Magnetic Specific Heat of Heavily p-Type Doped (Zn,Mn)Te:P

The magnetic contribution to the specific heat of bulk crystals of Zn_1–x Mn _x Te ( x = 0.03) heavily (up to 10¹⁹ cm^–3) p-type doped with P is studied over the temperature range 0.5–15 K and magnetic field range 0–3 T. The magnetic specific heat observed at zero magnetic field indicates that a substantial part of the magnetic ions has the degeneracy of their magnetic ground state lifted by d–d and p–d exchange interactions. The effect increases for doped and annealed samples with higher concentration of conducting holes. We have also carried out a theoretical analysis that takes into account the contributions due to small magnetic clusters, single magnetic ions in crystal field of distorted crystal lattice, and low energy excitations of the p–d exchange-coupled system of local moments and carriers.     

EPR and vibrational studies of YVO4:Tm3+, Yb3+ single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic materials.     

Effects of Bismuth Doping on the Physical Properties of La0.6−x Bi x Sr0.4CoO3 (0≤x≤0.15) Cobaltites

The structural and magnetic properties of cobaltites with the nominal composition La_0.6?x Bi _x Sr_0.4CoO₃ (0≤x≤0.15) have been investigated. X-ray diffraction analysis using Rietveld refinement show that all our samples crystallize in the rhombohedral structure. The zero field cooled (ZFC) and field cooled (FC) magnetization curves at 50 mT exhibits thermomagnetic irreversibility signature of short range ferromagnetic interactions in our samples. The ferromagnetic–paramagnetic transition temperature decreases with increasing Bi amount. In the paramagnetic phase, all our synthesized samples obey to the Curie–Weiss law. The Curie–Weiss analysis suggests that the spin state of Co³⁺ is IS while Co⁴⁺ ions are in IS for x=0 and LS for x≥0.05. The Bi doping also leads to a weakening in the magnetic moment. The magnetic entropy change exhibits a maximum value which decreases from 2.28 J/kg?K for x=0 to 1.24 J/kg?K for x=0.15 upon a magnetic field change of 5 T.     

First principles density functional calculations of half-metallic ferromagnetism in Zn1-xCrxS and Cd1-xCrxS

We employ the full-potential linearized augmented plane wave plus local orbital (FP-L/APW + lo) method based on spin-polarized density functional theory (DFT) in order to investigate the structural, electronic and magnetic properties of ordered dilute ferromagnetic semiconductors Zn_1?xCr_xS and Cd_1?xCr_xS (x = 0.25) in the zinc blende (B3) phase. For the exchange-correlation functional, the generalized gradient approximation GGA (Wu-Cohen 06) has been used. Results of calculated electronic band structures and density of states of these dilute magnetic semiconductors (DMSs) are discussed in terms of the contribution of Cr 3d⁵ 4s¹, Zn 3d¹⁰ 4s², Cd 4d¹⁰ 5s² and S 3s² 3p⁴ partial density of states. For Cr-based systems without n or p-type doping, the stability of the ferromagnetic spin state versus the antiferromagnetic state is predicted. Band structure and density of states studies show half-metallic ferromagnetic nature for both alloys, Zn_1?xCr_xS and Cd_1?xCr_xS. Calculations of the s–d exchange constant N₀α and p–d exchange constant N₀β clearly indicate the magnetic nature of these compounds. From the calculated total magnetic moments we observe that p–d hybridization reduces the local magnetic moment of Cr from its free space charge value and produces small local magnetic moments on the nonmagnetic Zn, Cd and S sites. The robustness of half-metallicity of Zn_1?xCr_xS and Cd_1?xCr_xS as a function of lattice constant is also discussed.     

Local Atomic and Electronic Structure with Magnetism of La0.7Ca0.3Mn1?x Cu x O3 (x=0, 0.03, 0.06, 0.1)

Local atomic and electronic structure with magnetic properties, especially Griffiths phase, of polycrystalline samples La_0.7Ca_0.3Mn_1?x Cu _x O₃ (x=0, 0.03, 0.06, 0.1) have been studied. The X-ray absorption spectra (XAS) of Cu 2p core level prove that the valence state of Cu ions exhibits trivalent state when doping content x≤0.06 and divalent Cu²⁺ ions begin to show for x=0.1. For the valence states of Mn ions, the X-ray photoelectron spectroscopy data show that they are in mixed states of Mn³⁺ and?Mn⁴⁺, and a shift to lower binding energy is observed, which is not attributed to the variation of valence states of Mn ions but the change of crystallographic surroundings, because there is no obvious change detected by X-ray absorption fine structure spectroscopy (XAFS). The Debye-Waller factor (σ ²) of x=0.1 sample is only slightly larger compared to x=0, which may be the origin of enhancement of Griffiths phase observed in the inverse-susceptibility as a function of temperature (H/M～T). The H/M～T curves of Cu doped samples indicate coexistence of FM, AFM and PM phase above Curie temperature?T _C , which may be related to the strong hybridization of O 2p and Mn 3d reflected by O 1s XAS spectra.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Effects of Gd2O3 on structure and magnetic properties of Ni-Mn ferrite

The emulsion method was used to prepare nanocrystalline Ni_0.7Mn_0.3Gd _x Fe_2-x O₄ ferrites. The growth of particles, the structure and the magnetic properties were investigated by X-ray diffraction (XRD), Mössbauer spectroscopy and vibrating sample magnetometer (VSM). Furthermore, the influence of Gd₂O₃ on magnetic properties of Ni-Mn ferrite powders has been investigated in detail. When the crystallite sizes are about 30–40 nm, all the samples have the similar Ms values. The variational rules of saturation magnetization (Ms) and coercivity (Hc) along with doped-Gd contents at different sintering temperatures show that the maximum Gd ions content doped into ferrite lattices is x = 0.06. When Gd-doped content x is larger than 0.06, the doped Gd ions can’t enter into the ferrite lattice totally but reside at grain boundary, as the ionic radii of the Gd³⁺ ions are larger than that of Fe³⁺ ions. The ferrimagnetism have not disappeared completely, even if the crystallite size is 7.8 nm.     

Carrier-Concentration and Magnetic-Field Effect on Mn2+ Luminescence in Bulk Zn1−x Mn x Te Crystals

Measurements of photoluminescence, reflectance, and Hall effect as functions of the phosphorus doping level, temperature, and magnetic field in p-Zn_1?x Mn _x Te crystals are reported. The photoluminescence reveals two competing intra-Mn recombination channels. The first channel originates in the energy transfer from the photogenerated carriers to the internal Mn²⁺(3d⁵) states leading to the intra-Mn radiative recombination. The second one originates in the energy transfer from Mn ions to thermally activated carriers leading to intra-Mn nonradiative recombination. The Mn emission can be controlled either by changing the doping level with the phosphorus impurities or by varying the temperature and/or an external magnetic field.     

EPR and vibrational studies of YVO4:Tm, Yb single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic materials.     

Microscopic State of Low Doped Manganites La1 − xSrxMnO3 Probed by ESR

The electron spin resonance (ESR) measurements were performed in single crystals of La_{1 ? x} Sr _x MnO₃ (0.05 ≤ x ≤ 0.125) in order to study the interplay of crystal field, Dzyaloshinsky–Moriya interaction, Jahn–Teller (JT) effect, and orbital order. The angular dependence of the ESR linewidth of an untwinned La_0.95Sr_0.05MnO₃ single crystal has been analyzed in the high-temperature approximation, which takes into account the microscopic geometry of the four nonequivalent Mn positions in the orthorhombic unit cell. A strong mixing of the |3z ² ? r ²> and |x ² ? y ²> states for the real orbital configuration was found. Magnetic inhomogeneities observed in the ESR spectra across the composition range 0.075 ≤ x ≤ 0.125 can be attributed to the presence of ferromagnetic clusters (magnetic spin polarons) in the paramagnetic state. New polaronic models are proposed.     

Magnetic susceptibility and specific heat of Pr2?xCexCuO4?y

We report here the measurements of magnetic susceptibility of Pr_2–xCe_xCuO_4–y (x=0, 0.05 and 0.15) from 2K to 300K and the specific heat of Pr_1.85Ce_0.15CuO₄ between 6K and 60K. Fitting of the magnetic susceptibility data to a Curie-Weiss law gave effective magnetic moment (p_eff) values close to the free ion value of 3.58_B for Pr³⁺. p_eff was found to decrease with increase in cerium concentration. The site symmetry of Pr³⁺ in Pr_2–xCe_xCuO_4–y (PCCO) host is D_4h and a crystal field (CF) Hamiltonian appropriate to tetragonal symmetry was used to analyze the magnetic susceptibility data. J-mixing of all the thirteen multiplets of Pr³⁺ and intermediate coupled wave functions have been included. A best set of CF parameters obtained not only explains the magnetic susceptibility but also the inelastic neutron scattering spectra (INS) reasonably well. The Schottky component together with Debye and Einstein contributions successfully accounts for the measured specific heat.     

Magnetic properties of LaInO<Subscript>3</Subscript>-based perovskite-structure photoluminescent materials doped with Nd<Superscript>3+</Superscript>, Cr<Superscript>3+</Superscript>, and Mn<Superscript>3+</Superscript> ions

Single-phase ceramic samples of La_1–xNd_xInO₃ (0.007 ≤ x ≤ 0.05), LaIn_0.99M_0.01O₃, and La_0.95Nd_0.05In_0.995M_0.005O₃ (M = Cr³⁺ and Mn³⁺) solid solutions have been prepared by solid-state reactions, and their crystal structure, magnetic field dependences of their specific magnetization at 5 and 300 K, and temperature dependences of their molar magnetic susceptibility have been studied. It has been shown that the 300-K specific magnetization of the La_1–xNd_xInO₃ (x = 0.02, 0.05), La_0.95Nd_0.05In_0.995M_0.005O₃ (M = Cr³⁺ and Mn³⁺), and LaIn_0.99Mn_0.01O₃ solid solutions increases linearly with increasing magnetic field strength up to 14 T and that the magnitude of the 300-K specific magnetization of the La_0.993Nd_0.007InO₃ and LaIn_0.99Cr_0.01O₃ solid solutions increases linearly, but they have diamagnetic magnetization. At a temperature of 5 K, the magnetization of all the indates studied here increases nonlinearly with increasing magnetic field strength, gradually approaching magnetic saturation, without, however, reaching it in a magnetic field of 14 T. In the temperature range where the Curie–Weiss law is obeyed (5–30 K), the effective magnetic moments obtained for the Nd³⁺ ion (\({\mu _{effN{d^{3 + }}}}\)) in the La_1–xNd_xInO₃ solid solutions with x = 0.007, 0.02, and 0.05 are 2.95μ_B, 3.09μ_B, and 2.75μ_B, respectively, which is well below the theoretical value \({\mu _{effN{d^{3 + }}}}\)= 3.62μ_B. The effective magnetic moments of the Cr³⁺ and Mn³⁺ ions in the LaIn_0.99Cr_0.01O₃ and LaIn_0.99Mn_0.01O₃ solid solutions are 3.87μ^B and 5.11μ^B, respectively, and differ only slightly from the theoretical values \({\mu _{effC{r^{3 + }}}}\)= 3.87μ^B and \({\mu _{effM{n^{3 + }}}}\)= 4.9μ^B.     

Ab initio, crystal field and experimental spectroscopic studies of pure and Ni-doped KZnF3 crystals

Pure and Ni²⁺ doped KZnF₃ single crystals were studied using the combination of the DFT-based ab initio methods, crystal field theory and experimental spectroscopic techniques. The electronic, optical and elastic properties have been calculated and compared with available experimental data and good agreement was achieved. Elastic anisotropy of pure KZnF₃ was modeled; calculations of the sound velocity, Debye temperature, Grüneisen parameter and specific heat capacity were performed. Comparison of the calculated results for the pure and doped material, which is reported for the first time for the considered material, enabled to identify the changes in the optical and electronic properties, which are due to the introduced nickel impurity ions. In particular, it was shown that the lowest Ni 3d states appear in the host's band gap at about 1.0 eV above the valence band. The changes of the electron density distribution after doping were also shown. Microscopic analysis of the crystal field effects based on the performed ab initio calculations of the Ni²⁺ density of states at different external pressures enabled to estimate the constants of the electron–vibrational interaction, Huang-Rhys factor, Stokes shift and local bulk modulus around impurity ions. The crystal field calculations of the Ni²⁺ energy levels were performed to analyze and assign the experimental absorption spectrum. Such a combination of the ab initio and semi-empirical calculating techniques leads to a complementary picture of the physical properties of KZnF₃:Ni²⁺ and can be applied to other doped crystals.     

Effect of La–Zn Substitution on the Structure and Magnetic Properties of Low Temperature Co-Fired M-Type Barium Ferrite

Ba(LaZn) _x Fe_12?2x O₁₉ (0≤x≤0.5) powders with Bi₂O₃ as an additive was synthesized by a sintered route at 900 °C or 950 °C. The structure and magnetic properties of La–Zn substituted M-type barium ferrites were also investigated. When 0≤x≤0.5, only one crystal phase existed in the sample, and the morphology of the grains were shown to be gradually irregular. The little amount of La³⁺ ions and Zn²⁺ ions changed the equilibrium of Fe²⁺ and Fe³⁺ at the 2a site, which increased the Fe³⁺–O–Fe²⁺ superexchange interaction strength, and the saturation magnetization (Ms) of the samples was also improved. Meanwhile, the substitution of La³⁺ and Zn²⁺ ions and the grains’ size bought great effects on the magnetocrystalline anisotropy field. As a result, with sintering at 950 °C for 6 h, the max Ms value of the samples with x=0.1 was 67.26 emu/g, and the minimum coercivity (H _c ) value was 1718.89 Oe with x=0.3, respectively.     

57Fe Mössbauer studies on MgAlxCrxFe2-2xO4 spinel system

Based on ⁵⁷Fe Mössbauer spectroscopy studies conducted at 300 K, the magnetic behaviour of the spinel ferrite system MgAl_xCr_xFe_2-2xO₄ (x=0.0–0.5) has been investigated. The Mössbauer spectra for x=0.0–0.2 exhibit two Zeeman sextets, one due to the Fe³⁺ octahedral ions and the other due to the Fe³⁺ tetrahedral ions, while the compositions x=0.3, 0.4 and 0.5 showed central paramagnetic doublet superimposed on the magnetic sextets. The variation of hyperfine parameters and origin of the central doublet on the magnetic sextets have been discussed.     

d-Hole localization and the suppression of superconductivity in YBa2(Cu1-xZnx)3O7−y

The temperature and Zn concentration dependence of the electrical resistivity, specific heat, magnetic susceptibility, and electron paramagnetic resonance (EPR) spectra of YBa₂(Cu_1?x Zn _x )₃O_7?y withy～0.1 has been measured forx≤0.16. In addition, the temperature and field dependence of the magnetization has been measured for 2<T<300K and 0<H<9.0T, along with the temperature and quasihydrostatic pressure dependence of the electrical resistivity for selected samples for 0<P<13 GPa. The substitution of Zn for Cu in YBa₂Cu₃O_7?y causes a rapid and nearly linear depression of the superconducting transition temperature,T _c , withT _c going to 0 K forx≥ 0.10. YBa₂(Cu_1?x Zn _x )₃O_7?y retains the YBa₂Cu₃O_7-y orthorhombic structure forx≤0.16 for both the superconducting and nonsuperconducting samples. Initially, the unit cell volume increases nearly linearly with Zn content; however, an abrupt change occurs in the vicinityx=0.8–0.10. Forx<0.10, the temperature dependence of the electrical resistivity,ρ(T), is metallic-like (dρ/dT>0) andρ increases gradually with increasing Zn content. However, forx≥ 0.10,ρ(T) becomes semiconductor-like, with a very rapid increase of the resistivity with increasingx. The electrical resistivity, magnetic susceptibility, EPR spectra, and specific heat all indicate that thed-holes associated with the Cu ions become localized in the nonsuperconducting phase,x>-0.10.     

Influence of the presence of Fe2+ ion in nickel-zinc ferrite

The presence of small amounts of Fe²⁺ ion in nickel zinc ferrite significantly influences some of its magnetic properties. The lattice parameter increases slightly and the increase Δa is independent ofx. The variation of magnetization with zinc concentration is explained on the basis of the Yafet-Kittel model. Increase in the Néel temperature on Fe²⁺ substitution in Zn _x Ni_1-x Fe₂O₄ is remarkable. This has been explained on the basis of a four sublattice model. Our analysis shows thatJ _AB (d ⁵-d ⁵) interaction is most affected. The influence of Fe²⁺ ions on the relaxation processes in the Mössbauer line shapes of Ni-Zn ferrite is also investigated and is compared with Cu²⁺ doped Ni-Zn ferrite.     

Structural and dielectric relaxor properties of A-site deficient samarium-doped (Ba1−x Sm2x/3)(Zr0.3Ti0.7O3) ceramics

Rare earth samarium (Sm)-doped barium zirconate titanate (Ba_1?x Sm_2x/3)(Zr_0.3Ti_0.7)O₃ (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were prepared using solid state reaction (SSR) route. The structural and microstructural characterizations of the materials were done by using X-ray diffraction and SEM analysis, respectively. Rietveld refinement technique employed to investigate the details of crystal structure revealed single-phase cubic perovskite structure belonging to space group Pm-3m. Microstructure of the doped ceramics were found to be porous and of irregular shape and size along with aggregative characteristic. FTIR technique was employed to study the influence of additives in ceramics compositions and to investigate the displacement of M–O bonds. Raman spectroscopic study revealed that the substitution of Ba²⁺ ions by Sm³⁺ ions shifted the Raman-active modes toward higher energy, which indicated that these materials undergo an increase in average cubicity with increase in Sm³⁺ ion concentration. The temperature dependence of dielectric properties was investigated in the frequency range from 1 kHz to 1 MHz. The dielectric measurement indicated a diffuse type of phase transition (DPT). The broadening in the dielectric permittivity and frequency dependence behavior with increase in frequency indicated a relaxor behavior of these materials. The relaxation strength of these materials was well adjusted by using the Vogel–Fulcher relation.     

Effect of additional Zn<Superscript>2+</Superscript> dopant on the ferromagnetic properties of Co-doped CeO<Subscript>2</Subscript> nanoparticles prepared by sol–gel method

Effect of additional Zn²⁺ dopant on the ferromagnetism (FM) of Co doped CeO₂ nanoparticles was studied. The Zn and Co co-doped CeO₂ nanoparticles (Ce_0.97?xZn _x Co_0.03O₂: where x?=?0, 0.01, 0.03, 0.05) were prepared by sol–gel technique. The crystal structure, morphology, and magnetic properties were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy (Raman) and physical property measurement system (PPMS). XRD and Raman studied showed that certain amount of Zn²⁺ can readily be incorporated into the lattice of Co doped CeO₂ with single-phase of CeO₂ original cubic fluorite crystal structure, and no ferromagnetic secondary phase was observed. SEM images show Zn and Co co-doped CeO₂ nanoparticles were spherical and uniform size. The PPMS studied indicate that the room-temperature FM of Co doped CeO₂ nanoparticles increase with additional Zn²⁺ dopant. This result is helpful in understanding the origin of FM in diluted magnetic oxides (DMO) as well as improving the magnetic property of DMO.     

Study of Half-Metallic Ferromagnetism in Be0.75Ti0.25Y (Y = S,Se, and Te) Using Ab Initio Calculations: Potential Candidate for Spintronic Devices

The structural, elastic, electronic, and magnetic properties of Be_0.75Ti_0.25Y (Y = S, Se, and Te) have been investigated to understand their potential applications in spintonic devices. Crystals of BeS, BeSe, and BeTe, individually doped with Ti with a dopant concentration of x = 0.25, have been evaluated by using full-potential linearized augmented plane-wave plus local orbital method within the framework of density functional theory. We employed the Wu–Cohen generalized gradient approximation for optimizing the crystal structure and evaluating elastic properties. In order improve bandgap values and optical parameters, the modified Becke and Johnson (mBJ) potential has been employed. The theoretical investigation of band structure and density of states confirms the half-metallic ferromagnetic nature of these compounds. The elastic constants are calculated by the charpin method which shows that the compounds under consideration are brittle and anisotropic. Moreover, it is noted that tetrahedral crystal field splits the 3d state of Ti into triple degenerate t_2g and double degenerate e_g states. The exchange splitting energies Δ _x (d) and Δ _x (pd) and exchange constants (N ₀ α) and (N ₀ β) are predicted from triple degenerate t_2g states, and negative values of N ₀ β justify that the nature of effective potential is more attractive in spin down case rather than that in the spin up case. We also find the crystal field splitting (ΔE _crystal = E _t2g?E _eg) energy and reduction of the local magnetic moment of Ti from its free space charge value and creation of small local magnetic moments on the non-magnetic Be, S, Se, and Te sites by p–d hybridization.