Neutron diffraction study of RECo2Si2 intermetallics

A neutron diffraction study of polycrystalline RECo₂Si₂ intermetallics (RE = Pr, Nd, Tb, Ho, Er) carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic ordering of +?+? type. Magnetic moment is localized on RE ions only and amounts to the RE³⁺ free ion value. In ErCo₂Si₂ the magnetic moment is normal to the tetragonal unique axis, whereas in the remaining compounds the magnetic moment is aligned along it. Néel points were determined from the temperature dependence of magnetic peak heights.     

Exponential depletion of neutral dangling bonds density (D) by rare-earth doping in amorphous Si films

In this work we study the effect reduction in the density of dangling bond species D⁰ states in rare-earth (RE) doped a-Si films as a function concentration for different RE-specimens. The films a-Si_1−xRE_x, RE=Y³⁺, Gd³⁺, Er³⁺, Lu³⁺) were prepared by co-sputtering and investigated by electron spin resonance (ESR) and Raman scattering experiments. According to our data the RE-doping reduces the ESR signal intensity of the D⁰ states with an exponential dependence on the rare-concentration. Furthermore, the reduction produced by the magnetic rare-earths Gd³⁺ and Er³⁺ is remarkably greater than that caused by Y³⁺ and Lu³⁺, which led us to suggest an exchange-like coupling between the spin of the magnetic REs³⁺ and the spin of silicon neutral dangling bonds.     

Novel charge density wave transition in crystals of R5Ir4Si10

We review the observation of novel charge density wave (CDW) transitions in ternary R₅Ir₄Si₁₀ compounds. A high quality single crystal of Lu₅Ir₄Si₁₀ shows the formation of a commensurate CDW along c-axis below 80 K in the (h, 0, l) plane that coexists with BCS type superconductivity below 3.9 K. However, in a single crystal of Er₅Ir₄Si₁₀, one observes the development of a 1D-incommensurate CDW at 155 K, which then locks into a purely commensurate state below 55 K. The well-localized Er³ moments are antiferromagnetically ordered below 2.8 K which results in the coexistence of strongly coupled CDW with local moment antiferromagnetism in Er₅Ir₄Si₁₀. Unlike conventional CDW systems, extremely sharp transition (width ∼ 1.5 K) in all bulk properties along with huge heat capacity anomalies in these compounds makes this CDW transition an interesting one.     

Magnetic and transport properties of Pr2Pt3Si5

We have investigated the magnetic and transport properties of a polycrystalline Pr₂Pt₃Si₅ sample through the dc and ac magnetic susceptibilities, electrical resistivity, and specific heat measurements. The Rietveld refinement of the powder X-ray diffraction data reveals that Pr₂Pt₃Si₅ crystallizes in the U₂Co₃Si₅-type orthorhombic structure (space group Ibam). Both the dc and ac magnetic susceptibility data measured at low fields exhibit sharp anomaly near 15 K. In contrast, the specific heat data exhibit only a broad anomaly implying no long range magnetic order down to 2 K. The broad Schottky-type anomaly in low temperature specific heat data is interpreted in terms of crystal electric field (CEF) effect, and a CEF-split singlet ground state is inferred. The absence of the long range order is attributed to the presence of nonmagnetic singlet ground state of the Pr³⁺ ion. The electrical resistivity data exhibit metallic behavior and are well described by the Bloch–Grüniesen–Mott relation.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Interplay of spin-allowed and spin-forbidden 5d–4f luminescence from rare earth ions

The conditions for co-existence of emissions from spin-allowed and spin-forbidden 5d–4f transitions in rare earth ions and for thermal quenching of these emissions have been analyzed by taking Tm³⁺ 5d–4f luminescence in LiYF₄:Tm³⁺ and Lu³⁺ 5d–4f luminescence in LuF₃ as examples. It is shown that temperature behavior of 5d–4f luminescence agrees with the common trends in decreasing energy splitting between the lowest high-spin and low-spin 5d levels as well as decreasing energy gap between the lowest 5d level and the bottom of the conduction band of the host crystal towards heavier rare earth ions (from Er³⁺ to Lu³⁺).     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Synthesis and luminescence properties of Er3+-doped Lu3Ga5O12 nanocrystals

The concentration-dependent luminescence properties of sol–gel-derived nanocrystalline Lu_3(1?x)Er_3xGa₅O₁₂ powders (where x=0.01, 0.05 and 0.1) have been studied. Laser-excited luminescence spectra, emission decays and upconversion luminescence of Er³⁺-doped Lu₃Ga₅O₁₂ nanocrystalline samples have been measured. The decay curve of the (²H_11/2,⁴S_3/2) emission exhibits a non-exponential behavior presumably due to cross-relaxation process. Moreover, near-infrared to visible upconversion luminescence has been observed in the green region for 1.0 mol% Er³⁺ ions in Lu₃Ga₅O₁₂ nanocrystals upon 815 nm excitation. The power dependence of the anti-Stokes luminescence suggests that upconversion is probably achieved through the sequential absorption of two photons. To the best of our knowledge, this is the first report on the preparation and optical properties of Er³⁺-doped Lu₃Ga₅O₁₂ in the form of nanocrystalline powders.     

Reentrant superconductivity in the orthorhombic system (Tm1−xLux)RuB2

The boundaries between the paramagnetic, superconducting and magnetically ordered phases in the orthorhombic pseudoternary system (Tm_1?xLu_x)RuB₂ have been established by means of ac magnetic susceptibility measurements down to 1.2 K. Reentrant superconductivity occurs between x = 0.52 and x ? 0.68. The absence of coexistence between superconductivity and long range magnetic order in this region suggests a ferromagnetic-like nature of the magnetic state. The initial linear depression of superconducting transition temperature (T_c) gives a coupling constant value N(E_F)$\text{J}$² between conduction electrons and magnetic Tm³⁺ moments of 6.7 × 10^?4 eV-atom-states/ spin direction.     

NIR luminescence from Er/Yb, Tm/Yb, Er/Tm and Nd ions-doped zincborotellurite glasses for optical amplification

In this paper, we report the near-infrared luminescence from the Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped TeO₂-ZnO-B₂O₃-Li₂O-Na₂O glasses for optical amplification. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) profiles of the host glass matrix have been carried out. From the DSC thermogram, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The near-infrared spectra of Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped glasses have shown full-width at half-maxima (FWHM) around 58, 127, 87 and 35 nm, respectively. These glasses with better thermal stability and broad near-infrared emissions should have potential applications in broadly tunable laser sources and broadband optical amplification at low-loss telecommunication windows.     

Photoluminescence spectra of thenardite Na2SO4 activated with rare-earth ions, Ce, Sm, Tb, Dy and Tm

Five Na₂SO₄:RE³⁺ phosphors activated with rare-earth (RE) ions (RE³⁺=Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) were synthesized by heating natural thenardite Na₂SO₄ from Ai-Ding Salt Lake, Xinjiang, China with small amounts of rare-earth fluorides, CeF₃, SmF₃, TbF₃, DyF₃ and TmF₃, at 920 °C in air. The photoluminescence (PL) and optical excitation spectra of the obtained phosphors were measured at 300 and 10 K. In the PL spectrum of Na₂SO₄:Ce³⁺ at 300 K, two overlapping bands with peaks at 335 and 356 nm due to Ce³⁺ were first observed. Narrow bands observed in PL and excitation spectra of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors were well identified with the electronic transitions within the 4fⁿ (n=5, 8, 9 and 12) configurations of RE³⁺. The existence of excitation bands with high luminescence efficiency at wavelengths shorter than 230 nm is characteristic of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors. The obtained results suggest that these phosphors are unfavorable as the phosphor for usual fluorescence tubes, i.e., mercury discharge tubes, but may be favorable as the phosphor for UV-LED fluorescent tubes and as cathodoluminescence, X-ray luminescence and thermoluminescence phosphors.     

Influence of Si and Co substitutions on magnetoelastic properties of R2Fe17 (R=Y, Er and Tm) intermetallic compounds

The magnetostriction of the off-stoichiometric R₂Fe₁₇-type intermetallic compounds based on R₂Fe_14−xCo_xSi₂ (R=Y, Er, Tm and x=0, 4) was measured, using the strain gauge method in the temperature range 77-460 K under applied magnetic fields up to 1.5 T. All compounds show sign change and reduction in magnetostriction values compared to the R₂Fe₁₇ compounds by Si substitution. For Y₂Fe₁₄Si₂ and Er₂Fe₁₄Si₂, saturation behaviour is observed near magnetic ordering temperature (T_C), whereas for Tm₂Fe₁₄Si₂, saturation starts from T>143 K. Also, Co substitution has different effects on the magnetostriction of R₂Fe₁₄Si₂ compounds. In Er₂Fe₁₀Co₄Si₂ and Tm₂Fe₁₀Co₄Si₂, saturation occurs below the spin reorientation temperature (T_SR). In addition, in Er₂Fe₁₄Si₂, a sign change occurs in the anisotropic magnetostriction (Δλ) as well as the volume magnetostriction (ΔV/V) at their T_SR values. The volume magnetostrictions of the Tm-containing compounds show an anomaly around their T_SR. In R₂Fe₁₄Si₂ compounds, parastrictive behaviour is also observed in ΔV/V near their T_C values. In addition, the magnetostriction of the sublattices is investigated. Results show that in R₂Fe₁₄Si₂ compounds, the rare-earth sublattice contribution to magnetostriction is negative and comparable to the iron sublattice, whereas, in R₂Fe₁₀Co₄Si₂ compounds, the rare-earth sublattice contribution is positive and larger than Fe sublattice. These results are discussed based on the effect of Si and Co substitutions on the anisotropy field of these compounds. Influence of the spin reorientation transition on the magnetostriction of these compounds is discussed in terms of the anisotropic sublattice interactions.     

Neutron diffraction studies of Tb2Rh3Si5 compound

In this work neutron diffraction studies of Tb₂Rh₃Si₅ compound are reported. The compound crystallizes in the monoclinic crystal structure of Lu₂Co₃Si₅-type. At 1.5 K an antiferromagnetic ordering with a propagation vector k=(1/2;1/2;1/2) was observed. The Tb magnetic moments of 9.8(2) μ_B form a non-collinear magnetic structure. In the vicinity of Néel temperature of 8 K a change of the magnetic ordering is evidenced. The change seems to be connected with phase transition from commensurate to incommensurate sine-wave modulation of the Tb magnetic moments.     

Destruction of pressure-induced superconductivity by long-range antiferromagnetic order in Tm2Fe3Si5

Reentrant superconductivity has been detected in a well characterized sample of Tm₂Fe₃Si₅ by ac susceptibility measurements under applied pressure. The superconducting transition temperature displays a pronounced, non-linear behavior under pressure, starting at low pressures with an increase which is among the largest known for any compound (dT_c1/dp = 0.47 K/kbar). The magnetic transition temperature is relatively pressure independent.     

Magnetic properties of amorphous rare-earth—Iron alloys

The magnetic properties of various amorphous alloys of the type R_1-xFe_x (R = Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu) have been determined in the concentration range 0.3 ? x ? 0.5. With the exception of the Gd and Lu alloys pronounced thermomagnetic history effects were observed in the temperature dependence of the magnetization. These effects are due to a strong temperature dependence of the coercive force (H_c) which is found to obey an exponential law of the form H_c ∞ exp(-αT). ⁵⁷Fe Mössbauer spectra were obtained on the alloys of a composition close to 40 at% Fe. From the combined results of the Mössbauer spectroscopy and magnetic measurements it is derived that the Fe moment decreases if one passes through the rare-earth series. It is postulated that this decrease is due to small differences in the compositional short-range order in the amorphous alloys caused by the heat of mixing becoming more negative in the same sense.     

Spectroscopy and energy level location of the trivalent lanthanides in LiYP4O12

The excitation and emission properties of the lanthanides Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Er³⁺, Tm³⁺, and Yb³⁺ in LiYP₄O₁₂ were studied by vacuum ultra-violet spectroscopy at 10 K. It provides information on the energies of 4f-5d excitation and emission bands. In the case of Er³⁺ spin forbidden emission was observed. Charge transfer excitation bands were identified for Eu³⁺, Sm³⁺, Tm³⁺, and Yb³⁺, and in the case of Yb³⁺ charge transfer luminescence is observed. All data appear to be consistent with each other and have been used to construct a level scheme showing the location of the energy levels of all trivalent and divalent lanthanides in LiYP₄O₁₂.     

The charge-density-wave transition in Lu5Ir4Si10 under uniaxial pressure

Abstract

An uniaxial pressure cell for low temperature use is described in detail. Then we present data of the electrical resistance of single crystals of Lu₅Ir₄Si₁₀, which is known to show a charge-density-wave transition around 83 K and to become superconducting near 3.8 K, both phenomena being anticorrelated under pressure. Since the CDW in Lu₅Ir₄Si₁₀ is a quasi one-dimensional phenomenon because of a chain-like structure, it responds to uniaxial pressure in a specific way.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

Sol–gel derived nanocrystalline multiferroic BiFeO3 and R (R=Er and Tm) doped therein: Magnetic phase transitions and enhancement of magnetic properties

Nanocrystalline BiFeO₃ and rare earth ion doped BiFeO₃ (Bi_0.9R_0.1FeO₃, R=Er and Tm) were prepared by sol–gel method. Rietveld analysis of the X-ray diffractograms of the samples revealed that small amount of impurity phase of Bi₂Fe₄O₉ was formed together with the desired phase. In the thermal variation of magnetic mass susceptibility (χ_m) of the samples, one sharp transition below T_M (T_M∼100 K, 50 K and 30 K for BiFeO₃, Bi_0.9Er_0.1FeO₃ and Bi_0.9Tm_0.1FeO₃, respectively) was observed, which clearly hint the change of the domination of the ferromagnetic exchange interaction over the usual antiferromagnetic exchange interaction. Also, static magnetization (M) and susceptibility of each doped sample have been drastically enhanced compared to that of BiFeO₃. The values of χ_m and M measured at different temperatures confirmed that the magnetic behavior of the doped systems has been dominated by the paramagnetic/ferromagnetic clusters below ∼T_M. Another phase transition were observed in the χ_m vs. T curve of the samples at relatively higher temperature T_B (∼260 K for BiFeO₃, ∼220 K for Bi_0.9Er_0.1FeO₃ and ∼180 K for Bi_0.9Tm_0.1FeO₃), which may be attributed to the charge ordering transition. Ferroelectric hysteresis loops of the samples observed at 100 Hz confirmed the presence of ferroelectric ordering of the samples. Measured values of dielectric constants at 1 kHz of each sample in presence and absence of magnetic field confirmed a substantial magnetoelectric coupling of all the samples.     

Spin reorientation and magnetization anomaly in Er2Fe14B and Tm2Fe14B

Static magnetic measurements have been carried out on single crystals of Er₂Fe₁₄B and Tm₂Fe₁₄B in a temperature range between 77 and 590 K. Spin reorientation phenomena have been found in both compounds slightly above room temperature. In Er₂Fe₁₄B, the easy direction of magnetization changes from [100] to [001] at 316 K as temperature increases, and Tm₂Fe₁₄B from [100] to [001] at 310 K. Anomalously large anisotropy in the saturation magnetization has been detected around the spin reorientation temperature.