintillation intensity of fluorozirconate‐based glass‐ceramic X‐ray detectors

The energy‐dependent scintillation intensity of Eu‐doped fluorozirconate glass‐ceramic X‐ray detectors has been investigated in the energy range from 10 to 40 keV. The experiments were performed at the Advanced Photon Source, Argonne National Laboratory, USA. The glass ceramics are based on Eu‐doped fluorozirconate glasses, which were additionally doped with chlorine to initiate the nucleation of BaCl₂ nanocrystals therein. The X‐ray excited scintillation is mainly due to the 5d–4f transition of Eu²⁺ embedded in the BaCl₂ nanocrystals; Eu²⁺ in the glass does not luminesce. Upon appropriate annealing the nanocrystals grow and undergo a phase transition from a hexagonal to an orthorhombic phase of BaCl₂. The scintillation intensity is investigated as a function of the X‐ray energy, particle size and structure of the embedded nanocrystals. The scintillation intensity versus X‐ray energy dependence shows that the intensity is inversely proportional to the photoelectric absorption of the material, i.e. the more photoelectric absorption the less scintillation. At 18 and 37.4 keV a significant decrease in the scintillation intensity can be observed; this energy corresponds to the K‐edge of Zr and Ba, respectively. The glass matrix as well as the structure and size of the embedded nanocrystals have an influence on the scintillation properties of the glass ceramics.     

Structure and properties of soda lime silicate glass doped with rare earth

Soda-lime-silicate glasses doped with different rare-earth oxides (La₂O₃, CeO₂, Nd₂O₃, Gd₂O₃ and Y₂O₃) of 1 mol% content were prepared with the traditional melting-quenching methods. In order to reveal the effects of rare-earth elements on the behavior of soda-lime-silicate glass, the structure of soda-lime-silicate glasses doped with different rare-earth oxides were determined with Fourier transform infrared spectrometer using the KBr method, and viscosity of glass melts were measured by the rotating crucible viscometer, the melting temperature of the studied glasses were derived on the basis of Arrhenius Equation, moreover the density, bending strength and molar volume were measured and calculated. The effect of rare-earth dopants on the structure of soda-lime-silicate was analyzed by a shift of peak position and variation in the full-width at half-maximum. The effect of doping rare-earth oxides into glass on the viscosity, density and bending strength was interpreted by changing in structure of soda-lime-silicate glasses doped with rare-earth oxides.     

提高能量上转换效率的实验探讨

通过以TeO₂,GeO₂,ZnF₂,SiO₂,PbF₂等为主体的氟氧化物玻璃陶瓷基质材料的研究提出了提高上转换效率的某些条件.选择低声子能量的基质,且基质的M系数接近稀土离子的M系数的氟氧化物基质材料是高效上转材料的基础,选择激发光光子能量与稀土离子、敏化稀土离子能级匹配是高效上转换材料的必要条件.为设计研究稀土掺杂能量上转换材料提供了有理论和应用价值的结果. 关键词： 能量上转换 氟氧化物玻璃陶瓷 稀土掺杂     

Lead fluorosilicate glass ceramics doped with Nd3+, Er3+, and Yb3+

Glasses in the PbF₂-PbO-SiO₂ system doped with 1 mol % of rare-earth elements (Nd³⁺, Er³⁺, or Yb³⁺) are synthesized and studied. The glasses were heat-treated in order to obtain glass ceramics with a fluoride crystalline phase. The changes in the structure and spectral optical properties of glass ceramics with respect to initial glasses were determined by using X-ray diffraction analysis and by studying the luminescent characteristics of dopant ions.     

Lead−barium fluoroborate glass ceramics doped with Nd<Superscript>3+</Superscript> or Er<Superscript>3+</Superscript>

Lead?barium fluoroborate glasses in the PbF₂–BaF₂–B₂O₃, PbF₂–BaO–B₂O₃, and PbO_– BaF₂–B₂O₃ systems doped with rare-earth ions (Nd³⁺ or Er³⁺) are synthesized and studied. It is shown that, based on these glasses, it is possible to produce transparent glass ceramics with fluoride crystalline phases, including ceramics with one crystalline phase of the fluorite structure. The spectral and luminescent properties of the doped glasses, glass ceramics, and polycrystalline complex fluorides containing Pb, Ba, and rare ions are studied.     

Photon down-shifting by energy transfer from Sm3+ to Eu3+ ions in sol-gel SiO2-LaF3 nano-glass-ceramics for photovoltaics

95SiO₂?C5LaF₃ sol-gel derived nano-glass-ceramics single doped with Eu³⁺ or Sm³⁺ and codoped with both of them were successfully obtained. XRD measurements confirm the precipitation of LaF₃ nanocrystals after the ceramming process, with mean size ranging from 10 to 20?nm which increases with the thermal treatment temperature. The incorporation of rare-earth ions into precipitated LaF₃ nanocrystals was confirmed from luminescence spectra. Intense yellow-red emissions were detected under UV and blue light excitation in single and codoped samples. The effect of codoping with Eu³⁺ and Sm³⁺ ions and the energy transfer mechanism between them have been analyzed in order to increase the yellow-red emissions.     

Bismuth silicate glass as host media for some selected rare-earth ions and effects of gamma irradiation

Ultraviolet, visible and infrared spectral measurements were used to investigate prepared undoped and rare-earth doped (2.5%) bismuth silicate glasses (80% Bi₂O₃–20%SiO₂) before and after being subjected to gamma irradiation (8?Mrad). The base bismuth silicate glass reveals strong extended UV–near visible absorption bands which are attributed to the presence of trace iron impurities in the raw materials together with absorption due to sharing of Bi³⁺ ions. The RE-doped samples show the same strong UV–near visible bands as the undoped glasses beside extra narrow characteristic bands mostly in the visible and near-infrared regions due to the respective studied rare-earth ions. The base undoped and all RE-doped samples except CeO₂ sample reveal quite resistance to the effect of gamma irradiation due to heavy atomic mass Bi³⁺ ions present in high content (80%) and the rare-earth ions are known to be weakly affected due to the known 5s, 5p shielding. The exceptional effect of CeO₂-doped sample is related to the ability of Ce³⁺ ions to change its oxidation state through photochemical reaction by irradiation or exchange with Fe³⁺ present as trace iron impurities. The FT infrared spectra of the prepared glasses reveal characteristic absorption bands which are related to the silicate groups together with the sharing of vibrational modes due to Bi–O groups. The IR spectra are slightly affected by gamma irradiation indicating the stability of the structural network groups consisting of SiO₄ and BiO₆ units.     

Size-dependent luminescence of Sm3+ doped SnO2 nano-particles dispersed in sol-gel silica glass

Sol-gel glasses with composition (100?x)SiO₂–xSnO₂ doped with 0.4 mol% of Sm³⁺, with x ranging from 1 to 10, have been successfully synthesized. Transparent doped nano-glass-ceramics were prepared by thermal treatment of the precursor glasses at 900°C during 4 hours, leading to nanocomposites comprising SnO₂ nanocrystals embedded into an amorphous SiO₂ phase. A structural analysis in terms of X-ray Diffraction and High Resolution Transmission Electron Microscopy confirms the precipitation of SnO₂ nanocrystals within the glassy matrix. The mean radius of the obtained SnO₂ nanocrystals, ranging from 2.1 to 4.7 nm calculated by the Scherrer and Brus equations, similar to the Bohr’s exciton radius, constitutes a wide band-gap semiconductor quantum-dot system. Energy transfer from SnO₂ nanocrystal host to Sm³⁺ ions is confirmed by luminescence spectra and analyzed as a function of SnO₂ concentration, showing an evolution that could be ascribed to selective excitation of nanocrystal sets with predetermined size. Besides, a study of the luminescence as a function of temperature helps to clarify the involved energy transfer mechanisms.     

Analysis of the optical properties of Er3+-doped strontium barium niobate nanocrystals using time-resolved laser spectroscopy

This paper reports the results obtained in strontium barium niobate (SBN) nanocrystals in glasses doped with 1, 2.5 and 5 mol% of Er³⁺ ions. The melt-quenching method was applied to fabricate the glasses with composition SrO–BaO–Nb₂O₅–B₂O₃ and further thermal treatment was used to obtain glass ceramic samples from the glass precursor. X-ray diffraction patterns confirmed the formation of SBN nanocrystals with an average size of about 50 nm in diameter. Time-resolved fluorescence spectra for the emission of Er³⁺ ions at 1550 nm have been analyzed in order to confirm the incorporation of the Er³⁺ ions into the nanocrystals. Green frequency upconversion emission under excitation at 975 nm coming from the ions in the nanocrystals has been obtained. This intense upconversion is about a factor of 500 higher than that obtained from the ions which reside in the glassy phase. Moreover, temporal evolution studies have been carried out with the purpose of determining the involved upconversion mechanism and the importance of these processes as a source of losses for the optical amplification at 1550 nm.     

Rare-earth doped YF3 nanocrystals embedded in sol–gel silica glass matrix for white light generation

YF₃ nanocrystals triply-doped with Yb³⁺, Ho³⁺ and Tm³⁺ ions embedded in amorphous silica matrix have been successfully obtained by heat treatment of precursor sol–gel glasses for the first time to our knowledge and confirmed by X-ray diffraction and luminescence measurements. Simultaneous UV and visible efficient up-conversion emissions, with well-resolved Stark structure, under 980 nm infrared pump are observed, indicating the effective partition of rare-earth ions into a crystalline-like environment of the YF₃ nanocrystals. Corresponding energy transfer mechanisms have been analyzed and overall colour emission has been quantified in terms of standard chromaticity diagram. By an adequate doping level and heat treatment temperature of precursor sol–gel glasses, a bright white colour has been accomplished, close to the standard equal energy white light illumination point, with potential applications in photo-electronic devices and information processing.     

Effect of induced crystallization in rare-earth doped lithium borate glass

Rare-earth doped borate glasses and glass ceramics are investigated for their potential as photon converters. Thermal processing of the as-made glass results in the formation of nanocrystals therein. For optical activation, the glasses are doped with Eu³⁺ and Tb³⁺, both enabling an intense emission under ultraviolet excitation. Differential scanning calorimetry and X-ray diffraction are applied to analyze the crystallization behavior. Compared to the undoped glass, the glass transition temperature as well as the crystallization temperature are increased with Eu³⁺ doping. Upon thermal processing of the as-made glasses, the transmittance is significantly reduced. Preliminary photoluminescence quantum efficiency measurements yield lower values for the glass ceramics.     

The effect of alkaline earth metallic ions on the photoluminescence properties of sol-gel silica glass

Mg²⁺-, Ca²⁺-, Sr²⁺- and Ba²⁺-doped silica glasses have been prepared using sol-gel processing by employing Si(OC₂H₅)₄, MgCl₂6H₂O, CaCl₂2H₂O, SrCl₂6H₂O and BaCl₂2H₂O as precursors, with HCl as a catalyst. The UV–visibleabsorption spectra of the doped samples are almost the same as those of the undoped sample. The absorption bands of alkaline earth metallic ions have not been observed in the doped samples. Strong visible light has been observed from sol- gel silica glasses doped with alkaline earth metallic ions. The relative fluorescence intensity of the Sr²⁺-doped (the impurity mole ratio of Sr²⁺ was 0.268%) and the Ba²⁺-doped (the impurity mole ratio of Ba²⁺ was 0.448%) samples was about 4 times that of the undoped sample. The relative fluorescence intensity of the Mg²⁺-doped (the impurity mole ratio of Mg²⁺ was 0.069%) sample was about 2.5 times that of the pure glass sample. The relative fluorescence intensity of the Ca²⁺- doped (the impurity mole ratio of Ca²⁺ was 0.179%) sample was about 3 times that of the pure glass sample. Alkaline earth metallic ions affect the formation and conversion of luminescent defects in sol-gel silica glass. Thus, the relative fluorescence intensity of the doped samples increases more than that of the undoped sample. Received: 17 April 2001 / Accepted: 6 June 2001 / Published online: 30 August 2001     

The photoluminescent properties of Eu in MgO-Ga2O3-SiO2 nanocrystalline glass-ceramic

The MgO-Ga₂O₃-SiO₂ glass-ceramic (GC) containing MgGa₂O₄ nanocrystals and glasses doped with Eu³⁺ ions were prepared by the sol-gel method. The down-conversion and up-conversion luminescence (UCL) properties were studied. The results indicated that the relative intensity of f-f transitions of Eu³⁺ decreased in contrast with that of charge transfer (CT) absorption with the increase in heating temperature. Using a Xe lamp and 800 nm femtosecond (fs) laser excitation, strong red luminescence of Eu³⁺ in MgO-Ga₂O₃-SiO₂ glasses and GC was observed.     

Structure and intense UV up-conversion emissions in RE3+-doped sol–gel glass-ceramics containing KYF4 nanocrystals

Transparent nano-glass-ceramics containing KYF₄ nanocrystals were successfully obtained by the sol–gel method, doped with Eu³⁺ and co-doped with Yb³⁺ and Tm³⁺ ions. Precipitation of cubic KYF₄ nanocrystals was confirmed by X-ray diffraction and high-resolution transmission electron microscope images. Excitation and emission spectra let us to discern between ions into KYF₄ nanocrystals and those remaining in a glassy environment, supplemented with time-resolved photoluminescence decays, that also clearly reveal differences between local environments. Unusual high-energy up-conversion emissions in the UV range were obtained in Yb³⁺–Tm³⁺ co-doped samples, and involved mechanisms were discussed. The intensity of these high-energy emissions was analyzed as a function of Yb³⁺ concentration, heat treatment temperature of precursor sol–gel glasses and pump power, determining the optimum values for potential optical applications as highly efficient UV up-conversion materials in UV solid-state lasers.     

Additive colouring of CaF2:Yb crystals: determination of Yb2+ concentration in CaF2:Yb crystals and ceramics

When growing CaF₂ crystal doped with rare-earth ions, most of these ions are present in a trivalent state. However, due to contact with graphite crucible, a small proportion of a number of ions (Eu, Sm, Yb and Tm) are reduced to a bivalent state. A similar situation takes place during fabrication of CaF₂ ceramics doped with rare-earth metals. This fact is of particular importance for laser CaF₂:Yb crystals (ceramics), a promising material for short-pulse, high-power, high-energy diode-pumped solid state lasers since the presence of bivalent Yb ions can be a source of thermal losses. To date, there has been no technique to determine Yb²⁺ concentration in as-grown crystals. The proposed technique is based on a total reduction of Yb³⁺ ions via the heating of as-grown CaF₂ crystals with known concentration of Yb in the reducing atmosphere of metal vapour and determining the cross section of absorption bands of Yb²⁺ ions. The knowledge of these parameters allows estimation of the Yb²⁺ content in CaF₂:Yb crystals or ceramics by analysing their absorption spectra. Examples of using this technique are given. The technology of CdF₂ crystals reduction (an “additive colouring”) and features of colouring of crystals doped with rare-earth ions are considered.     

Photoluminescence from germanate glasses containing silicon nanocrystals and erbium ions

We report the first observation of photoluminescence enhancement in Er³⁺ doped GeO₂–Bi₂O₃ glasses containing silicon nanocrystals (Si-NCs) excited by a laser operating at 980 nm. The growth of ≈200% in the intensity of the Er³⁺ transition ⁴S_3/2→⁴I_15/2 (545 nm) and of ≈100% for transitions ²H_11/2→⁴I_15/2 (525 nm), ⁴F_9/2→⁴I_15/2 (660 nm), and ⁴I_5/2→⁴I_13/2 (1530 nm) was observed in comparison with a reference sample that does not contain Si-NCs. The results open a new road for obtaining efficient Stokes and anti-Stokes emissions in germanate composites doped with rare-earth ions.     

Influence of nanoenvironment on luminescence of Euactivated SnO2 nanocrystals

The emission intensity of the peak at 612 nm (⁵D₀→⁷F₂) of the Eu³⁺ ions activated SnO₂ nanocrystals (doped and coated) is found to be sensitive to the nanoenvironment. We have compared the luminescence efficiencies of the nanocrystals of SnO₂ doped by Eu₂O₃ with those of SnO₂ coated by Eu₂O₃ and we found that the intensities are significantly higher in coated nanocrystals. Furthermore, it is clear from luminescence intensity measurements that Eu³⁺ ions occupy low symmetry sites in the Eu₂O₃ coated SnO₂ nanocrystal. The analysis suggests that the radiative relaxation rate is higher in Eu₂O₃ coated SnO₂ nanocrystals than Eu₂O₃ doped SnO₂ nanocrystals due to the asymmetric environment of Eu³⁺ ions in coated samples.     

Strong segregation of doped ions in Y2SiO5:Pr3+ nanocrystals

Strong temperature controlled segregation of doped ions in Y₂SiO₅:Pr³⁺ nanocrystals detected by spectroscopic techniques is reported. The elastic interactions stimulate Pr³⁺ segregation thus leading to non-uniform distribution of doped ions, pair formation and, as a consequence, to abnormal low threshold of luminescence concentration quenching for Y₂SiO₅:Pr³⁺ nanocrystals.     

Hyperfine characterization of the crystallization of nanocrystalline NiFe2O4 from the amorphous silica gel

Nanocrystalline NiFe₂O₄ was in‐situ prepared in amorphous silica using tetramethylor‐thosilicate and nickel (iron) nitrate hydrate as the starting materials in a sol‐gel reaction. The magnetic nanocrystals in the amorphous silica glasses grew slowly with increasing temperature. Above 600^○C, nickel ferrite nanoparticles began to precipitate from the amorphous silica matrix. Mössbauer spectroscopy of the nanocomposites suggested that in the silica glasses, Fe ions were present exclusively as Fe³⁺ in octahedral coordination, and the chemical environment of the Fe³⁺ ions appeared to remain unchanged until the crystallization of nickel ferrite nanocrystals. The formation of NiFe₂O₄ nanocrystals was the result of partial transformation of the FeO₆ octahedra to FeO₄ tetrahedra. The nanocrystalline NiFe₂O₄ are characterized by super‐paramagnetic behaviour at room temperature.     

Spectroscopic properties of Ni and rare-earth codoped Ge-Ga-Sb-S glass

The infrared emission properties of rare-earth (i.e., Dy³⁺, Pr³⁺ or Sm³⁺) and nickel-codoped Ge-Ga-Sb-S glasses were investigated by photoluminescence measurements. It was found that the emission intensities of the rare-earth doped glasses were significantly weakened even with very few amount of nickel (i.e., 500 at. ppm). On the other hand, the nickel-doped glasses show larger indices of refraction, which property will be desirable in nonlinear optics. Our results, however, suggest that to obtain rare-earth doped chalcogenide glasses of better infrared emission property it is necessary to keep the nickel dopant as low as possible.