Spectral-kinetic studies of SrAlF5 doped by trivalent rare-earth ions

Photochemical properties of Ce³⁺:SrAlF₅ and Ce³⁺,Yb³⁺:SrAlF₅ single crystals together with spectroscopic and kinetic characteristics of several optically nonequivalent impurity centers and energy transfer between them are described. It is shown that co-activation by Yb³⁺ ions effectively suppresses color centers in Ce,Yb:SAF crystals. It was found out that in Ce,Yb:SAF crystals Yb ions exist simultaneously in 2+ and 3+ valent state. Three types of optically nonequivalent luminescent centers corresponding to the doublets in luminescence spectrum centered at 290, 305 and 370 nm (Ce^I, Ce^II, Ce^III, respectively) have been observed. Analysis of luminescence spectra and decays leads to the conclusion that there is no energy transfer between either cerium centers or from Ce³⁺ to Yb²⁺ apart from the Ce^III center which luminescence is slightly quenched by Yb²⁺.     

Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Superhyperfine structure of the EPR spectra of Ce<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The EPR spectra of Ce³⁺ impurity ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals have been investigated at a frequency of ∼9.3 GHz in the temperature range 5–25 K. The effective g factors of the ground Kramers doublet of the cerium ions in three crystals are close to each other (g _‖ = 2.737, g _⊥ = 1.475 for LiYF₄:Ce³⁺). A superhyperfine structure of the EPR spectrum of Ce³⁺ ions in the LiTmF₄ Van Vleck paramagnet has been observed in the external magnetic field B oriented along the crystallographic axis c (B ‖ c). The superhyperfine structure of the EPR soectra of the Ce³⁺ ions in the LiYF₄ and LiLuF₄ diamagnetic matrices is resolved for B ⊥ c. Possible factors responsible for this pronounced difference in the properties of the systems studied have been discussed.     

Low-energy scattering of muonic hydrogen on hydrogen molecules: a semi-classical approach

We present results of PAC measurements in heavy-fermion compound Yb₄As₃. The quadrupole hyperfine interaction has been investigated over the temperature range 78–850 K. The interpretation of the experimental data yields a microscopic proof of the existence of a charge-ordered state with periodic arrangement of Yb²⁺ and Yb³⁺ ions in the low temperature phase. In the high temperature phase all Yb ions are in a valence fluctuating state.     

ESR of Yb3+ ions in a single crystal of the fluctuating-valence compound YbB12

The temperature and angular dependences of electron spin resonance (ESR) spectra of Yb³⁺ ions in a single crystal of fluctuating-valence compound YbB₁₂ were studied. The existence of Yb?Yb ion pairs was observed in a cubic-symmetry crystal. The ions forming the pairs are coupled by the isotropic exchange but interact also with the other pairs by the dipole and exchange coupling. The occurrence of a slight anisotropy in a cubic semiconductor may be the result of a spontaneous break of symmetry specific for the ground state of the Kondo dielectric. A strong temperature dependence of the amplitude of the ESR signals is found at 1.6–4.2 K and interpreted as a result of the capture of electrons by Yb³⁺ ions from electron traps with a binding energy of 18 K. ESR spectra of Yb³⁺ single ions in the Γ₆ state were observed also. The decrease of temperature from 4.2 to 1.6 K indicates a tendency to the ferromagnetic ordering of Yb?Yb pairs.     

Effect of substitution of Ce on superconducting properties of Bi1.7Pb0.3Sr2Ca2−x Ce x Cu3O10+δ system

We have investigated the superconducting properties of the Bi_1.7 Pb_0.3Sr₂Ca_2−xCe _x Cu₃O_10+δ system with x=0.00, 0.02, 0.04, 0.08 and 0.1 by X-ray diffraction and magnetic susceptibility. The substitution of Ce for Ca has been found to drastically change the superconducting properties of the system. X-ray diffraction studies on these compounds indicate decrease in the c-parameter with increased substitution of Ce at Ca site and volume fraction of high T _c (2 : 2 : 2 : 3) phase decreases and low T _c phase increases. The magnetic susceptibility of this compound shows that the diamagnetic on set superconducting transition temperature (onset) varies from 109 K to 51 K for x=0.00, 0.02, 0.04, 0.08 and 0.1. These results suggest the possible existence of Ce in a tetravalent state rather than a trivalent state in this system; that is, Ca²⁺ → Ce⁴⁺ replacement changes the hole carrier concentration. Hole filling is the cause of lowering T _c of the system.     

Additive colouring of CaF2:Yb crystals: determination of Yb2+ concentration in CaF2:Yb crystals and ceramics

When growing CaF₂ crystal doped with rare-earth ions, most of these ions are present in a trivalent state. However, due to contact with graphite crucible, a small proportion of a number of ions (Eu, Sm, Yb and Tm) are reduced to a bivalent state. A similar situation takes place during fabrication of CaF₂ ceramics doped with rare-earth metals. This fact is of particular importance for laser CaF₂:Yb crystals (ceramics), a promising material for short-pulse, high-power, high-energy diode-pumped solid state lasers since the presence of bivalent Yb ions can be a source of thermal losses. To date, there has been no technique to determine Yb²⁺ concentration in as-grown crystals. The proposed technique is based on a total reduction of Yb³⁺ ions via the heating of as-grown CaF₂ crystals with known concentration of Yb in the reducing atmosphere of metal vapour and determining the cross section of absorption bands of Yb²⁺ ions. The knowledge of these parameters allows estimation of the Yb²⁺ content in CaF₂:Yb crystals or ceramics by analysing their absorption spectra. Examples of using this technique are given. The technology of CdF₂ crystals reduction (an “additive colouring”) and features of colouring of crystals doped with rare-earth ions are considered.     

EPR and optical spectroscopy of Yb<Superscript>3+</Superscript> ions in CaF<Subscript>2</Subscript>: an analysis of the structure of tetragonal centers

CaF₂ crystals doped with Yb³⁺ ions have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy. EPR spectra of paramagnetic centers (PCs) for cubic (T_c) and tetragonal (T_tet) symmetries were identified. Empirical energy level diagrams were established and crystal field parameters were determined. Information on the CaF₂∶Yb³⁺ phonon spectra was obtained from the electron-vibrational structure of the optical spectra. The crystal field parameters were used to analyze the crystal lattice distortions in the vicinity of the Yb³⁺ ion. Within the framework of a superposition model, it is established that four F⁻ ions located symmetrically with respect to the fourfold axis from the side of the ion-compensator approach the impurity ion and deviate from the PC axis. The second set of four fluorine ions also approaches the Yb³⁺ ion and the PC axis. The ion-compensator F⁻ also approaches considerably the impurity ion.     

Up and down conversion fluorescence studies on combustion synthesized Yb/Yb: MO-Al2O3 (M=Ca, Sr and Ba) phosphors

The ytterbium ions doped MO-Al₂O₃ (M=Ca, Sr and Ba) phosphors have been synthesized through combustion technique and their up and down conversion fluorescence properties have been studied and compared. The samples were calcinated at different temperatures and their FTIR and XRD spectra have shown a close relationship. With 976 nm excitation all these phosphors show cooperative upconversion emission at 488 nm from the pairs of two Yb³⁺ ions along with an unexpected broad upconversion band in the blue green region and has been assigned to arise from the defect centers. Contrary to this upconversion emission, calcium aluminate phosphor exhibits bright and very broad down-conversion fluorescence (FWHM≈160 nm) upon UV (266 nm) excitation due to Yb²⁺ ions. The inter-conversion between the 3+ and 2+ valence states of Yb ion has been observed on calcinations of samples in open atmosphere and has been correlated to the emission properties. The Yb²⁺ ions containing calcium aluminate phosphor has been found suitable for producing broad band light in the visible region (white light). Lifetime of the emitting states of Yb³⁺ and Yb²⁺ ions have also been measured and discussed.     

UV and VUV spectroscopic study of Na0.4Y0.6F2.2 crystals doped with rare-earth ions

The short-wavelength transmission spectra of Na_0.4 R _0.6F_2.2 crystals with R = Y, Yb, or Lu have been investigated. For these crystals, the VUV transmission cutoffs are 78750, 58820, and 75200 cm^?1, respectively. The 4f ⁿ–4f ^n?15d absorption and excitation spectra of Na_0.4Y_0.6F_2.2 crystals activated with Ce³⁺, Pr³⁺, Nd³⁺, Er³⁺, Tm³⁺, and Yb³⁺ ions have been analyzed in the range 30000–80000 cm^?1. The energy positions of the lowest levels of the 4f ^n?15d configurations of these ions in the fluorite crystal matrix Na_0.4Y_0.6F_2.2 are determined. The absorption band in the spectral range 60600–70000 cm^?1 in Na_0.4(Y, Yb)_0.6F_2.2 crystals is due to the charge transfer from F^? to Yb³⁺. It is shown that the environmental symmetry of Ce³⁺ ions in Na_0.4R_0.6F_2.2 (R = Y, Yb, Lu) crystals is almost identical.     

Cooperative down-conversion of UV light in disordered scheelitelike Yb-doped NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

Concentration series of disordered scheelitelike Yb:NaGd(MoO₄)₂ and Yb:NaLa(MoO₄)₂ single crystals are grown by the Czochralski method. The actual concentrations of Yb³⁺ ions in the crystals are determined by optical-absorption spectroscopy. The luminescence of Yb³⁺ ions in these crystals in the region of 1 μm is studied under UV and IR excitation. In the case of UV excitation, this luminescence appears as a result of nonradiative excited state energy transfer from donor centers of unknown nature to ytterbium. The character of the concentration dependence of Yb³⁺ luminescence indicates that the energy transfer at high Yb concentrations occurs with active participation of a cooperative mechanism, according to which the excitation energy of one donor center is transferred simultaneously to two Yb³⁺ ions. In other words, the quantum yield of this transfer exceeds unity, which can be used to increase the efficiency of crystalline silicon (c-Si) solar cells.     

Er/Yb共掺体系的光致荧光行为及相关物理过程研究

采用固相反应方法，制备了Er₂O₃浓度固定为0.5mol%，Yb₂O₃浓度范围为0.0mol%—5.5mol%的Er/Yb共掺激光玻璃.通过吸收光谱、光致荧光光谱和上转换荧光光谱，研究了Yb₂O₃浓度对Er³⁺荧光特性的影响，并探讨了相关的物理机制.研究结果表明：Yb³⁺共掺对Er³⁺的⁴ 关键词： Er/Yb共掺 光致荧光 能量传递 合作上转换     

The laser-diode-excited 5d-4f luminescence of Ce3+ and Pr3+ ions embedded into a BaR2F8 matrix

We show the possibility of obtaining UV luminescence from 5d-4f transitions of rare-earth ions in the BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) crystal under upconversion excitation by standard laser diodes with lasing wavelengths of 960, 808, and 840 nm. Various upconversion mechanisms of pumping for populating the higher-lying energy levels of the active ions, as well as methods of adaptation of the active medium BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) to these mechanisms, are considered.     

Growth and spectroscopic properties of RE, Mn:YAP (RE=Yb and Ce) photorefractive crystals

RE, Mn:YAP (RE=Yb and Ce) crystals with dimension of Φ 25×60 mm were successfully grown by the Czochralski method. The spectroscopic properties of RE, Mn:YAP (RE=Yb and Ce) crystals before and after γ-irradiation were investigated at room temperature. The results show that the content of Mn⁴⁺ ions was increased with the Yb³⁺ ions co-doping, but decreased by Ce³⁺ ions co-doping. Thermoluminescence (TL) spectra of the crystals indicate three steps of recombination, and the probable recombination processes were discussed.     

Transport and magnetic properties of the compounds YbNi4In and YbNiIn4 with valence-unstable Yb

The electrical resistance, thermal emf, and magnetic susceptibility of the compounds YbNi₄In and YbNiIn₄, with valence-unstable Yb, are measured at temperatures of 4.2–300 K. The valence state of Yb is identified by measuring the x-ray L _III absorption spectra at T=300 K. YbNi₄In is shown to have a Kondo magnetic lattice and exhibit crystal-field effects. The preferred scheme is splitting of the 4f level of Yb³⁺ with doublet formation in the ground and first excited states. In the case of YbNiIn₄, a valence-unstable state of Yb is formed that makes no significant additional contributions to the transport coefficients. Fiz. Tverd. Tela (St. Petersburg) 41, 1918–1921 (November 1999)     

Structure and phase stability of nanocrystalline Ce1−x Ln x O2−x/2−δ (Ln = Yb, Lu) in oxidizing and reducing atmosphere

The structure and phase evolution of nanocrystalline Ce_{1− x} Ln _x O_{2− x/2−δ} (Ln = Yb, Lu, x = 0 − 1) oxides upon heating in H₂ was studied for the first time. Up to 950 °C the samples were single-phase, with structure changing smoothly with x from fluorite type (F) to bixbyite type (C). For the Lu-doped samples heated at 1100 °C in the air and H₂, phase separation into coexisting F- and C-type structures was observed for ~0.40 < x < ~0.70 and ~0.25 < x < ~0.70, respectively. It was found also that addition of Lu³⁺ and Yb³⁺ strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C in both atmospheres. Valency of Ce and Yb in Ce_0.1Lu_0.9O_1.55−δ and Ce_0.95Yb_0.05O_1.975−δ samples heated at 1100 °C was studied by XANES and magnetic measurements. In the former Ce was dominated by Ce⁴⁺, with small contribution of Ce³⁺ after heating in H₂. In the latter, Yb existed exclusively as 3+ in both O₂ and H₂.     

Synthesis,crystal structure and magnetic properties of Yb8Ag18.5Al47.5, Yb2Pd2Cd and Yb1.35Pd2Cd0.65

We report the synthesis of three new Yb-based compounds, Yb₈Ag_18.5Al_47.5 (Yb₈Cu₁₇Al₄₉-type, tetragonal tI74–I4/mmm), Yb₂Pd₂Cd (Mo₂B₂Fe-type, tetragonal tP10-P4/mbm) and Yb_1.35Pd₂Cd_0.65 (MnCu₂Al-type, cubic cF16–Fm3¯m). The crystal symmetry of these compounds has been determined and the complete structural characterisation carried out by single crystal and powder diffraction techniques. Two symmetry in-equivalent sites are available for the Yb ions in Yb₈Ag_18.5Al_47.5 and Yb_1.35Pd₂Cd_0.65. The 4f levels of the Yb ions are appreciably hybridised in Yb₈Ag_18.5Al_47.5 and to a lesser extent in Yb₂Pd₂Cd as inferred from the magnetisation and heat capacity data. Signatures of heavy fermion behaviour are observed in the heat capacity data of Yb₂Pd₂Cd in which the heat capacity, C/T, increases at low temperatures attaining a value of ≈600 mJ/mol K² at 1.8 K. The electrical resistivity of Yb₂Pd₂Cd follows a linear variation with temperature, T, between 1.4 and 5 K, thus indicating a possible non-Fermi liquid behaviour. In contrast, Yb ions are trivalent in Yb_1.35Pd₂Cd_0.65 and order magnetically near 1.4 K.     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

Mössbauer effect in YbBe13: Mixed valence and magnetic ordering

Mössbauer effect investigations on the cubic intermetallic compound YbBe₁₃ in the temperature range between 0.065 K and 81 K are reported. Above the magnetic ordering temperatureT _Neel=1.27 K the results cannot be explained by a Γ₇ groundstate of Yb³⁺. There is evidence for the Yb ion being in a mixed valent state and the degree of hybridisasation being dependent on the magnetic ordering. Below the magnetic ordering temperature a Γ₇ groundstate of a 3⁺ Yb ion is found.