Defect concentration in Ti-substituted YIG from TG curves

The article discusses theory and experiment about the measurement of defect concentration in Ti-substituted yttrium iron garnet by means of thermogravimetry techniques. The two possible cases arising from oxygen interchange with atmosphere, oxygen vacancies and interstitial cations, may be analyzed quantitatively from the derived expressions. The possibility of another type of defects being present in the samples, not associated to oxygen evolution, is not excluded. Measurements were carried out in air and CO₂ for different Ti contents. The substitution tends to increase slightly the defect parameter θ in YIG, while a CO₂ reducing atmosphere is much more effective than the Ti substitution for increasing θ. Calculations for a given single-phased sample sintered in air show two possibilities: a deficit of one oxygen atom for every 2.5 unit cells of 96 atoms, or one excess cation for every 3.5 cells. Other samples show very similar results. The accuracy involved in the measurements is about 2–3%.     

High‐perfomance Ce‐doped multicomponent garnet single crystalline film scintillators

We report for the first time the optimized content and excellent scintillation properties of single crystalline film (SCF) scintillators of multicomponent Gd_3–xLu_x Al_5–yGa_y O₁₂:Ce garnet compounds grown by liquid phase epitaxy (LPE) method. The Gd_1.5Lu_1.5Al_2.75Ga_2.25O₁₂:Ce and Gd₃Al_2.75–2Ga_2.25–3O₁₂:Ce SCF show the light yield (LY) comparable with that of high‐quality bulk crystal analogues of these garnets but faster scintillation decay and very low thermoluminescence in the above room temperature range. To our knowledge, these SCF possess the highest LY values ever obtained in LPE grown garnet SCF scintillators exceeding by at least 1.5–1.6 times the values previously reported for SCF scintillators.

     

Influence of the Grain Boundaries on the Heat Transfer in Laser Ceramics

Grain boundaries play a key role in determining several key properties of polycrystalline laser ceramics. Heat transfer measurements at low temperature constitute a good tool to probe grain boundaries. We review the results of heat transfer measurements in polycrystalline Y₃Al₅O₁₂ garnets as well as Y₂O₃ and Lu₂O₃ sesquioxide materials obtained by self-energy-driven sintering of nano-particles. The average phonon mean free path in Y₃Al₅O₁₂ was found to be significantly larger than the average grain size and to scale with temperature as T ⁻² at low temperature. Existing models describing the interaction between phonons and grain boundaries are reviewed. Correct temperature dependence of the mean free path and order of magnitude of scattering rates were found by assuming the existence of a grain boundary layer having acoustic properties different from those of the bulk. A different temperature dependence of phonon mean free path was found for the sesquioxides and was ascribed to the stronger elastic anisotropy of these materials. The thermal resistance associated to the grain boundaries of laser ceramics was found to be lower than in other dense polycrystalline ceramic materials reported in the literature.     

Absorption spectra and magneto-optic figures of merit in the Bi x Sm3-x Fe5-y Ga y O12 system

The absorption (α) and Faraday rotation (θ) spectra of 14 garnets belonging to the series Bi _x Sm_3-x Fe_5-y Ga _y O₁₂ (0<x<1.05, 0.8<y<1.15) have been measured between 15 000 cm⁻¹ and 19 000 cm⁻¹. The figure of merit (θ/α) at 17 850 cm⁻¹ (560 nm) increases linearly with increasing bismuth concentration up tox∼0.6 where it begins to increase less rapidly. For operation of magneto-optic display devices at 17 850 cm⁻¹ there is no advantage in using garnets in this series withx>0.8. The Faraday rotation at 17 850 cm⁻¹ increases linearly with bismuth concentration whereas the absorption coefficient increases more rapidly. The presence of Bi³⁺ increases the intensity of all Fe³⁺ pair transitions in the garnet system as a result of the increased superexchange induced by Bi³⁺. This is in keeping with the observation that the intensity of the⁶A_1g (S)→⁴T_1g (G) transition in (RE)₃Fe₅O₁₂ (RE=Er, Y, Dy, Gd, Eu) increases on traversing the above RE series as do the Curie temperatures of these iron garnets.     

Non-stoichiometry and magneto-optic properties of magnetic bubble thin films of TmIG substituted with bismuth and gallium

Thulium iron garnet thin films substituted with bismuth and gallium were prepared by LPE from a PbO.B₂O₃ flux. Radioactive isotope tracers were added to the melt as the chemical analysis technique. The deviation from the ratio (Pb+Bi+Tm)/(Fe+Ga)=0.6 of the layers was large and a proportion of the thulium ions possibly lie on the octahedral crystallographic sites. The concentration of Bi, Pb, and Ga as a function of the growth temperature was studied. The magneto-optic properties show that the layers are well suited for use in a magneto-optic device. A figure of merit of 2.5 degree per decibel at λ=560 nm was obtained and some magnetic bubble parameters are also presented.     

Assessing the Importance of Cation Size in the Tetragonal-Cubic Phase Transition in Lithium-Garnet Electrolytes**

Lithium garnets are promising solid-state electrolytes for next-generation lithium-ion batteries. These materials have high ionic conductivity, a wide electrochemical window and stability with Li metal. However, lithium garnets have a maximum limit of seven lithium atoms per formula unit (e.g., La₃Zr₂Li₇O₁₂), before the system transitions from a cubic to a tetragonal phase with poor ionic mobility. This arises from full occupation of the Li sites. Hence, the most conductive lithium garnets have Li between 6–6.55 Li per formula unit, which maintains the cubic symmetry and the disordered Li sub-lattice. The tetragonal phase, however, forms the highly conducting cubic phase at higher temperatures, thought to arise from increased cell volume and entropic stabilisation permitting Li disorder. However, little work has been undertaken in understanding the controlling factors of this phase transition, which could enable enhanced dopant strategies to maintain room temperature cubic garnet at higher Li contents. Here, a series of nine tetragonal garnets were synthesised and analysed by variable temperature XRD to understand the dependence of site substitution on the phase transition temperature. Interestingly the octahedral site cation radius was identified as the key parameter for the transition temperature with larger or smaller dopants altering the transition temperature noticeably. A site substitution was, however, found to make little difference irrespective of significant changes to cell volume.     

Heat capacities, order-disorder transitions, and thermodynamic properties of rare-earth orthoferrites and rare-earth iron garnets

Rare-earth orthoferrites, RFeO₃, and rare-earth iron garnets (RIGs) R₃Fe₅O₁₂ (R=rare-earth elements) were prepared by citrate-nitrate gel combustion method and characterized by X-ray diffraction method. Isobaric molar heat capacities of these oxides were determined by using differential scanning calorimetry from 130 to 860 K. Order-disorder transition temperatures were determined from the heat capacity measurements. The Néel temperatures (T_N) due to antiferromagentic to paramagnetic transitions in orthoferrites and the Curie temperatures (T_C) due to ferrimagnetic to paramagnetic transitions in garnets were determined from the heat capacity data. Both T_N and T_C systematically decrease with increasing atomic number of R across the series. Lattice, electronic and magnetic contributions to the total heat capacity were calculated. Debye temperatures as a function of absolute temperature were calculated for these compounds. Thermodynamic functions like , , H^o, G^o, , , , , and have been generated for the compounds RFeO₃(s) and R₃Fe₅O₁₂(s) based on the experimental data obtained in this study and the available data in the literature.     

Trap levels in Y-aluminum garnet scintillating crystals

Point defects acting as trap levels were investigated on undoped, Ce- and (Ce, Si)-doped Y₃Al₅O₁₂ (YAG) crystals by TSL measurements performed over a wide temperature range (10–800 K). Below room temperature, a composite glow curve was observed, whose intensity strongly increased after Ce doping. Moreover, Ce doping introduced new trap levels giving rise to glow peaks in the 100–200 K range. On the other hand, Si co-doping did not influence the low T glow curve in a significant way. The spectral emission of the TSL was found to be governed by the Ce³⁺ 5d–4f radiative transition, while defect related higher energy emission bands were detected only in the undoped crystal. Above RT, the glow curve was found to be much more influenced by Si co-doping since a strong increase of a glow peak at about 250°C was noticed. Scintillation time decays of Ce- and Ce,Si-doped samples are also reported and compared with TSL data. The significance of the results and the potential impact of defect states on the scintillation properties are discussed.     

Improvement of the scintillation properties of Gd3Ga3Al2O12:Ce,B single crystals having tailored defect structure

A novel approach is reported to minimize various defect centers in Ce doped Gd₃Ga₃Al₂O₁₂ single crystals to improve the scintillation properties. The crystals of Gd₃Ga₃Al₂O₁₂ codoped with 0.2 at% Ce and B (GGAG:Ce,B) have been grown in air and argon ambient using the Czochralski technique. The scintillation light output of crystals grown in Ar ambient was significantly increased after annealing the crystals in air. The measured light output of 60000 ph/MeV for annealed crystals is the highest value reported among this class of materials. As a consequence, the energy resolution at 662 keV gamma‐rays from a ¹³⁷Cs source was improved from 8% for the crystals grown in air to 6% for crystals grown in Ar and subsequently annealed in air. Further, the thermal quenching energy of photoluminescence (PL) emission was increased to be 470 meV for the annealed crystals. The thermoluminescence (TL) measurements suggest that the crystals grown in Ar ambient and post‐growth annealed in air may have a lesser concentration of trap centers which subsequently lead to the improvement in optical and scintillation properties leading to a superior detector performance. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Electrical transport properties of gadolinium scandium gallium garnet

Electrical conductivity and thermoelectric power are measured on a single crystal of Gd_3.0Sc_1.8Ga_3.2O₁₂ (GSGG) between 1273 and 1673 K. The measurements are made both in air and in controlled atmospheres, and P_O2 varies from 10^?1.68 to 10^?5.6 MPa. The data indicate GSGG may well be a mixed conductor in this temperature and P_O2 range, with n-type electronic conductivity and ionic transport on the oxygen sublattice. Changes in temperature induce long-lived disequilibrium in electrical conductivity of GSGG (over 30 h at T < 1373 K) that can be explained by temperature dependent cation redistribution. The effective activation energy for equilibrium electrical conductivity is E_a = 2.40 ± 0.05 eV, as opposed to values of E_a between 1.8 and 2.2 eV during actual temperature changes. An additional contribution in the equilibrium E_a, due to thermally activated cation redistribution, can account for the higher value seen.