EPR Study of Fe3+- and Ni2+-Doped Macroporous CaSiO3 Ceramics

Thermally stable macroporous CaSiO₃, Fe³⁺- and Ni²⁺-doped (0.5 to 5 mol%) ceramics have been prepared by solution combustion process by mixing respective metal nitrates (oxidizers), fumed silica. Diformol hydrazine is used as a fuel. The combustion products were identified by their X-ray diffraction and thermal gravimetry/differential thermal analysis. Single phases of β-CaSiO₃ and α-CaSiO₃ were observed at 950 and 1200 °C, respectively. The phase transition temperatures of combustion-derived CaSiO₃ were found to be lower compared to those obtained via solid-state reaction method. It is interesting to note that with an increase in the calcination temperature the samples become more porous with an increase in the pore diameter from 0.2 to 8 μm. The electron paramagnetic resonance (EPR) spectrum of Fe³⁺ ions in CaSiO₃ exhibits a weak signal at g = 4.20 ± 0.1 followed by an intense signal at g = 2.0 ± 0.1. The signal at g = 4.20 is ascribed to isolated Fe³⁺ ions at rhombic site. The signal at g = 2.0 is due to Fe³⁺ coupled together with dipolar interaction. In Ni²⁺-doped CaSiO₃ ceramics the EPR spectrum exhibits a symmetric absorption at g = 2.23 ± 0.1. This deviation from the free electron g-value is ascribed to octahedrally coordinated Ni²⁺ ions with moderately high spin–orbit coupling. The number of spins participating in resonance and the paramagnetic susceptibilities have been evaluated from EPR data as a function of Fe³⁺ as well as Ni²⁺ content. The effect of alkali ions (Li, Na and K) on the EPR spectra of these ceramics has also been studied. Authors' address: R. P. Sreekanth Chakradhar, Glass Technology Laboratory, Central Glass and Ceramic Research Institute, Kolkata 700032, India     

窄带隙KNb1-xFexO3-δ的室温铁磁性

We have investigated the structure, optical and magnetic properties of ferroelectric KNb_1-xFexO_3-δ (X=0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25) synthesized by a traditional solid-state reaction method. According to the X-ray diffraction and the results of Rietveld refinement, all the samples maintain orthorhombic distorted perovskite structures with Amm2 space group without any secondary phase, suggesting the well incorporation of Fe ions into the KNbO₃ matrix. With the increase of Fe concentration, the band gap of each sample is decreased gradually, which is much smaller than the 3.18 eV band gap of pure KNbO₃. Through X-ray photoelectron spectrum analysis, the increased density of oxygen vacancy and Fe ions may be responsible for the observed decrease in band gap. Compared with the pure KNbO₃, Fe doped samples exhibit room-temperature weak ferromagnetism. The ferromagnetism in KNb_1-xFexO_3-δ with low-concentration dopants (X=0.01-0.10) can be attributed to the bound magnetic polaron mediated exchange. The enhancement of magnetism for the high-concentration (X=0.10-0.20) doped samples may arise from the further increase of magnetic Fe ions.     

CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF La1.2Sr1.8-xCaxMn2O7

The effect of divalent cation substitution on the structure and magnetic properties of La_1.2Sr_1.8-xCa_xMn₂O₇ (x = 0－0.900) is investigated in this paper. Partly replacing divalent cation Sr²⁺ by Ca²⁺ ions results in the weakening and then disappearance of long-range ferromagnetic ordering, and the formation of spin canting and low-temperature spin-glass. Based on structural analysis by Rietveld profile fitting, we suggest that this variation of magnetic property be related to a Jahn－Teller-type attice distortion of MnO₆ octahedra due to the introduction of the smaller sized Ca²⁺ ions.     

Spectral dependence of photoinduced optical absorption in doped yttrium iron garnet single crystals

The photoinduced optical absorption α of doped yttrium iron garnets (YIG) is investigated. It is found that the optical absorption α at a wavelength of 1.1 μm depends on the wavelength of irradiating light in the range 0.6–1.9 μm. It is demonstrated that, in the Y₃Fe₅O₁₂ crystal with an acceptor Ba impurity, the photoinduced increase in α is due to the formation of Fe⁴⁺ ions in octahedral sites. The charge transfer occurs through photoexcitation of the ⁶ A _1g (⁶ S) → ⁴ T _1g (⁴ G) and ⁶ A _1g (⁶ S) → ⁴ T _2g (⁴ G) transitions of octahedral Fe³⁺ ions. In the crystal with a donor Si impurity, the increase in α is caused by the formation of Fe²⁺ ions upon photoionization of silicon. __________ Translated from Fizika Tverdogo Tela, Vol. 43, No. 7, 2001, pp. 1233–1235. Original Russian Text Copyright ? 2001 by Doroshenko, Nadezhdin.     

Magnetocaloric effects in Mn1.35Fe0.65P1-xSix compounds

The structural and magnetocaloric properties of Mn_1.35Fe_0.65P_1-xSi_x compounds are investigated. The Si-substituted compounds, Mn_1.35Fe_0.65P_1-xSi_x with x = 0.52, 0.54, 0.55, 0.56, and 0.57, are prepared by high-energy ball milling and the solid-state reaction. The X-ray diffraction shows that the compounds crystallize into the Fe₂P-type hexagonal structure with space group P62m. The magnetic measurements show that the Curie temperature of the compound increases from 253 K for x = 0.52 to 296 K for x = 0.56. The isothermal magnetic-entropy change of the Mn_1.35Fe_0.65P_1-xSi_x compound decreases with the Si content increasing. The maximal value of the magnetic-entropy change is about 7.0 J/kg稫 in the Mn_1.35Fe_0.65P_0.48Si_0.52 compound with a field change of 1.5 T. The compound quenched in water possesses a larger magnetic entropy change and a smaller thermal hysteresis than the non-quenched samples. The thermal hysteresis of the compound is less than 3.5 K. The maximum adiabatic temperature change is about 1.4 K in the Mn_1.35Fe_0.65P_0.45Si_0.55 compound with a field change of 1.48 T.     

Multiferroic properties of solben gel derived Bi5Fe1-xCoxTi3O15 thin films

Co-doped Bi₅FeTi₃O₁₅ thin films (BFCT-x, Bi₅Fe_1-xCo_xTi₃O₁₅) were prepared using a sol—gel technique. XRD patterns confirm their single phase Aurivillius structure, and the corresponding powder Rietveld analysis indicates the change of space group around x=0.12. The magnetic hysteresis loops are obtained and ferromagnetism is therefore confirmed in BFCT-x thin films. The remanent magnetization (M_r) first increases and reaches the maximum value of 0.42 emu/cm³ at x=0.12 due to the possible Fe³⁺—O—Co³⁺ ferromagnetic coupling. When x = 0.25, the M_r increases again because of the dominant Fe³⁺—O—Co³⁺ ferromagnetic coupling. The remanent polarization (2P_r) of BFCT-0.25 was measured to be as high as 62 μC/cm², a 75% increase when compared with the non-doped BFCT-0 films. The 2P_r remains almost unchanged after being subjected to 5.2 × 10⁹ read/write cycles. Greatly enhanced ferroelectric properties are considered to be associated with decreased leakage current density.     

Stability of the positively charged manganese centre in GaAs heterostructures examined theoretically by the effective mass approximation calculation near the Γ critical point

This paper describes an n-i-p-i-n model heterostructure with a manganese (Mn)-doped p-type base region to check the stability of a positively charged manganese A_Mn⁺ centre with two holes weakly bound by a negatively charged 3d⁵(Mn) core of a local spin S=5/2 in the framework of the effective mass approximation near the Γ critical point (k～0). By including the carrier screening effect, the ground state energy and the binding energy of the second hole in the positively charged centre A_Mn⁺ are calculated within a hole concentration range from 1 × 10¹⁶ cm^-3 to 1 × 10¹⁷ cm^-3, which is achievable by biasing the structure under photo-excitation. For comparison, the ground-state energy of a single hole in the neutral A_Mn⁰ centre is calculated in the same concentration range. It turns out that the binding energy of the second hole in the A_Mn⁺ centre varies from 9.27 meV to 4.57 meV. We propose that the presence of the A_Mn⁺ centre can be examined by measuring the photoluminescence from recombination of electrons in the conduction band with the bound holes in the A_Mn⁺ centre since a high frequency dielectric constant of varepsilon _∞ =10.66 can be safely adopted in this case. The novel feature of the ability to tune the impurity level of the A_Mn⁺ centre makes it attractive for optically and electrically manipulating local magnetic spins in semiconductors.     

Quantum transformation of spin structure of a Fe8 nanocluster in ultrastrong magnetic fields

The transformation of the spin structure of a high-spin Fe₈ cluster in a strong magnetic field has been investigated. The magnetization and magnetic susceptibility of the material are calculated at different external magnetic fields and temperatures. It is shown that the magnetic field induces transformation of the spin structure of a Fe₈ cluster from the quasi-ferrimagnetic structure with an average magnetic moment of 20 μ_B per molecule to the quasi-ferromagnetic structure with a magnetic moment of 40 μ_B. Unlike a similar transformation of a Néel ferrimagnet, which is continuous and occurs through an intermediate angular phase, this process in Fe₈ at low temperatures manifests itself as a cascade of discrete quantum jumps, each being the transition accompanied by an increase in the spin number of the complex. At high temperatures, the behavior of the magnetic cluster approaches the cluster behavior described by the classical theory. The nature of quantum jumps is discussed in terms of the magnetic-field-induced energy level crossing in the ground state of a magnetic cluster. __________ Translated from Fizika Tverdogo Tela, Vol. 42, No. 6, 2000, pp. 1068–1072. Original Russian Text Copyright ? 2000 by Zvezdin, Plis, Popov.     

Transmission of 18 keV negative ions Cl through nanocapillariesin Al2O3 membrane

We investigate the angular distribution of the transmitted 18keV negative ions Cl^- through Al₂O₃ nanocapillaries of 50 nm in diameter and 10 μm in length. Elastic scattering ions and inelastic scattering ions are obtained simultaneously. The experimental result is partially consistent with the guiding effect. We can qualitatively explain our experimental result through a dynamic process.     

Comparative studies of microwave absorption in the singlet paramagnets HoVO<Subscript>4</Subscript> and HoBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in strong pulsed magnetic fields

Microwave absorption in the tetragonal singlet paramagnets HoVO₄ (zircon structure) and HoBa₂Cu₃O _x (x ≈ 6, layered perovskite structure) is studied and compared in pulsed magnetic fields up to 40 T at low temperatures. These paramagnets are characterized by a singlet-doublet scheme of the low-lying levels of the Ho³⁺ ion in a crystal field. In a magnetic field directed along the tetragonal axis, HoVO₄ exhibits resonance absorption lines at wavelengths of 871, 406, and 305 μm, which correspond to electron transitions between the low-lying levels of the Ho³⁺ ion in the crystal field. The positions and intensities of these absorption lines in HoVO₄ are well described in terms of the crystal-field formalism with the well-known interaction parameters. The absorption spectra of HoBa₂Cu₃O _x at a wavelength of 871 μm exhibit broad resonance absorption lines against the background of strong nonresonance absorption. The effects of low-symmetry (orthorhombic, monoclinic) crystal-field components, the deviation of a magnetic field from a symmetry axis, and various pair interactions on the absorption spectra of the HoVO₄ and HoBa₂Cu₃O _x crystals are discussed. Original Russian Text ? Z.A. Kazeĭ, V.V. Snegirev, M. Goaran, L.P. Kozeeva, M.Yu. Kameneva, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 133, No. 3, pp. 632–645.     

LiMn2O4 films grown by pulsed-laser deposition

LiMn₂O₄ films have been deposited onto silicon wafer by pulsed-laser deposition (PLD) technique in order to test their reliability as cathode materials in rechargeable lithium microbatteries. The film formation has been studied as a function of the preparation conditions, i.e., composition of the target, substrate temperature, and oxygen partial pressure in the deposition chamber. Depending on the conditions of deposition, Mn₂O₃ was present as an impurity phase. When deposited onto silicon substrate maintained at 300 °C in an oxygen pressure of 100 mTorr from the target LiMn₂O₄+15 % Li₂O, the PLD films are well-textured with crystallite size of 300 nm. It is found that such a film crystallizes in the spinel structure (Fd3m symmetry) as evidenced by x-ray diffraction and Raman scattering measurements. Surface morphologies of layers were investigated by SEM. The cells Li//LiMn₂O₄ have been tested by cyclic voltammetry and galvanostatic charge-discharge techniques in the range 3.0–4.2 V. The voltage profiles show the two expected steps for Li_xMn₂O₄ with a specific capacity as high as 120 mC/cm² μm. The chemical diffusion coefficients for the Li_xMn₂O₄ thin films appear to be in the range of 10⁻¹¹-10⁻¹² cm²/s. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

PHASE DEPENDENCE OF LUMINESCENT EMISSION OF Eu2+ DOPED SrAl2O4

In this work, we made five samples of SrAl₂O₄: Eu²⁺, Dy³⁺, the α phase and β phase SrAl₂O₄:Eu²⁺,Dy³⁺ powder and pellet samples, and α phase single crystal. We have measured the emission spectra of all the samples. All the emission peaks are around 520 nm, which correspond to the transition from 4f⁶5d¹(²E_g) to 4f⁷(⁸S_7/2) of Eu²⁺ in SrAl₂O₄ host. The intensity of emission of the β phase is stronger than that of the α phase. We believe that it is because the Eu²⁺ ions have occupied the two types of sites in the α phase SrAl₂O₄ host and the lifetime of the transition of Eu²⁺ in the A site is longer than that in the B site. This result also proves that the β phase of the material is brighter than the α phase. In addition, the β phase can be achieved by quenching technique.     

利用原位傅里叶变换红外光谱诊断催化剂的特性和催化活性

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy (FTIR) for the investigation of the crystal structure, thermal stability, redox behavior (temperature-programmed reduction/temperatureprogrammed re-oxidation) as well as the catalytic properties of Co₃O₄ thin films. The syntheses of Co₃O₄ were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm^-1 (υ₁) and 650 cm^-1 (υ₂) respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co₃O₄ spinel. The lattice stability limit of Co₃O₄ was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ₁ and υ₂ as a function of the temperature. Moreover, Co₃O₄ has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO₂ and H₂O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co₃O₄ follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.     

Spectroscopic properties in Er Er3+/Yb3+Co-doped fluorophosphate glass

Using the technique of high-temperature melting, a new Er³⁺/Yb³⁺ co-doped fluorophosphate glass was prepared. The absorption and fluorescence spectra were investigated in depth. The effect of Er³⁺ and Yb³⁺ concentration on the spectroscopic properties of the glass sample was also discussed. According to the Judd-Ofelt theory, the oscillator strength was computed. The lifetime of ⁴I_13/2 level (τ_m) of Er³⁺ ions was 8.23 ms, and the full width at half maximum of the dominating emission peak was 68 nm at 1.53 τ_m. The large stimulated emission cross section of the Er³⁺ was calculated by the McCumber theory. The spectroscopic properties of Er³⁺ ion were compared with those in different glasses. The full width at half maximum and σ_e are larger than those of other glass hosts, indicating this studied glass may be a potentially useful candidate for high-gain erbium-doped fiber amplifier.     

Weak ferromagnetism in copper metaborate CuB2O4

CuB₂O₄ single crystals have been grown and their magnetic and resonance properties have been investigated for the first time. The temperature dependence of the susceptibility was found to contain features at T=21 and 10 K. The CuB₂O₄ single crystal transformed at T=21 K to a weakly ferromagnetic state. The sharp drop in susceptibility at T<10 K is caused by a transition of the magnetic system of CuB₂O₄ to an antiferromagnetic state. The effective magnetic moment of the Cu₂₊ ion, determined from the high-temperature part of the magnetic susceptibility, is 1.77 μ _B. The room-temperature g factors are, respectively, 2.170 and 2.133 for magnetic field parallel and perpendicular to the c axis of the crystal. The antiferromagnetic resonance parameters in the weakly ferromagnetic and antiferromagnetic phases were measured. Fiz. Tverd. Tela (St. Petersburg) 41, 1267–1271 (July 1999)     

Edge photoluminescence spectra and the intensity of the intracenter <Emphasis Type="Italic">f</Emphasis>-<Emphasis Type="Italic">f</Emphasis> transitions in Er-and Sm-doped GaN crystals

Doping of GaN crystals prepared by various methods (HVPE and MOCVD) with various degrees of perfection of the mosaic structure, using rare-earth (RE) ions has been studied. An analysis of the shape of the photoluminescence spectra obtained before and after the doping showed that, as the defect concentration decreases, the intracenter f-f transitions characteristic of RE ions, at 1.54 and 0.54 μm in Er³⁺ and 0.72 μm in Sm²⁺, become observable. The intracenter f-f transitions of RE ions are seen, as a rule, in epitaxial layers with well-aggregated and relaxed domains and are absent in the case of a mosaic structure containing domains in the near-surface part of the epitaxial layer that are not fully coalesced. RE doping of the crystals under study was observed to initiate defect gettering. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 814–819. Original Russian Text Copyright ? 2004 by Krivolapchuk, Lundin, Mezdrogina, Nasonov, Rodin, Shmidt.     

Transport properties and battery discharge characteristics of the Ag+ ion conducting composite electrolyte system (1−x)[0.75AgI: 0.25AgCl]: xFe2O3

Ion transport and battery discharge characteristic studies are reported for a new Ag⁺ ion conducting two-phase composite electrolyte system (1−x)[0.75AgI: 0.25AgCl]: xFe₂O₃, where 0 ≤ x ≤ 0.5 in molar weight fraction. An alternative single-phase host-matrix ‘annealed [0.75AgI: 0.25AgCl] mixed system/ solid solution’ has been used in place of the traditional host, AgI. Submicron size particles (<1 μm) of Fe₂O₃ has been used as second phase dispersoid. The composition 0.8[0.75AgI: 0.25AgCl]: 0.2Fe₂O₃, exhibiting the highest room temperature conductivity has been referred to as the optimum conducting composition (OCC). The reason for an enhancement of an order of magnitude in the conductivity from that of the pure host has been identified through direct determination of ionic mobility (μ) and mobile ion concentration (n) using transient ionic current (TIC) technique. The XRD study confirmed the coexistence of the constituent phases. The ionic transference number is found to be very close to unity. This reveals the fact that the silver ions are the sole charge carriers in the system. The results are discussed in the light of space-charge models proposed for the two-phase composite electrolyte systems. Solid state batteries, fabricated using OCC as electrolyte, Ag-metal as anode and mixtures of iodine & graphite, viz. (C+I₂), (C+KI₃), (C+(CH₃)₄NI₃), (C+(C₂H₅)₄NI₃), etc. as cathodes, were discharged under different load conditions. The battery with (C+I₂) cathode performed satisfactorily specially under low current drain states. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Optical parameters of Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses and their energy transfers at high temperature

This paper reports that a series of Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J--O intensity parameters Ω_k (k=2, 4, 6), spontaneous radiative lifetime τ_rad, spontaneous transition probability A, fluorescence branching ratio β and oscillator strength f_ed of the Nd³⁺ ions at room temperature are calculated based on Judd--Ofelt (J--O) theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd³⁺:Er³⁺:Yb³⁺ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb³⁺, Er³⁺ and Nd³⁺ ions are analysed. The results show that the J--O intensity parameters Ω₂ increase when the Nd³⁺ concentration of the Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of ⁴F_5/2 and ⁴F_3/2. The intensity of Nd³⁺ emissions at 595, 691, 753, 813 and 887 nm are markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Er³⁺ to Nd³⁺ and the contribution of a multi-phonon.     

FORMATION AND MAGNETIC PROPERTIES OF Dy2Fe17-xMnxC(x = 0-17) PREPARED BY ARC-MELTING

We report on alloys formed by replacing iron with manganese in the compound Dy₂Fe₁₇C_1.0 Samples were characterized by X-ray diffraction and magnetic measure-ments, The 2:17-type structure can be crystallized in the whole range of manganese substitution. The Curie temperature of the series of Dy₂Fe_17-xMn_xC_1.0(x= 0-17) drops down considerably from 515K for x = 0 to about 20K for compounds with high manganese concentration, and the compensation point was observed in a narrow range of x≈4-6. The rapid decrease of the magnetization shows that the manganese substitution is not a simple magnetic dilution to the transition-metal sublattice mo-ment, it indicates that the moment of Mn may be antiparallel to that of Fe. The field dependence of the magnetization of Dy₂Fe_17-xMn_xC_1.0 may indicate the existence of the nonlinear magnetic structure for the samples with high Mn conoentrations.     

Erbium in silicon carbide crystals: EPR and high-temperature luminescence

Erbium ions have been incorporated for the first time in bulk 6H-SiC crystals during growth, and they were unambiguously identified from the ¹⁶⁷Er EPR hyperfine structure. High-temperature luminescence of erbium ions at a wavelength of 1.54 μm has been detected. The observed luminescence exhibits an increase in intensity with increasing temperature. The observation of Er luminescence in 6H-SiC offers a promising potential for development of semiconductor light-emitting devices at a wavelength within the fiber-optics transparency window. Fiz. Tverd. Tela (St. Petersburg) 41, 38–40 (January 1999)