High-pressure optical studies of Y2O3:Eu3+ nanoparticles

Abstract

The fluorescence spectra of Y₂O₃:Eu³⁺ nanoparticles have been measured under the pressure of up to 78 kbar at room temperature. In this pressure range, a red-shift of 0.02(1) nm/kbar^?1 is noticed for the 0–2 line (⁵D₀→⁷F₂ transition). This shift is explained by the change of negative charge of the surrounding ligands. Compatibility between measured and calculated values for the 0–2 line position was obtained. The luminescence decay curves of the ⁵D₀→⁷F₂ transition were studied up to 78 kbar and were found to behave exponentially for all pressures studied. The fluorescence lifetime τ for the 0–2 line (⁵D₀→⁷F₂ transition) slowly decreased with pressure. The pressure effect on τ for the 0–2 line (⁵D₀→⁷F₂ transition) was explained by a model which considers the pressure effect on the line position, inter-ionic distance, ion volume and polarizability, molecular volume and polarizability, molecular refractive index and the refractive index medium n _med of the surrounding hydrostatic medium. The fluorescence lifetime calculated by the present model is in close correspondence with the experimental values.     

Effect of pressure and temperature on the wavelength shift of the fluorescence line of SrB 4O 7:Sm 2+ scale

The pressure shift of ⁷D ₀?⁵F ₀ fluorescence line of SrB ₄O ₇:Sm ²⁺ has been recalibrated at high temperature and high pressure, respectively. Combined with the high pressure and high-temperature experimental data given by previous study, a quantitative analysis of the temperature effect on pressure shift of the ⁷D ₀?⁵F ₀ fluorescence line has been performed. The results show that there is an overall negligible coupling effect of temperature and pressure on the wavelength shift of the ⁷D ₀?⁵F ₀ fluorescence line below 770 K and 35 GPa. But above 770 K, the temperature effect on pressure shift could not be ignored at least in a relatively high pressure range. A proposed calibration relation is recommended to predict more accurate pressures in high pressure and high-temperature experiments with SrB ₄O ₇:Sm ²⁺ as the pressure scale.     

The pressure dependence of the electric field gradient at tantalum in group IIIb metals: Sc,Y, and Lu

The electric field gradientq acting on¹⁸¹Ta nuclei embedded into Sc, Y, and Lu was found to increase with hydrostatic pressure with relative slopes of (dlnq/dP) _T=300K=+8.0(3)10^?3 kbar^?1, +9.2(6)10^?3 kbar^?1, +10.2(1.3)10^?3 kbar^?1 for Sc, Y, and Lu, respectively.     

Volume properties and compressibility of the graphite-potassium-mercury compounds

Abstract

The volume properties of graphite intercalation compounds (GIGS) C4KHg and of the initial intermetallic compounds KHg and KHg₂ have been investigated in the piston-cylinder apparatus, using the direct volumetric technique, under pressures up to 25 kbar. The compounds, average compressibility K₊, was determined to be 3.8×10^?3 kbar^?1 for C₄KHg, 3.0×10^?3 kbar-^?1 for C₈KHg, 4.8×10^?1 kbar^?1 for KHg, and 4.0 ×10^?1 kbar^?1 for KHg₂ at pressures of 0-20 kbar. The compressibility of the “two-dimensional” KHg layer in the GIC under various pressure conditions has been estimated. These estimates permit comparison of KHg properties in the “three dimensional” and “quasi-two dimensional” states. It was concluded that the influence of the graphite matrix on the intercalant is insignificant for this type ternary GIC.     

Study of the high pressure effect on nanoparticles GdVO4: Eu3+ optical properties

This study considers the effects of hydrostatic pressure on the line position and fluorescence lifetime τ for ⁵D₀ → ⁷F₂ transitions in GdVO₄: Eu³⁺ nanocrystals. The results indicate that the pressure induced the red shift toward longer wavelengths for all the considered lines with different rate. The fluorescence lifetime τ nonlinearly decreases with pressure in the considered pressure range. High pressure induced the fluorescence lifetime τ that can be explained with a simple theoretical model. The measured line position and τ are in a satisfactory agreement with the theoretical calculations.     

Pressure-dependent luminescence properties of Tb3+-doped K–Ba–Al fluorophosphate glass

Tb³⁺-doped fluorophosphate glass with a composition of P₂O₅+K₂O+KF+BaO+Al₂O₃+Tb₄O₇ was prepared by melt quenching technique and characterized through emission spectra and decay curves as a function of pressure up to 37.7 GPa. The ⁵D₄→⁷F₃, ⁷F₄ and ⁷F₅ emission transitions shift toward lower energy in the order of?4.7,?2.4 and?4.0 cm^?1 GPa^?1, respectively, with increasing pressure. A strong increase in the splitting of the ⁵D₄→⁷F₅ Stark levels with pressure is observed. The decay curves for the ⁵D₄ level are found to be almost perfectly single exponential in the entire pressure range studied. Lifetimes of the ⁵D₄ level are found to decrease strongly from 2564 to 886 μs when pressure is increased from ambient to 37.7 GPa. The pressure dependence of all the derived values of the present study is compared with Tb³⁺ in other glasses.     

The effect of high pressure on the electric field gradients at two inequivalent lattice sites of tantalum in ω-zirconium

The pressure variation of the electric field gradients at substitutional tantalum atoms on the two lattice sites (A and B) of ω-zirconium have been determined to be (? lnq ^A/?P)_T = ?1.05(26)10^?3 kbar^?1 and (? lnq ^B/?P)_T = +6.03(40)10^?3 kbar^?1. In addition the thermal expansion coefficients of the unit cell of ω-Zr were found to be α_‖ = +3.5(3)10^?6 K^?6 and α_⊥ = +7.9(4)10^?6 K^?1. A combined analysis of the pressure dependence and the previously determined temperature dependence of the electric field gradients supports the assumption of two different bonding types at the A and B sites.     

Hydrostatic pressure effect on Tc of Ba0.9K0.1Pb0.75Bi0.25O3

The superconducting transition temperature of Ba_0.9K_0.1Pb_0.75Bi_0.25O₃ has been found to be suppressed smoothly by the application of hydrostatic pressure at a rate of —(2.9 ± 0.2) × 10^?5 kbar^?1 up to 15 kbar. The implications of these results are discussed.     

用高压显微光谱系统研究非晶态As2S3的光学折射率随流体静压力变化的规律

用金刚石对顶砧高压显微光谱系统在高达66kbar的流体静压力和光谱波段为400—900nm范围内,用透射光干涉谱法测量了非晶态As₂S₃(a-As₂S₃)的光学折射率n与压力p以及波长λ的变化关系。a-As₂S₃的折射率对压力极为敏感,在波长为650nm,压力从1bar变到66kbar时,它增加35％。在计算机上用最小二乘法对实验点进行拟合的结果得到:对某一波长λ来说,遵循n(P)=n(0)+Ap+Bp²的非线性关系。其中n(p)和n(0)是p压和常压下的折射率,A和B是与波长有关的系数,文中给出了A和B的具体参数。这个关系与Weinstein和Galkiewicz等人公布的n(p)和p之间遵循线性关系不同。 关键词：     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

Studies of the local compressibility of Cr 3+-centered octahedron in LiSc (WO 4)2 crystal from the pressure dependence of the optical spectra

The pressure-induced shifts of optical spectral bands ⁴T₂ and ²E for the preferential Cr³⁺-centered octahedron for Cr³⁺ at the Sc³⁺ site of the LiSc (WO ₄)₂ crystal have been calculated from crystal-field theory. From the calculation, the local linear compressibility d ln R/d p≈?3.3×10^?4 kbar^?1 for the Cr³⁺ center in a LiSc (WO ₄)₂ crystal is obtained. The result is discussed.     

EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate

X-band electron paramagnetic resonance (EPR) study of Cr³⁺-doped dipotassium tetrachloropalladate single crystal is done at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters have been evaluated by employing hyperfine resonance lines observed in EPR spectra for different orientations of crystal in externally applied magnetic field. The values of spin-Hamiltonian and zero-field splitting (ZFS) parameters of Cr³⁺ ion-doped DTP for site I are: g _x  = 2.096 ± 0.002, g _y  = 2.167 ± 0.002, g _z  = 2.220 ± 0.002, D = (89 ± 2) × 10^?4 cm^?1, E = (16 ± 2) × 10^?4 cm^?1. EPR study indicates that Cr³⁺ ion enters the host lattice substitutionally replacing K⁺ ion and local site symmetry reduces to orthorhombic. Optical absorption spectra are recorded at room temperature. From the optical absorption study, the Racah parameters (B = 521 cm^?1, C = 2,861 cm^?1), cubic crystal field splitting parameter (Dq = 1,851 cm^?1) and nephelauxetic parameters (h = 2.06, k = 0.21) are determined. These parameters together with EPR data are used to discuss the nature of bonding in the crystal.     

EPR, Optical Absorption and Superposition Model Study of Fe3+-Doped Ammonium Dihydrogen Phosphate Single Crystals

X-band electron paramagnetic resonance (EPR) studies are carried out on Fe³⁺ ions doped in ammonium dihydrogen phosphate (ADP) single crystals at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations. The obtained values of spin Hamiltonian and zero-field parameters of the Fe³⁺ ion in ADP are: g = 1.994 ± 0.002, |D| = (220 ± 5) × 10^?4 cm^?1 and a = (640 ± 5) × 10^?4 cm^?1. On the basis of EPR data, the site symmetry of the Fe³⁺ ion in the crystal is discussed. The Fe³⁺ ion enters the lattice substitutionally replacing the NH₄ ⁺ sites. The optical absorption of the crystal is also studied at room temperature in the wavelength range of 195–925 nm. The energy values of different orbital levels are calculated. The observed bands are assigned as transitions from the ⁶ A _1g (S) ground state to various excited quartet levels of the Fe³⁺ ion in a cubic crystalline field. From the observed band positions, Racah interelectronic repulsion parameters (B and C), cubic crystal field splitting parameter (D _q ) and Trees correction are calculated. There values are: B = 970, C = 1,923, D _q  = 1,380 cm^?1 and α = 90 cm^?1, respectively. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The zero-field splitting (ZFS) parameters are also determined theoretically using B _kq parameters estimated from the superposition model. The values of ZFS parameters thus obtained are |D| = (213 ± 5) × 10^?4 cm^?1 and |E| = (21 ± 5) × 10^?4 cm^?1.     

Etude de grenats ferrimagnetiques d'yttrium substitues au scandium: Influence de la pression sur leur stabilite et leur temperature de curie

The garnets Y₃Fe₅O₁₂ and Y₃Fe_4.1Sc_0.9O₁₂ are unstable under high temperature and high pressure. They decompose into YFeO₃ and an iron oxide, usually Fe₃O₄. The high temperature decomposition is favoured by pressure and it spreads over a range of temperature which is larger for the substituted garnet than for the pure garnet. The experiments carried out on Y₃Fe₅O₁₂ corroborate the results of Marezio and Geller but do not show the existence of a dense form of this compound, in opposition to the conclusions presented by Shimada.The Curie temperature θ of the garnets Y₃Fe_5?xSc_x O₁₂ (x = 0,35, 0,70 and 0,90) has been measured under pressure up to 60 kbar. The Curie temperature increases under pressure according to the law θ_x (P) = θ_x (0)[ 1 + fP + hp²]. Thef and h coefficients are almost the same for the studied garnets and their average values are f = 2,07 · 10^?3kbar^?1andh = minus;8,37 · 10^?6kbar^?2. Our results are in agreement with what can be inferred from the theories of Geller and Rosencwaig. In addition, the law suggested by Bloch for the Néel ferrimagnetic compounds d Log θ/d Log $\text{V ? ?}\text{10}\text{3}$ can be also applied to these compounds.     

Luminescence of Ca(NbO3)2:Pr3+: Pr3+ and self-trapped exciton emission

Photoluminescence and time resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺, excited under 37,000 cm^?1 (270 nm), obtained at high hydrostatic pressure up to 20 kbar applied in a sapphire anvil cells, are presented. At ambient conditions, the emission spectrum obtained in the time interval 0–1 μs is dominated by spin allowed transitions from the ³P₀ state. The luminescence related to transitions from ¹D₂, characterized by a decay time equal to 33 μs, is observed when one excites directly the Pr³⁺ ion with 30,770 cm^?1 (325 nm) wavelength. The introduction of Pr³⁺ impurities in Ca(NbO₃)₂ does not quench the self-trapped exciton (STE) luminescence. This luminescence, peaking at 20,000 cm^?1 (500 nm), having a decay time of 61 ± 1 μs, still occurs when the crystal is excited with a wavelength of 37,000 cm^?1 (270 nm) or shorter. Under such excitation a fraction of the STE luminescence is reabsorbed by Pr³⁺ ions; in this case the emission lifetime of the ¹D₂ → ³H₄ transition of Pr³⁺ is 64 ± 3 μs. This effect is stable also at high pressure.     

A Quinoline Derivative as an Efficient Sensor to Detect Selectively Al3+ ion

A quinoline-based Schiff base 1 has been utilized as a fluorescence chemosensor for the selective detection of Al³⁺. The receptor 1 exhibited a high association constant (3.67?×?10⁵ M^?1) with submicromolar detection limit (0.18 ppm) towards Al³⁺ in CH₃CN solution.     

Rare earth ions (Eu3+ and Nd3+) doped BaSnF4: transport and photoluminescence characteristics

Investigation on the X-ray diffraction results of rare earth ions such as Eu³⁺ and Nd³⁺ doped BaSnF₄ materials indicates that the doped materials show a similar pattern of BaSnF₄ with the same tetragonal structure (P₄/nmm). The transport properties of the materials have been investigated by impedance spectroscopy, and the results show that the conductivity values are closely related to both concentration and type of the dopant ion. All of these doped materials show an increase in conductivity over un-doped BaSnF₄. The highest conductivity is observed in 3 mol% Nd³⁺ ion-doped BaSnF₄ system (9.01?×?10^?4 Scm^?1), which is about one order higher in comparison to BaSnF₄ conductivity (1.1?×?10^?4 Scm^?1). The room temperature emission spectrum of BaSnF₄:Eu³⁺ and BaSnF₄:Nd³⁺ shows the characteristic bands arising from ⁵D₀?→?⁷F _j (j?=?1, 2, 3, and 4) and ⁴F_3/2 to ⁴I _j (j?=?9/2 and 11/2) transitions of Eu³⁺ and Nd³⁺ ions, respectively.     

Pressure dependence of the absorption edge for Cd1-xMnxTe

The effect of pressure on the optical absorption edge of mixed crystals Cd_1-xMn_xTe with different manganese concentrations is reported. The observed absorption edge shifts to higher energy with increasing pressure at a rate of α=7?8×10^?3 eV/kbar and a second order coefficient of β=-4×10^?5 eV/kbar² for x<0.5, to lower energy with increasing pressure at a rate of α=-5.0 ×10^?3 eV/kbar for x?0.5. A phase transition occurs for all the samples studied. The absorption edge of the new phase is outside the wavenumber range of the instrument. The physical origins of different pressure coefficients are discussed in the light of the deformation potentials of energy band states and the hybridization of the Mn²⁺ 3d levels with the p-like states in the valence band.     

Photoluminescence and Raman spectroscopy studies of Eu3+-doped rutile TiO2 nanocrystals at high pressures

Nanocrystal samples (particle size about 90 nm) of Eu³⁺-doped rutile titanium dioxide (TiO₂) nanocrystals (rutile Eu³⁺/TiO₂ nanocrystals) were synthesized by the sol–gel method with hydrothermal treatment. The pressure effect on photoluminescence (PL) and Raman spectra of the rutile Eu³⁺/TiO₂ nanocrystals was investigated with a diamond anvil cell under hydrostatic pressure condition. Raman spectra of the samples at high pressures indicated that the critical pressure for the transition from the rutile phase to a new baddeleyite-type phase was between 10 and 14.2 GPa. The position of Raman bands shifted to high wavenumbers and the PL intensity of ⁵D ₀→⁷F ₂ transition of Eu³⁺ decreased down to zero with the increase of pressure before the phase transition occurred. After releasing the pressure, the rutile phase was not recovered and a α-PbO₂-type phase was observed at ambient pressure.     

The upconversion luminescence and magnetism in Yb<Superscript>3+</Superscript>/Ho<Superscript>3+</Superscript> co-doped LaF<Subscript>3</Subscript> nanocrystals for potential bimodal imaging

Biocompatible upconversion nanoparticles with multifunctional properties can serve as potential nanoprobes for multimodal imaging. Herein, we report an upconversion nanocrystal based on lanthanum fluoride which is developed to address the imaging modalities, upconversion luminescence imaging and magnetic resonance imaging (MRI). Lanthanide ions (Yb³⁺ and Ho³⁺) doped LaF₃ nanocrystals (LaF₃ Yb³⁺/Ho³⁺) are fabricated through a rapid microwave-assisted synthesis. The hexagonal phase LaF₃ nanocrystals exhibit nearly spherical morphology with average diameter of 9.8 nm. The inductively coupled plasma mass spectrometry (ICP-MS) analysis estimated the doping concentration of Yb³⁺ and Ho³⁺ as 3.99 and 0.41%, respectively. The nanocrystals show upconversion luminescence when irradiated with near-infrared (NIR) photons of wavelength 980 nm. The emission spectrum consists of bands centred at 542, 645 and 658 nm. The stronger green emission at 542 nm and the weak red emissions at 645 and 658 nm are assigned to ⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺, respectively. The pump power dependence of luminescence intensity confirmed the two-photon upconversion process. The nanocrystals exhibit paramagnetism due to the presence of lanthanide ion dopant Ho³⁺ and the magnetization is 19.81 emu/g at room temperature. The nanocrystals exhibit a longitudinal relaxivity (r ₁) of 0.12 s^?1 mM^?1 and transverse relaxivity (r ₂) of 28.18 s^?1 mM^?1, which makes the system suitable for developing T2 MRI contrast agents based on holmium. The LaF₃ Yb³⁺/Ho³⁺ nanocrystals are surface modified by PEGylation to improve biocompatibility and enhance further functionalisation. The PEGylated nanocrystals are found to be non-toxic up to 50 μg/mL for 48 h of incubation, which is confirmed by the MTT assay as well as morphological studies in HeLa cells. The upconversion luminescence and magnetism together with biocompatibility enables the adaptability of the present system as a nanoprobe for potential bimodal imaging.