Growth, structure, and temperature dependent emission processes in emerging metal hexachloride scintillators Cs2HfCl6 and Cs2ZrCl6.

Crystals of metal hexachlorides Cs2MCl6 (M = Hf or Zr) have recently emerged as promising materials for scintillation applications due to their excellent energy resolution. In this work, we investigated the crystal structure and scintillation properties of Cs2HfCl6 and Cs2ZrCl6 crystals in the broad temperature range from 9 to 300 K. X-ray diffraction data confirmed the same cubic structure (space group Fm3m) for Cs2HfCl6 and Cs2ZrCl6 over the entire examined temperature range. The room temperature scintillation light yield of Cs2HfCl6 excited with a 137Cs γ-source is measured to be 24 800 photons per MeV, while Cs2ZrCl6 exhibits 33 900 photons per MeV resulting in energy resolutions of 5.3% and 4.5%, respectively. The alpha-to-beta ratio determined at room temperature for 5.5 MeV α-particles from an 241Am source is equal to 0.39 for Cs2HfCl6 and 0.35 for Cs2ZrCl6. The measurements of scintillation decay curves revealed complex kinetics due to delayed recombination processes. A tangible enhancement of the scintillation yield with heating is observed in the 125-150 K range. This effect is a manifestation of negative thermal quenching explained by thermal activation of trapped carriers. A model of the emission centre is proposed that consistently explains the observed changes of emission intensity with temperature in the crystals under study.

Al2O3 co-doped with Cr3+ and Mn4+, a dual-emitter probe for multimodal non-contact luminescence thermometry.

Luminescence probes that facilitate multimodal non-contact measurements of temperature are of particular interest due to the possibility of cross-referencing results across different readout techniques. This intrinsic referencing is an essential addition that enhances accuracy and reliability of the technique. A further enhancement of sensor performance can be achieved by using two luminescent ions acting as independent emitters, thereby adding in-built redundancy to non-contact temperature sensing, using a single readout technique. In this study we combine both approaches by engineering a material with two luminescent ions that can be independently probed through different readout modes of non-contact temperature sensing. The approach was tested using Al2O3 co-doped with Cr3+ and Mn4+, exhibiting sharp emission lines due to 2E → 4A2 transitions. The temperature sensing performance was examined by measuring three characteristics: temperature-induced changes of the intensity ratio of the emission lines, their spectral position, and the luminescence decay time constant. The processes responsible for the changes with temperature of the measured luminescence characteristics are discussed in terms of relevant models. By comparing temperature resolutions achievable by different modes of temperature sensing it is established that in Al2O3-Cr,Mn spectroscopic methods provide the best measurement accuracy over a broad temperature range. A temperature resolution better than ±2.8 K can be achieved by monitoring the luminescence intensity ratio (40-145 K) and the spectral shift of the R-line of Mn4+ (145-300 K range).

Multiple fermion scattering in the weakly coupled spin-chain compound YbAlO3.

The Heisenberg antiferromagnetic spin-1/2 chain, originally introduced almost a century ago, is one of the best studied models in quantum mechanics due to its exact solution, but nevertheless it continues to present new discoveries. Its low-energy physics is described by the Tomonaga-Luttinger liquid of spinless fermions, similar to the conduction electrons in one-dimensional metals. In this work we investigate the Heisenberg spin-chain compound YbAlO3 and show that the weak interchain coupling causes Umklapp scattering between the left- and right-moving fermions and stabilizes an incommensurate spin-density wave order at q = 2kF under finite magnetic fields. These Umklapp processes open a route to multiple coherent scattering of fermions, which results in the formation of satellites at integer multiples of the incommensurate fundamental wavevector Q = nq. Our work provides surprising and profound insight into bandstructure control for emergent fermions in quantum materials, and shows how neutron diffraction can be applied to investigate the phenomenon of coherent multiple scattering in metals through the proxy of quantum magnetic systems.

Mn2+ luminescence of Gd(Zn,Mg)B5O10 pentaborate under high pressure.

The results of X-ray diffraction studies of the Gd(Mg0.95-x,ZnxMn-0.05)B5O10 down-converting phosphor as a function of Mg-Zn composition are presented. The lattice parameters and unit cell volumes of GdMg0.95-xZnxMn0.05B5O10 pentaborates are examined. The relationships between the structure and optical properties of these materials are explicated based on the results of theoretical calculations of the energy structure. The effect of pressure on the luminescence of Mn2+ in this system was studied up to ca. 32 GPa. The observed quenching of Mn2+ luminescence is due to the crossing of the emitting 4T1g level with the non-emitting 2T2g state. This crossing sets a long-wavelength limit on the possibility of observing the emission of Mn2+ ions, which is around 850 nm.

Tomonaga-Luttinger liquid behavior and spinon confinement in YbAlO3.

Low dimensional quantum magnets are interesting because of the emerging collective behavior arising from strong quantum fluctuations. The one-dimensional (1D) S = 1/2 Heisenberg antiferromagnet is a paradigmatic example, whose low-energy excitations, known as spinons, carry fractional spin S = 1/2. These fractional modes can be reconfined by the application of a staggered magnetic field. Even though considerable progress has been made in the theoretical understanding of such magnets, experimental realizations of this low-dimensional physics are relatively rare. This is particularly true for rare-earth-based magnets because of the large effective spin anisotropy induced by the combination of strong spin-orbit coupling and crystal field splitting. Here, we demonstrate that the rare-earth perovskite YbAlO3 provides a realization of a quantum spin S = 1/2 chain material exhibiting both quantum critical Tomonaga-Luttinger liquid behavior and spinon confinement-deconfinement transitions in different regions of magnetic field-temperature phase diagram.

Sorption-luminescence method for determination of terbium using Transcarpathian clinoptilolite.

Sorption-luminescent method for terbium determination based on natural Transcarpathian clinoptilolite without using of complex synthetic organic compounds and toxic solvents was proposed. Optimal luminophore preparation conditions are sorption of Tb(III) on zeolite in the borate buffer solution with pH 8.25 and further calcination of clinoptilolite-Tb(III) samples at 500°C. For luminescence excitation the rays with wavelength of λ = 220nm of were used. Luminescence intensity at λ = 545nm was selected as analytical parameter for a quantitative terbium determination. Definable range of Tb(III) concentration with the detection limit of 1ngmL-1 is within of 3-1140ngmL-1. The proposed method can be used for the terbium determination in the presence of many rare earths. Sorption-luminescent method can be applied for determination of trace terbium ions in synthetic water solutions and in intermetallics. The proposed analytical method gave recoveries from 90% to 108% and R.S.D. from 0.78% to 6.2% determination of terbium.

Structure Peculiarities of Micro- and Nanocrystalline Perovskite Ferrites La1-x Sm x FeO3.

Micro- and nanocrystalline lanthanum-samarium ferrites La1-x Sm x FeO3 with orthorhombic perovskite structure were obtained by using both solid state reactions (x = 0.2, 0.4, 0.6 and 0.8) and sol-gel synthesis (x = 0.5) techniques. Obtained structural parameters of both series of La1-x Sm x FeO3 are in excellent agreement with the "pure" LaFeO3 and SmFeO3 compounds, thus proving formation of continuous solid solution in the LaFeO3-SmFeO3 system. Peculiarity of La1-x Sm x FeO3 solid solution is divergence behaviour of unit cell dimensions with increasing x: systematic decrease of the a and c lattice parameters is accompanied with increasing b parameter. Such behaviour of the unit cell dimensions in La1-x Sm x FeO3 series led to crossover of the a and c perovskite lattice parameters and formation of dimensionally tetragonal structure near x = 0.04. Linear decrease of the unit cell volume of La1-x Sm x FeO3 with decreasing x according with the Vegard's rule indicate absence of short-range ordering of R-cations in the LaFeO3-SmFeO3 system.

k=0 magnetic structure and absence of ferroelectricity in SmFeO3.

SmFeO3 has attracted considerable attention very recently due to its reported multiferroic properties above room temperature. We have performed powder and single crystal neutron diffraction as well as complementary polarization dependent soft X-ray absorption spectroscopy measurements on floating-zone grown SmFeO3 single crystals in order to determine its magnetic structure. We found a k=0 G-type collinear antiferromagnetic structure that is not compatible with inverse Dzyaloshinskii-Moriya interaction driven ferroelectricity. While the structural data reveal a clear sign for magneto-elastic coupling at the Néel-temperature of ∼675 K, the dielectric measurements remain silent as far as ferroelectricity is concerned.

Thermal changes of the crystal structure and the influence of thermo-chemical annealing on the optical properties of YbAlO3 crystals.

The paper presents experimental results of investigations on the influence of temperature and thermo-chemical annealing on the structural and optical properties of YbAlO(3) crystals. Thermal behaviour of the crystal structure has been studied in the temperature range of 19-1173 K by means of in situ high-resolution x-ray powder diffraction using synchrotron radiation. Lattice expansion of YbAlO(3) displays a strongly anisotropic character: the relative expansion along the b direction is about two times smaller than that along the a and c axes. The influence of thermo-chemical annealing in oxidizing and reducing atmospheres has been studied by means of in situ optical spectroscopy. The increase of the absorption in the range of 300-600 nm during annealing in an oxidizing atmosphere as well as its bleaching during reduction has been observed in the temperature range 700-1000 K. The oxidation and reduction kinetics have been analysed by means of mathematical models taking into account diffusion and the quasi-chemical reaction of the defect centres.

Crystal structure of ZnWO(4) scintillator material in the range of 3-1423 K.

The behaviour of the crystal structure of ZnWO(4) was investigated by means of synchrotron and neutron powder diffraction in the range of 3-300 K. Thermal analysis showed the sample's melting around 1486 K upon heating and subsequent solidification at 1442 K upon cooling. Therefore, the structure was also investigated at 1423 K by means of neutron diffraction. It is found that the compound adopts the wolframite structure type over the whole temperature range investigated. The lattice parameters and volume of ZnWO(4) at low temperatures were parametrized on the basis of the first order Grüneisen approximation and a Debye model for an internal energy. The expansivities along the a- and b-axes adopt similar values and saturate close to 8 × 10(-6) K(-1), whereas the expansion along the c-axis is much smaller and shows no saturation up to 300 K. The minimum expansivity corresponds to the direction close to the c-axis where edge-sharing linkages of octahedra occur.

Anomalous thermal expansion in rare-earth gallium perovskites: a comprehensive powder diffraction study.

Crystal structures of rare-earth gallium perovskites LaGaO(3), PrGaO(3), NdGaO(3) and Pr(1-x)Nd(x)GaO(3) (x = 0.25, 0.50, 0.75) solid solutions were investigated in the temperature range 12-300 K by high-resolution powder diffraction using synchrotron or neutron radiation. The previously reported negative thermal expansion in the b direction of the PrGaO(3) lattice has been found to be persistent in Pr(1-x)Nd(x)GaO(3) solid solutions and its magnitude has been revealed as proportional to the amount of praseodymium. Evaluation of the obtained temperature evolution of cell dimensions indicated a weak anomalous behaviour of the b lattice parameter in NdGaO(3), and its origin is supposed to be the same as in PrGaO(3), i.e. a coupling of the crystal electric field levels with phonon excitations of about 23-25 meV energy. The performed bond length analysis revealed an anomalous behaviour of both LnO(12) (Ln-rare-earth) and GaO(6) coordination polyhedra, which can be a structural manifestation of anomalous thermal expansion in the considered compounds.