Effect of post-annealing temperature on the microstructure and magnetic properties of Ce:YIG thin films deposited on Si substrates

Amorphous Ce₁Y₂Fe₅O₁₂ (Ce:YIG) thin films deposited on single crystal Si(1 0 0) and thermally oxidized Si(1 0 0) substrates by pulsed laser deposition were annealed in the temperature range of 700-1000 °C in air. The annealing temperature dependence of microstructure and magnetic properties of Ce:YIG films was studied using X-ray diffraction combined with vibrating sample magnetometer. The results show that single phase of polycrystalline Ce:YIG thin films can be obtained by the post-annealing of as-deposited films at the temperature of 700 °C. However, two steps of phase segregation of Ce:YIG occur as the post-annealing temperature increases: at first, Ce:YIG is decomposed into YIG and non-magnetic CeO₂ when annealed at 800 °C; then YIG continues to be decomposed forming Fe₂O₃ when the temperature is increased up to 900 °C. Consequently, the saturation magnetization of Ce:YIG films decreases first and then increases with the post-annealing temperature going up, which indicates that the saturation magnetization of Ce:YIG films is mainly related to the phase composition of the films. Meanwhile, the presence of SiO₂ buffer layer can significantly enhance the saturation magnetization of Ce:YIG films.     

Electronic and magnetic properties of layered LnFePO (Ln=La and Ce)

Effects of the replacement of La with Ce on the electronic and magnetic properties of a layered superconductor LaFePO (T_c=∼5 K) were studied. Polycrystalline samples of CeFePO, prepared by a solid-state reaction, showed metallic conduction down to 2 K without exhibiting superconducting transition, although the resistivity decreased largely at temperatures below 30 K. Further, they showed an apparent positive magnetoresistance (MR) below ∼2 K, superposed on a negative MR. Temperature dependence of magnetic susceptibility is decomposed to a temperature-sensitive Curie-Weiss component presumably due to the Ce³⁺ ions with a magnetic moment of 1.98μ_B and a less temperature-sensitive component attributable to itinerant electrons. The magnetic interaction between Ce³⁺ ions and itinerant electrons in CeFePO likely suppresses the superconducting transition observed in LaFePO.     

Synthesis of Fe3O4@LaF3:Ce,Tb nanocomposites with bright fluorescence and strong magnetism

In this paper, fluorescent-magnetic Fe₃O₄@LaF₃:Ce,Tb nanocomposites were synthesized by combining fluorescent LaF₃:Ce,Tb and magnetic Fe₃O₄ nanoparticles into new ‘two-in-one’ entities. The obtained Fe₃O₄@LaF₃:Ce,Tb nanocomposites were small (about 30 nm in diameter) and well dispersed in water. Under ultraviolet light irradiation, the Fe₃O₄@LaF₃:Ce,Tb nanocomposites emitted bright green fluorescence, and they could be easily manipulated by an external magnetic field. Such bifunctional nanocomposites may find many biomedical applications, such as cancer detection and drug delivery. And the method we used can be extended to the synthesis of other nanocomposites based on lanthanide-doped materials and metal oxides.     

Electrical and magnetic properties of pseudo-one-dimensional calcium iridium oxide Ca5Ir3O12

The electrical and magnetic properties of one-dimensional calcium iridium oxide Ca₅Ir₃O₁₂ are investigated. A weak ferromagnetic transition has been found at 7.5 K through magnetic susceptibility measurements. At the same temperature, a λ-type specific heat anomaly has been observed. The effective magnetic moments in the paramagnetic temperature range and the magnetic entropy due to the magnetic transition indicates that the tetravalent and pentavalent Ir ions exist in the ratio of 1:2. Another λ-type anomaly has been observed at 105 K in the temperature dependence of the specific heat. The electrical conductivity shows one-dimensional Mott variable-range hopping conduction behavior.     

Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Magnetocrystalline anisotropy in RAu2Ge2 (R = La, Ce and Pr) single crystals

Anisotropic magnetic properties of single crystalline RAu₂Ge₂ (R=La, Ce and Pr) compounds are reported. LaAu₂Ge₂ exhibits a Pauli-paramagnetic behaviour whereas CeAu₂Ge₂ and PrAu₂Ge₂ show an antiferromagnetic ordering with Nèel temperatures T_N = 13.5 and 9 K, respectively. The anisotropic magnetic response of Ce and Pr compounds establishes [0 0 1] as the easy axis of magnetization and a sharp spin-flip type metamagnetic transition is observed in the magnetic isotherms with H // [0 0 1]. The transport and magnetotransport behaviour of these compounds, in particular LaAu₂Ge₂, indicate an anisotropic Fermi surface. The magnetoresistivity of CeAu₂Ge₂ apparently reveals the presence of a residual Kondo interaction. A crystal electric field analysis of the anisotropic susceptibility in conjunction with the experimentally inferred Schottky heat capacity enables us to propose a crystal electric field level scheme for Ce and Pr compounds. For CeAu₂Ge₂ our values are in excellent agreement with the previous reports on neutron diffraction. The heat capacity data in LaAu₂Ge₂ show clearly the existence of Einstein contribution to the heat capacity.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Magnetic ordering in CeMnCuSi2

Temperature and field-dependent magnetization measurements on polycrystalline CeMnCuSi₂ reveal that the Mn moments in this compound exhibit ordering with a ferromagnetic (FM) component ordered instead of the previously reported purely antiferromagnetic (AFM) ordering. The FM ordering temperature, T_c, is about 120 K and almost unchanged with external fields up to 50 kOe. Furthermore, an AFM component (such as in a canted spin structure) is observed to be present in this phase, and its orientation is modified rapidly by the external magnetic field. The Ce L₃-edge X-ray absorption result shows that the Ce ions in this compound are nearly trivalent, very similar to that in the heavy fermion system CeCu₂Si₂. Large thermomagnetic irreversibility is observed between the zero-field-cooled (ZFC) and field-cooled (FC) M(T) curves below T_c indicating strong magnetocrystalline anisotropy in the ordered phase. At 5 K, a metamagnetic-type transition is observed to occur at a critical field of about 8 kOe, and this critical field decreases with increasing temperature. The FM ordering of the Mn moments in CeMnCuSi₂ is consistent with the value of the intralayer Mn–Mn distance R^a_Mn–Mn=2.890 Å, which is greater than the critical value 2.865 Å for FM ordering. Finally, a magnetic phase diagram is constructed for CeMnCuSi₂.     

Integrated chemical process for exothermic wave synthesis of high luminance YAG:Ce phosphors

In this paper, high-luminance yellow-emitting Y₃Al₅O₁₂:Ce³⁺ phosphor (YAG:Ce) microparticles were prepared in a solid flame using a 1.425Y₂O₃+2.5Al₂O₃+0.15CeO₂+k(KClO₃+urea)+mNH₄F precursor mixture (here k is the number of moles of the KClO₃+urea red-ox mixture, and m is the number of moles of NH₄F). The self-sustaining combustion process for the entire reaction sample was provided by the heat generated from the KClO₃+urea mixture. Parametric studies demonstrated that the maximum temperature in the combustion wave varied from 885 to 1200 °C for k=2.0-3.0 mole and m=0-1.5 mole. X-ray analysis results showed that the product obtained in the solid flame consisted of Y₃Al₅O₁₂:Ce³⁺ and KCl phases. Therefore, after dissolving potassium chloride in distillated water, pure-phase YAG:Ce phosphor powder was obtained. The as-prepared YAG:Ce phosphor particles had diameters of 10-25 μm and good dispersity and exhibited luminescence properties comparable to those of YAG:Ce phosphor powders prepared by conventional high-temperature processing.     

Nonvolatile hologram storage properties of tri-doped Zn:Ce:Cu:LiNbO3 crystals

Congruent Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was grown by the Czochralski method in air. The occupation mechanism of the Zn²⁺ was discussed by an infrared transmittance spectrum. The nonvolatile holographic recording in Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was measured by two-photon fixed method. Zn(7 mol%):Ce:Cu:LiNbO₃ single crystals present the faster recording time and higher light-induced scattering resistance ability comparing with Ce:Cu:LiNbO₃ single crystals.     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

In-situ XAS study on the Cu and Ce local structural changes in a CuO-CeO2/Al2O3 catalyst under propane reduction and re-oxidation

The redox behaviour of a CuO-CeO₂/Al₂O₃ catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L₃ absorption edges.CuO and CeO₂ structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu²⁺ cations towards metallic Cu⁰. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu¹⁺ species. Parallel to the CuO reduction, CeO₂ is also reduced in the same temperature range. About 25% of the Ce⁴⁺ reduces rapidly to Ce³⁺ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce⁴⁺ to Ce³⁺ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce³⁺.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO₂/Al₂O₃ catalyst involves both CuO and CeO₂ reduction at similar temperatures, which is ascribed to an interaction between the two compounds.     

Magnetic behavior of MnCo2O4+δ spinel obtained by thermal decomposition of binary oxalates

Manganese cobaltites MnCo₂O_4.62 and MnCo₂O_4.275 having a spinel structure were studied by measuring magnetization, AC susceptibility and by XANES spectroscopy. These compounds were synthesized by decomposition of the binary oxalate Mn_1/3Co_2/3C₂O₄·2H₂O in air at 220 and 500 °C, respectively. It was found that the differences in magnetic characteristics of these cation-deficient spinels are due mainly to variations in the degree of oxidation of manganese. It was shown that the complex oxide MnCo₂O_4.62 formed right after decomposition of the binary oxalate contains about 5×10⁻⁴ mass% metallic cobalt, which determines the dependence of magnetic susceptibility χ on the magnetic field at 300 K. The magnetic transition peculiar to the stoichiometric spinel MnCo₂O₄ at 183 K decreases to 167.5 K for MnCo₂O_4.275 and 67.5 K for MnCo₂O_4.62.     

Effect of Y-doping on the magnetic and charge orderings in Nd2/3Ca1/3MnO3

The shifts of the magnetic and charge ordering transition temperatures caused by Nd substitution for Y in Nd_2/3Ca_1/3MnO₃ CMR narrow-band perovskite manganite have been studied. At low temperatures, three different long-range magnetic orderings consistent with a phase separation scenario have been observed in the doped compound (Nd_0.9Y_0.1)_2/3Ca_1/3MnO₃ by neutron-diffraction study: the antiferromagnetic orderings of PCE and DE types existing below ∼110 and ∼60 K, respectively, and the ferromagnetic one of B type existing below ∼42. Magnetic phase transformations temperatures as well as those of charge ordering have been found to be structural-dependent. Y-doping leads to the decrease of the anisotropy of the orthorhombic Pnma crystal lattice b/√2c, which causes a decrease of the indirect exchange parameters in the system and thus a decrease in the magnetic transformation temperatures for 20-30 K in the doped compound. Doping leads as well to the higher level of the coherent Jahn-Teller distortions of the MnO₆ octahedra in the 200-300 K temperature region, which results in the increase of the charge ordering temperature for ∼80 K.     

Spin-glass-like behaviour and magnetic order in Mn[Cr0.5Ga1.5]S4 spinels

Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr_0.5Ga_1.5]S₄ spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θ_CW=−55 K and an effective magnetic moment of 5.96 μ_B close to the spin-only value of 6.52 μ_B for Cr³⁺ and Mn²⁺ ions in the 3d³ and 3d⁵ configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature T_N=3.9 K, a minimum at the Yafet-Kittel temperature T_YK=5 K, a broad maximum at the freezing temperature T_f=7.9 K, and an inflection point at the Curie temperature T_C=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than T_C suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.     

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.     

Structural and magnetic ordering in the VxNb1+yS2 system

The influence of composition on the structural ordering and magnetism in the V_xNb_1+yS₂ system has been investigated by X-ray diffraction and magnetic measurements. Stoichiometric V_1/3NbS₂ did not exhibit the structural ordering of vanadium between the NbS₂ layers. In the ordered structure, the vanadium composition deviated from the ideal value of to both higher and lower values, while the niobium composition was in the range of 0.05?y?0.18. Excess niobium, y>0, is thought to play an essential role in the structural ordering in this system. For samples with excess niobium and ordered structures, a magnetic transition was observed at 20-50 K, depending on the composition. The spontaneous magnetization of 3-5×10⁻³ μ_B/V atom is thought to be intrinsic to this system. The magnetization curves consisted of a constant and a proportional parts of the magnetic field, which correspond to the spontaneous magnetization and high-field susceptibility, respectively. The magnetization curves and the temperature dependencies of the high-field susceptibility were quite similar to those of the canted antiferromagnetic NiS₂. A correlation between the structural and magnetic ordering is suggested.     

Magnetoelectric behavior in the complex CaMn7O12 perovskite

We report a magnetoelectric effect in the double perovskite CaMn₇O₁₂, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (T_N2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (T_N2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′_r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic field.     

Crystal field investigation on the magnetic properties of Yb in Yb(CF3SO3)3·9H2O

Ytterbium tri-fluoromethanesulfonate (YbTFMS) single crystals are prepared from the slow evaporation of the aqueous solution of YbTFMS and the principal magnetic susceptibility perpendicular to the c-axis of the hexagonal crystal (χ_⊥) is measured from 300 K down to 13 K. Principal magnetic anisotropy Δχ(=χ_∥−χ_⊥) is measured from 300 K down to 80 K which provides principal magnetic susceptibility parallel to the c-axis (χ_∥) down to 80 K. Very good theoretical simulation of the observed magnetic properties of YbTFMS has been obtained using one electron crystal field (CF) analysis having C_3h site symmetry. No signature of ordering effect in the observed magnetic data is noticed down to the lowest temperature (13 K) attained, indicating the inter-ionic interaction to be of predominantly dipolar type. The calculated g-values are found to be g_∥=2.67 and g_⊥=2.51, respectively. CF analysis provides the electronic specific heat which gives two Schottky anomalies in its thermal variation down to ∼13 K. The temperature dependences of quadrupole splitting and hyperfine heat capacity are studied from the necessary information obtained from the CF analysis.     

Phase coexistence in annealed CaMn7O12

The structural phase transition in annealed CaMn₇O₁₂ has been investigated by using high resolution synchrotron radiation powder diffraction. There is a phase coexistence phenomenon: two different crystallographic phases coexist in the material between 410 and 458 K. The first one is trigonal and it has a charge ordering (CO) of the Mn³⁺ and Mn⁴⁺ ions, while the second one is cubic and charge delocalized (CD). The volume fraction of the CD phase increases with temperature from 22% at 418 K up to 100% at 468 K. Both phases have domains of at least 150 nm at each temperature. The annealing of CaMn₇O₁₂ relaxed a part of the strains in the lattice, but did not influence the phase coexistence phenomenon.