Influence of pressure on the inhomogeneous mixed-valent state in Eu3S4

The 21.7-keV nuclear gamma resonance of ¹⁵¹Eu was used for studying the inhomogeneous mixed-valent compound Eu₃S₄ in the presence range 0 to 15 kbar. At room temperature the activation energy for electron hopping between the crystallographically equivalent divalent and trivalent Eu sites was found to decrease with pressure by dE_a/dP = -1.8 ± 0.3 meV/kbar. No change of the mean valence of Eu with pressure was observed.     

Pressure dependence of the superconducting transition temperature of a (Mo0.6Ru0.4)86B14 metallic glass

We have studied the pressure dependence of the superconducting transition temperature of amorphous (Mo_0.6Ru_0.4)₈₆B₁₄ for hydrostatic pressures up to P ～ 9 kbar. The transition temperature T_c decreases with pressure at a rate dT_c/dP=-(9±1) mK kbar^-1. We estimate the Grüneisen parameter and the volume dependence of the electron-phonon coupling constant.     

基质发光晶体Na5Eu(MoO4)4在高压下的光谱与晶体场参数

对白钨矿型化学计量的基质发光晶体四钼酸铕钠Na₅Eu(MoO₄)₄在室温下的高压光谱用金刚石对顶砧高压显微光谱系统进行了研究。确定了Eu³⁺各发射谱线的压力红移率。按晶场理论简化方法推导了能级的晶场参数表达式,并按实验数据拟会出晶场参数随压力的移动率。还将上述结果与掺杂发光材料YVO₄:Eu的高压光谱结果作了对比。 关键词：     

Photoluminescence in MgxSr1−xAl2O4:Eu, Ndand electron-vibrational interaction in the Eu 5d states

Green phosphor compositions Mg_xSr_1−xAl₂O₄:Eu, Nd (with x=0.05-0.25) were prepared by solid state reaction method. The effect of Mg substitution on photoluminescence characteristics was investigated. The photoluminescence show intense green emission for MgSrAl₂O₄:Eu²⁺, Nd³⁺ with long persistence. This green emission corresponds to transitions from 4f⁶5d¹ to 4f⁷ of Eu²⁺ ion. Comparative analysis of the excitation and emission spectra were used to evaluate the crystal field splitting of the 5d states of Eu²⁺ and the parameters of electron-vibrational interaction, such as Huang-Rhys factor, effective phonon energy, and zero-phonon line position.     

Pressure dependence of elastic constants of orthorhombic Li2Ge7O15 above and below the ferroelectric transition

The pressure derivatives of the elastic constants c_ij of orthorhombic Li₂Ge₇O₁₅ have been determined at 293 K by the method of pressure-induced shifts of resonance frequencies of thick plates at ca. 15 MHz in the range between 0 and 1500 bar. Approaching the transition at ca. 630 bar, all P_ij = dc_ij/dp (i, j = 1, 2, 3; p pressure) develop strongly negative values. At higher pressures a similar behaviour with reversed sign is observed. The pressure derivatives of the pure “shear resistances” c₄₄, c₅₅, and c₆₆ depend only slightly on pressure even in the vicinity of the transition. The main interactions driving the transition are of the totally symmetric type. The values dK^?1/dp (K volume compressibility) deviate strongly from the quasi-invariant value of ca. 5 observed in almost all stable crystals (dK^?1/dp = ? 1750 at 620 bar and 1380 at 700 bar). The anomalous piezoelastic behaviour reflects the anomalous thermoelastic behaviour: negative P_ij in the low pressure (high temperature) phase correspond to positive T_ij = d log c_ij/dT (T temperature) and vice versa.     

The pressure influence on the incommensurate-commensurate ferroelectric phase transition in [4-NH2C5H4NH][SbCl4]

The dielectric properties of the [4-NH₂C₅H₄NH] SbCl₄ (abbreviated as 4-APCA) crystal were investigated under hydrostatic pressure up to 300 Mpa. The pressure-temperature phase diagram was given. The paraelectric-ferroelectric phase transition (II→III) temperature (T_c) increases linearly with increasing pressure with a slope dT_c/dp=21×10⁻² K/MPa. The pressure dependence of Curie-Weiss constants has been evaluated also. In the paraelectric phase (II) the Curie constant (C₊) was pressure dependent whereas the C₋ constant over the ferroelectric phase (III) was almost constant. The results are interpreted in terms of improper and displacive type phase transition model with a soft phonon at a zone boundary.     

Pressure dependence of phase transitions in K2SnCl6 from NQR frequency measurements

The influence of hydrostatic pressure 0 ? p ? 4 kbar on the ³⁵Cl NQR in K₂SnCl₆ was studied in the temperature range 238 K ? T ? 300 K. The phase transition temperatures T_C1 and T_C2 were determined from changes in the NQR line pattern.The phase boundaries in the p-T diagram are straight lines in the region studied. The pressure coefficients are given by dT_C1/dP = 1.35 (10) K kbar^?1 and dT_C2/dP=?1.25 (20) K kbar^?1.     

Dependence of the fundamental absorption edge of CdInGaS4 on hydrostatic pressure

The optical absorption of CdInGaS₄ single crystals has been measured over a hydrostatic pressure range up to 40 kbar in the 2.0–3.0 eV photon energy range at room temperature. The interband gap for the indirect allowed transition was found to have a pressure coefficient, dEg/dP, of +6.4 × 10^-6ev/bar.     

Pressure dependence of temperature variation of AC susceptibility for Fe50Ni37Mn13 and comparison to Fe68.1Ni31.9

Fe₅₀Ni₃₇Mn₁₃, which is a ferromagnetic alloy with FCC crystal structure, has been reported to show the Invar effect below the Curie temperature; however, this alloy shows a typical anti-Invar effect above the Curie temperature. In this paper, we discuss the pressure dependence of the temperature variation of the alternative current (AC) susceptibility at a frequency of 1 kHz for Fe₅₀Ni₃₇Mn₁₃ at various pressures up to 7.5 GPa above 77 K; we then compare the results with those for Fe_68.1Ni_31.9, which were obtained in a previous study. Fe₅₀Ni₃₇Mn₁₃ was in a ferromagnetic state throughout the entire pressure range measured. T_C decreases in inverse proportion to the increasing pressure; dT_C/dp and dln T_C/dp for Fe₅₀Ni₃₇Mn₁₃ are −26 K GPa⁻¹ and −0.07 GPa⁻¹, respectively. Further, the temperature variation of the shape of the χ′-T curve for different pressures indicates continuous combining of magnetic interactions occurs at high pressures. These results are similar to those obtained for Fe_68.1Ni_31.9.     

Synthesis and photoluminescence characteristics of (Sr, Ca)3B2O6:Eu for application in white light-emitting diodes

A series of yellow-green (Sr, Ca)₃B₂O₆:Eu phosphors have been synthesized using precursors prepared via a facile sol-gel route. The solid-solution phases crystallized to materials with the formula of Sr_3−x−yCa_xEu_yB₂O₆ with varied Ca²⁺ and Eu²⁺ contents. The emission peak centered at 540 nm under near-UV excitation exhibited a broad-band distribution in the range of 450-650 nm. The dependences of the luminescence intensity on the contents of Ca²⁺ substitution and Eu²⁺ dopant were also investigated. The composition in the host lattice sensitively affected the chromaticity index. Sr_1.21Ca_1.7Eu_0.09B₂O₆ (SCB:0.09Eu) was shown to possess the highest intensity and broadest emission band. Calcining temperature was shown to greatly influence the luminescent properties of SCB:0.09Eu. It is concluded that SCB:0.09Eu can be used as an efficient yellow-green phosphor for white light-emitting diodes (white LEDs) applications.     

Intense blue-emitting Ca5Al8O14: Eu phosphor for mercury free lamp

The calcium aluminates doped with Eu ions, Ca₅Al₈O₁₄: Eu, phosphors are prepared by the combustion method. The formation of crystalline aluminates was confirmed by X-ray diffraction pattern. The prepared phosphors were characterized by SEM, TGA, DTA, particle size analyzer and Photoluminescence (PL) techniques. From the UV-excited luminescence spectra it was found that the Eu ions acts as a luminescent centre with luminescence at the blue (λ _max = 470 nm) region due to 4f ⁶5d ¹ → 4f ⁷ transition. The excitation spectra show the broad band at 355 nm wavelength (λ _em = 470 nm). The excitation 355 nm is a mercury free excitation and therefore Ca₅Al₈O₁₄: Eu may be useful for the solid state lighting phosphor in lamp industry.      

Hydrostatic pressure effect on commensurate—incommensurate transition in K2SeO4-Elastic anomalies studied by Brillouin scattering

A Brillouin scattering study of the commensurate—incommensurate transition in K₂SeO₄ submitted to a hydrostatic pressure was performed. It was found that an increasing pressure lowers the transition temperature (dT_i/dP_i = ?59 K/GPa). The strong anomalies of velocity and damping of the longitudinal acoustic wave propagating along [0 0 1] are weakly affected when pressure acts. The effect of pressure on these anomalies has been calculated on the basis of the lowest order couplings eQ² and e²Q² between strain e and order parameter Q.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Preparation and characterization of LiAEAlF6:Eu (AE=Mg, Ca, Sr or Ba) phosphors

Wet chemical synthesis of LiAEAlF₆:Eu (AE=Mg, Ca, Sr or Ba) phosphors is described. Formation of single-phase compounds LiCaAlF₆ and LiSrAlF₆ was confirmed by XRD. LiCaAlF₆:Eu and LiSrAlF₆:Eu phosphors exhibited broadband emission corresponding to intraconfigurational transition 4f⁶5d¹→4f⁷(⁸S_7/2). LiMgAlF₆:Eu exhibits a narrow line emission corresponding to ⁶P_J→⁸S_7/2 transition of 4f⁷ configuration besides the band emission. LiBaAlF₆:Eu, on the other hand, was found to yield predominantly line emission.     

Piezo-optic behavior of forsterite,Mg2SiO4

The piezo-optic behavior of forsterite, crystallizing in the orthorhombic system, has been investigated up to a maximum pressure of 7 kbars. It is found that the variation of the refractive indices with pressure, dn/dP, are 0·03₅×10⁻³/kbar, 0·04₆×10⁻³/kbar, and 0·06₃×10⁻³/kbar for the n_α, n_β, and n_γ respectively. These values are the lowest on record. The corresponding values for the variation of the refractive indices with volume strain are 0·04₄, 0·05₉ and 0·08₀ respectively. These results are interpreted in terms of the bonding and coordination number of the oxygen ions.     

Luminescence study of the 4f5d configuration of Nd in LiYF4, LiLuF4 and BaY2F8 crystals

Ultraviolet fluorescence of Nd³⁺ ions induced by triphotonic excitation process was studied in Nd-doped LiYF₄, LiLuF₄ and BaY₂F₈ crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f²5d configuration and 4f³ states of Nd³⁺ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of ⁴K_11/2(5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f² configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f-f characteristics to the f-d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262 nm observed in LiYF₄, LiLuF₄ and BaY₂F₈ crystals, respectively. Although the 5d-4f² interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f²5d configuration to 4f³ states that preserves the total spin S=3/2.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

Quadratic electrostrictive effects in NaCl and KA1(SO4)2·12H2O derived from stress dependence of dielectric constants

The equivalence of quadratic electrostrictive coefficients and certain stress derivatives of dielectric constants provides a chance for an independent determination of the tensor of quadratic electrostriction. The experimental values obtained by the aid of stress-induced shifts of the dielectric constants allow a clarification of the contradictory results of different authors on NaCl and KA1(SO₄)₂·12H₂O. The new values for 293 K are: NaCl: d₁₁₁₁ = 0.68, d₁₁₂₂ =-0.215, d₁₂₁₂ = 0.12; KA1(SO₄)₂·12H₂O: d₁₁₁₁ = 0.63, (d₁₁₂₂ + d₁₂₁₁)/2 = -0.15, d₁₂₁₂ = 0.46 (Unit: 10^-20 m² V^-2). These crystals exhibit a mechanical dilatation parallel to an electric field and a contraction in perpendicular directions. This is accompanied by by a small increase in volume. Further, it is shown that certain relations between different electrostrictive effects of second order given in literature are erroneous in respect to sign..     

Hyperfine interaction of Eu in Eu2TiO4

The hyperfine interaction of ¹⁵¹Eu in Eu₂TiO₄ has been measured using the Mössbauer Effect. Using the four-fold symmetry of the Eu²⁺ site, it has been found that the nuclear quadrupole moment ratio of the first-excited to the ground states of ¹⁵¹Eu is R = 1.34 ±0.03, and the quadrupole interaction energy is ρ²qQ_o = -(190 ± 7) MHZ. Below T_c = 7.8K, the magnetic hyperfine field H_hf points close to the direction of the four-fold axis. The zero-degree value of H_hf is estimated to be (305 ± 3) kOe.     

Influence of colloidal-gold films on the luminescence of Eu(TTFA)3 in PMMA

The effects of colloidal-gold layers on the luminescent properties of thin films of Eu(TTFA)₃(TTFA=thenoyltrifluoroacetonate) in PMMA (PMMA=poly(methyl methacrylate)) were investigated. Layers of spherical gold nanoparticles (12 nm) were formed by self-assembly on the surface of amino-derivatized glass slides. Eu(TTFA)₃-PMMA films were then spin-coated either directly onto the Au metal surfaces or onto spacer layers covering the gold. The luminescence properties were characterized both as a function of the density of Au particles in the colloidal layer, and as a function of the distance between the Au layer and the luminescent film. The distance between the metal and luminescent layers was controlled using polyelectrolyte spacer layers deposited on the colloidal-gold films by a spin-assisted, layer-by-layer (SA-LBL) method. It was found that the colloidal gold layer has a net quenching effect on Eu(TTFA)₃ luminescence under all conditions considered in this study. The luminescence intensities and lifetimes decrease with increasing density of Au nanoparticles and with decreasing separation (d) between the luminescent film and the gold layer. The measured luminescence intensity drops more quickly with decreasing distance than one would predict based solely on lifetime data, if one assumes a constant radiative relaxation rate. Fits of the luminescence decay kinetics to a model for non-radiative energy-transfer from Eu(TTFA)₃ to the gold layer yields a 1/d² dependence, where d is the distance from the gold layer to the nearest face of the luminescent film. It is suggested that there is no reasonable physical interpretation of this result within the constraints of the model and, therefore, the interaction between the luminescent and gold layer cannot be explained solely in terms of non-radiative energy transfer.