Adsorption-desorption studies using ESD of CCl2F2, C2H2F2 and C2F6 on tungsten

The behavior of the desorbing F⁺ ion current from electron bombarded CCl₂F₂, C₂H₂F₂ and C₂F₆ adsorbed on tungsten has been used to investigate the processes of adsorption and desorption of these gases. For tungsten near room temperature, measurements of the F⁺ ion current as a function of electron bombardment time indicated very similar or even identical F⁺-yielding adsorbed species resulting from adsorption of either CCl₂F₂ or C₂H₂F₂ and widely different species from C₂F₆. Cl⁺ ions were also observed to desorb from CCl₂F₂ ad-layers. The behavior of the Cl⁺ ion current with time during electron bombardment indicated electronic conversion between adsorbed binding modes. Complementary investigations on the interaction of CCl₂F₂, C₂H₂F₂ and C₂F₆ with tungsten were carried out by thermal desorption experiments in which the F⁺ ion signal was used to observe the coverage decrease of the F⁺-yielding species. The experiments were performed at tungsten temperatures in the 1200–1600 K range. It was concluded that the F⁺-yielding adsorbed species from CCl₂F₂ and C₂H₂F₂ were strongly bound to the tungsten surface. The F⁺-yielding species from C₂F₆ were found to be weakly bound. From a comparison of the ESD and thermal desorption results, the possibility of dissociative adsorption as well as the nature of the adsorbed species is discussed.     

X-ray absorption spectroscopic study of mixed valence systems EuCu2Si2, YbCu2Si2 and Sm4Bi3

X-ray absorption spectroscopy technique is employed to determine the valence of the rare earth ions in EuCu₂Si₂, YbCu₂Si₂ and Sm₄Bi₃. In each case, two absorption peaks corresponding to two different valence states of respective rare earth ions have been observed. Low temperature (77 K) study of EuCu₂Si₂ indicates distinct change in the relative intensities of the absorption peaks compared to those registered at room temperature (300 K). It is inferred from the change in the relative intensities that the population of Eu²⁺ in EuCu₂Si₂ decreases at liquid nitrogen temperature compared to Eu³⁺. Conclusions drawn from these results agree well with those reported by others using different experimental techniques. In Sm₄Bi₃, Sm²⁺ and Sm³⁺ are found to occur in the ratio of 3:1.     

Luminescence characteristics of Eu2+ activated Ca2SiO4 Sr2SiO4 and Ba2SiO4 phosphorsfor white LEDs

<正>This paper investigates the luminescence characteristics of Eu²⁺ activated Ca₂SiO₄,Sr₂SiO₄ and Ba₂SiO₄ phosphors. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices,and show different emission colour variation caused by substituting M²⁺ cations for smaller cations.This behaviour is discussed in terms of two competing factors of the crystal field strength and covalence.These phosphors with maximum excitation of around 370 nm can be applied as a colour-tunable phosphor for light-emitting diodes（LEDs） based on ultraviolet chip/phosphor technology.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

Mössbauer study of fluorides: Ba2MFeF9 and NaBaFe2F9

The Mössbauer spectra of the compounds Ba₂NiFeF₉, Ba₂FeCrF₉ and NaBaFe₂F₉ have been studied as a function of temperature. Values of the Néel temperature are obtained and the effects of cationic inversion between the two sites of M^II and M^III in compounds Ni^IIFe^III and Fe^IICr^III are observed. In the latter compound, we observe broad lines at all temperatures and a smearing of the magnetic ordering temperature. However, the Fe^IIFe^III compound shows strict structural order. The two sites of Fe^III in NaBaFe₂F₉ have not been resolved.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Crystal structure,NMR study,dielectric relaxation and AC conductivity of a new compound [Cd3(SCN)2Br6(C2H9N2)2]n

The crystal structure, the ¹³C NMR spectroscopy and the complex impedance have been carried out on [Cd₃(SCN)₂Br₆(C₂H₉N₂)₂]_n. Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355±2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of ¹³C CP/MAS line shapes shows indirect spin–spin coupling (¹⁴N and ¹³C) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325–376 K and the frequency range from 10⁻² Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of σ(ω,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism.     

Electron spin resonance of diluted solid solutions of MnO2 in Y2O3

Electron spin resonance spectra of Mn²⁺ in diluted solid solutions of MnO₂ in Y₂O₃ have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn²⁺ ions in sites with two different symmetries were observed, as well as Mn²⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn²⁺ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn²⁺ ions of 0.53 nm, of the same order as that of Mn²⁺ ions in CaO.     

Pseudo potential calculations for Na+2, K+2, Rb+2 and Cs+2

A Hellmann type pseudopotential, is used to calculate the six lowest Σ potential energy curves of Na⁺₂, K⁺₂, Rb⁺₂ and Cs⁺₂ molecular ions.     

The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands of 15NH3

The ir absorption of gaseous ¹⁵NH₃ between 510 and 3040 cm^?1 was recorded with a resolution of 0.06 cm^?1. The ν₂, 2ν₂, 3ν₂, ν₄, and ν₂ + ν₄ bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. ?pirko, J. M. R. Stone, and D. Papou?ek (J. Mol. Spectrosc.60, 159–178 (1976)). A set of effective molecular parameters for the ν₂ = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν₄ and ν₂ + ν₄ bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν₄ in ¹⁴NH₃ by ?. Urban et al. (J. Mol. Spectrosc.79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.     

The origin of K2, Rb2 and Cs2 triplet 13Πg−X3Σ+u bands in discharge

The absorption and emission spectra of potassium, rubidium and caesium low-pressure discharges have been studied at the far blue wings of resonance D2-lines. The observed diffuse bands were attributed to the 1³Π_g?X³Σ⁺_u transition. Experiments revealed the recombination ²P + ²S nature of these bands, and the corresponding rate coefficients were obtained. Energies of the higher excited states as well as the X³Σ⁺_u -state well depths for K₂, Rb₂ and Cs₂ molecules were estimated.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

Thermal expansion of lT-TaS2 and 2H-NbSe2

The thermal expansion of the a and c axes of lT-TaS₂ and of the a axis of 2H-NbSe₂ have been measured between 4 K and 360 K. Discontinuities in the lattice parameters of TaS₂ were observed at the known charge density wave phase transitions near 200 K and 352 K, and a new transition was found near 283 K. These results are used to estimate the entropy changes occurring at the phase transitions. At the charge density wave onset temperature in NbSe₂ we find an upper limit to any discontinuity in the a axis of 2 × 10^-7 and to any discontinuity in the expansion coefficient of 3 × 10^-7 K^-1.     

Magnetic properties of NdCo2Ge2, ErCo2Ge2 and PrFe2Ge2 compounds

Magnetometric and neutron diffraction studies of polycrystalline NdCo₂GE₂, ErCo₂Ge₂ and PrFe₂Ge₂ compounds were carried out in the temperature range between 4.2 and 300 K. All samples are antiferromagnetic with Néel temperature 26.5, ～ 4.2 and 13 K, respectively. The RECo₂Ge₂ compounds have collinear antiferromagnetic order of +?+? type. For PrFe₂Ge₂ a sinusoidal magnetic structure is observed. Magnetic moment is localized on RE atoms only and is equal to that of RE³⁺ free ion value. In ErCo₂Ge₂ the magnetic moment of Er atoms is perpendicular to the c-axis, whereas for remaining compounds it is parallel to the c-axis.     

Infrared laser magnetic resonance (LMR) spectroscopy of NO2 (ν2) with a CO2 laser

The infrared laser magnetic resonance spectra for the ν₂ band of NO₂ were observed by using a CO₂ laser. High-K vibration-rotation transitions from ^rR₆(N) to ^rR₁₁(N) (v₂ = 1 ← 0) were observed. The analysis yielded some molecular parameters including two g factors for the excited vibrational state (v₂ = 1).     

Magnetic excitations in the two dimensional planar antiferromagnets K2FeF4 and Rb2FeF4

The magnetic excitation spectrum of K₂FeF₄ and Rb₂FeF₄, two K₂NiF₄-structure planar antiferromagnets with rather large anisotropy and spins perpendicular to the c-axis, has been measured by Raman and FIR-spectroscopy. One of the two predicted one-magnon transitions and the two-magnon mode have been observed in K₂FeF₄ (Rb₂FeF₄) at 48.5 cm^-1 (37.6 cm^-1) and 182.0 cm^-1 (160.5 cm^-1) respectively. The magnetic field and temperature dependence of the spectra are reported too. The data are discussed on the basis of an easy plane spin model Hamiltonian. In K₂FeF₄: Mn²⁺ a low lying magnetic impurity mode is observed at 40.5 cm^-1.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.     

EPR study of Ce ions in lutetium silicate scintillators Lu2Si2O7 and Lu2SiO5

Two Ce³⁺-doped scintillator crystals, LSO (Lu₂SiO₅:Ce) and LPS (Lu₂Si₂O₇:Ce), are studied by EPR spectroscopy. The analysis indicates that Ce³⁺ substitutes for Lu³⁺ ion in a C₂-symmetry site for LPS and in two C₁-symmetry sites for LSO, with a preference for the largest one, with 6+1 oxygen neighbors. Angular dependence of the EPR spectrum shows that the electronic ground state of Ce³⁺ is different in these two matrices. It is mainly composed of |M_J|=5/2 state in LPS and |M_J|=3/2 state in LSO. The temperature dependence of the linewidth shows a noticeably long spin lattice relaxation time, especially in LPS, which is the result of a stronger crystal field in LPS than in LSO.     

Ferroelectric properties of bilayer structured Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films on Pt/TiO2/SiO2/Si substrates

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films with large remanent polarization and SrBi₂Ta₂O₉ (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages_, bilayered Pb(Zr_0.52Ti_0.48)O₃/SrBi₂Ta₂O₉ (PZT/SBT) thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2P_r) of 18.37 μC/cm² than pure SBT and less polarization fatigue up to 1 × 10⁹ switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.