Low-temperature thermal-expansion anomaly in Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CuO<Subscript>6</Subscript>

Single-crystal samples of the Bi_{2 + x}Sr_{2 ? x ? y}Cu_{1 + y}O_{6 + δ} system revealed anomalous (negative) thermal expansion in the temperature range 10–20 K. Magnetic fields of 1–3 T were found to strongly affect the position and width of the anomaly region. A thermal-expansion singularity was detected at temperatures T≈30–50 K, which may be related to the formation of a pseudogap.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Substitution effects on the bulk and surface properties of (Li,Ni)Mn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Manganese oxides of spinel structure, LiMn₂O₄, Li_1-x Ni _x Mn₂O₄ (0.25 ≤ x≤ 0.75), and NiMn₂O₄, were studied by EDS, XRD, SEM, magnetic (M-H, M-T), and XPS measurements. The samples were synthesized by an ultrasound-assisted sol-gel method. EDS analysis showed good agreement with the formulations of the oxides. XRD and Rietveld refinement of X-ray data indicate that all samples crystallize in the Fd3m space group characteristic of the cubic spinel structure. The a-cell parameter ranges from a = 8.2276 Å (x = 0) to a = 8.3980 Å (x = 1). SEM results showed particle agglomerates ranging in size from 2.3 μm (x = 0) down to 0.8 μm (x = 1). Hysteresis magnetization vs. applied field curves in the 5–300K range was recorded. ZFC-FC measurements indicate the presence of two magnetic paramagnetic-ferrimagnetic transitions. The experimental Curie constant was found to vary from 5 to 7.1 cm³ K mol^?1 for the range of compositions studied (0 ≤ x ≤ 1). XPS studies of these oxides revealed the presence of Ni²⁺, Mn³⁺, and Mn⁴⁺. The experimental Ni/Mn atomic ratios obtained by XPS were in good agreement with the nominal values. A linear relationship of the average oxidation state of Mn with Ni content was observed. The oxide’s cation distributions as a function of Ni content from x = 0 ?Li⁺[Mn³⁺Mn⁴⁺]O₄ to x = 1 \( {\mathrm{Ni}}_{0.35}^{2+}{\mathrm{Mn}}_{0.65}^{3+}\left[{\mathrm{Ni}}_{0.65}^{2+}\right.\left.{\mathrm{Mn}}_{1.35}^{3+}\right]{\mathrm{O}}_4 \) were proposed.     

Electrospun Dy-doped SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers: microstructure and magnetic properties

SrDy _x Fe_12?x O₁₉ (x ≤ 0.08) nanofibers have been synthesized by the electrospinning method followed by calcinations process. The partial substitution of rare earth ions Dy³⁺ (10.5 μ _B of magnetic moments) mainly occupying 12k sublattice sites in the SrFe₁₂O₁₉ crystal structure is investigated and discussed in this work. An enhanced coercivity of 7155 Oe has been obtained when the doped content reached to 0.08 at a relative low calcination temperature of 800 °C. As a result, we believe the synthesized SrDy _x Fe_12?x O₁₉ nanofibers can potentially be useful in high-density recording media as well as permanent magnets.     

Photocatalytic ability of Bi<Subscript>6</Subscript>Ti<Subscript>3</Subscript>WO<Subscript>18</Subscript> nanoparticles with a mix-layered Aurivillius structure

Aurivillius phase layered perovskites Bi₆Ti₃WO₁₈ was prepared by the sol-gel citrate-complexation synthesis. The sample developed into the plate-like nanoparticles with the exposed (001) facets. The phase formation and structure have been verified via X-ray polycrystalline powder diffraction (XRD) Rietveld refinements. The nanoparticles were investigated via the measurements such as FE-SEM, TEM, EDS, and the surface analyses. UV–Vis absorption data revealed that the Aurivillius compound has a direct band characteristic with the band energy of 2.214 eV. The band structure of Bi₆Ti₃WO₁₈ nanoparticles was discussed on the base of the experiments and theoretical calculation. Bi³⁺-containing Aurivillius Bi₆Ti₃WO₁₈ shows efficient photocatalytic degradation for rhodamine B dye (RhB) with the visible light irradiation (λ?>?420 nm). Dynamic characteristic of the light-created excitons was measured by the luminescence and decay lifetime. The multivalent properties of W and Ti ions in the Aurivillius-like lattices of Bi₆Ti₃WO₁₈ photocatalyst were discussed.     

Suppression of superconductivity in layered Bi<Subscript>4</Subscript>O<Subscript>4</Subscript>S<Subscript>3</Subscript> by Ag doping

We report X-ray diffraction, magnetization and transport measurements for polycrystalline samples of the new layered superconductor Bi_4?x Ag _x O₄S₃(0 ≤ x ≤ 0.2). The superconducting transition temperature (T _C) decreases gradually and finally suppressed when x < 0.10. Accordingly, the resistivity changes from a metallic behavior for x < 0.1 to a semiconductor-like behavior for x > 0.1. The analysis of Seebeck coefficient shows there are two types of electron-like carriers dominate at different temperature regions, indicative of a multiband effect responsible for the transport properties. The suppression of superconductivity and the increased resistivity can be attributed to a shift of the Fermi level to the lower-energy side upon doping, which reduces the density of states at E _F. Further, our result indicates the superconductivity in Bi₄O₄S₃ is intrinsic and the dopant Ag prefers to enter the BiS₂ layers, which may essentially modify the electronic structure.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Spin-spin interaction and the EPR spectrum of KDy(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The EPR spectrum of a KDy(WO₄)₂ monoclinic crystal is investigated. It is found that the EPR spectrum of magnetically concentrated materials at a low frequency (9.2 GHz) undergoes a substantial transformation in addition to the well-known broadening of the EPR lines. At low Dy³⁺ concentrations (x<10^?2), the EPR spectrum of an isomorphic crystal, namely, KY_(1?x)Dy_x(WO₄)₂, is characterized by the parameters g_x=0, g_y=1.54, and g_z=14.6. For a magnetically concentrated crystal KDy(WO₄)₂, the g values are as follows: g_x=0, g_y=0.82, and g_z=2.52. It is demonstrated that the difference in the parameters is associated with the specific spin-spin interaction between Dy³⁺ ions, including the Dzyaloshinski interaction, which is not observed at high frequencies.     

Mn-doped Bi<Subscript>26</Subscript>Mo<Subscript>10</Subscript>O<Subscript>69-d</Subscript>: synthesis and characterization

In this work, we research two series of Mn-substituted bismuth molybdates: Bi_26-2xMn_2xMo₁₀O_69-d and Bi₂₆Mo_10-2yMn_2yO_69-d. The synthesis of powder samples is performed by the conventional solid state technology. Samples are characterized by X-ray diffraction, scanning electron microscopy, and chemical analysis methods, and it is shown that single phase Bi_26-2xMn_2xMo₁₀O_69-d and Bi₂₆Mo_10-2yMn_2yO_69-d complex oxides form up to x = 0.8 and y = 0. We use densitometry, grain size measurements and scanning electron microscopy to study the morphology of ceramic pellets and powders. This issue reveals formation of dense ceramic samples with low porosity (≤3%). High-temperature X-ray diffraction is used to define small deviation of unit cell parameters from their linear dependence on temperature. Measurement of electrical conductivity is made using a.c. impedance spectroscopy method. We observe the decrease of electrical conductivity in Bi_26-2xMn_2xMo₁₀O_69-d series depending on dopant concentration.     

Weak ferromagnetism in BiFeO<Subscript>3</Subscript>-based multiferroics

The magnetic properties of the Bi_{1 ? x} Ln _x FeO₃ (Ln is a rare-earth ion), Bi_{1 ? x} A _x FeO_{3 ? x/2} (A is an alkali earth ion), and BiFe_{1 ? x} Ti _x O_{3 + δ} solid solutions in magnetic fields up to 14 T have been studied. The concentration ranges of the existence of the ferroelectric phase described by the space group R3c have been determined. It is shown that the substitution of the rare-earth ions for the Bi³⁺ ions leads to a sharp decrease in the critical fields inducing the metamagnetic transition from a modulated antiferromagnetic state to a weakly ferromagnetic one; however, the modulated structure in the concentration range of the R3c phase is mainly retained. The substitution of the alkali earth ions (x ～ 0.1) for the bismuth ions leads to the total destruction of the modulated structure and to the implementation of the weakly ferromagnetic state within the R3c phase. A homogeneous weakly ferromagnetic state has been revealed when the Ti⁴⁺ ions (x = 0.1) are substituted for the Fe³⁺ ions in the ferroelectric R3c phase.     

Spin-dimerization in rare-earth substituted La<Subscript>2</Subscript>RuO<Subscript>5</Subscript>

The Ru-Ru spin-singlet formation in La_2 ? x L n _x RuO₅ (Ln = Pr, Nd, Sm, Gd, Dy) was investigated by measurements of the specific heat and magnetic susceptibility. After subtraction of the lattice contribution from the specific heat (C _p ), similar excess entropy values were obtained for all compounds. These entropies can be explained by the formation of antiferromagnetic Ru-spin dimers at low temperatures and provide a lower estimate for the intradimer exchange strength. Pronounced changes in the transition temperatures and a broadening of the corresponding peak in C _p were observed. These changes depend on the rare-earth element and are due to local structural changes and heterogeneities caused by the substitution. The magnetic susceptibilities can be described by the sum of a rare-earth paramagnetic moment and the susceptibility of the unsubstituted La₂RuO₅. Density functional theory (DFT) calculations were performed for various compounds to investigate the origin of the magnetic transition and the relationship between structural changes and the spin-dimerization temperature. The combination of the present results with previous structural investigations supports the model of a spin-pairing of the Ru moments which occurs as a reason of the structural phase transition in La_2 ? x L n _x RuO₅.     

Crystal-structure and magnetic phase transformations in solid solutions of BiFeO<Subscript>3</Subscript>-AFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (A = Ca,Sr, Ba,Pb)

Solid solutions of Bi_{1 ? x} A _x (Fe_{1 ? x/2}Nb _x/2)O₃, where A = Ca, Ba, and Pb, are obtained and their crystal structure and magnetic properties are investigated. It is shown that for A = Ca and x ≈ 0.15, the symmetry of the unit cell changes from rhombohedral (space group R3c) to orthorhombic (Pbnm). The transformation leads to the emergence of spontaneous magnetization due to the Dzyaloshinskii-Moriya interaction. Solid solutions with A = Pb remain rhombohedral up to a concentration of x = 0.3. Spontaneous magnetization sharply increases in the compound with x ≈ 1 at low temperatures and is due to the formation of the spin-glass component.     

The magnetization reversal in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript> granular systems

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M _FC and M _ZFC, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T _irr. For the sample with less CoFe₂, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad peak at an intermediate temperature T ₂ below T _irr , and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the ?d(M _FC ? M _ZFC)/dT curves of the sample with more CoFe₂, besides a broad peat at an intermediate temperature T ₂, a rapid rise around the low temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

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Graphical abstract CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂ were prepared by reducing CoFe₂O₄ in H₂ for 4 h (S4H) and 8 h (S8H). The temperature-dependent FC and ZFC magnetizations, i.e., M _FC and M _ZFC, under different magnetic fields from 500 Oe to 20 kOe have been investigated. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at field-dependent irreversible temperature T _irr. For the S4H sample, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad and field-dependent relaxing peak at T ₂ below T _irr (figure a), and the moments were suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the S8H sample, it exhibits the reentrant spin-glass state around 50 K, as evidenced by a peak in the M _FC curve (inset in figure b) and as a result of the cooperative effects of the random anisotropy of CoFe₂O₄, exchange–spring occurring at the interface of CoFe₂O₄ and CoFe₂ together with the inter-particle dipolar interaction (figure c); in ?d(M _FC ? M _ZFC)/dT curves, besides a broad relaxing peat at T ₂, a rapid rise around the low-temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

     

Magnetic Resonance Study of the Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Doped with Manganese

Crystals of 3D topological insulators, bismuth telluride Bi₂Te₃, doped with manganese were studied using electron spin resonance (ESR) spectroscopy together with the SQUID magnetometry, transport measurements, and X-ray characterization. The obtained ESR data, such as the temperature and the angular dependence of the resonance field, reveal the specific critical behavior and confirm the ferromagnetic ordering of Mn spins even at modest doping. In addition to the studies of the critical behavior of diluted ferromagnet Bi_2?x Mn _x Te_3, we also discuss the effects of the limited solubility of Mn ions giving rise to microscopic inclusions of the spurious magnetic phases which were revealed using ESR technique.     

Magnetic properties of the Gd<Subscript>2</Subscript>V<Subscript>0.67</Subscript>Mo<Subscript>1.33</Subscript>O<Subscript>7</Subscript> and Y<Subscript>2</Subscript>VMoO<Subscript>7</Subscript> pyrochlore compounds

It is demonstrated that 50% substitution of vanadium for molybdenum in the pyrochlore lattice of the complex oxide Y₂(V _x Mo_{1 ? x} )₂O₇ results in a transition from the spin-glass ground state (at x = 0) to the ferromagnetic state in Y₂VMoO₇ (a = 10.1645(2) Å, T _C = 55 K). The Gd₂V_0.67Mo_1.33O₇ compound (a = 10.2862(3) Å) is a ferromagnet with T _C (84 K) exceeding that of undoped Gd₂MnO₂O₇.     

Magnetic phase diagram of the Bi<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganites

The magnetic and elastic properties of the Bi_1-xCa_xMnO₃ manganites are studied. The phase transformations revealed are ferromagnet-spin glass (x≥0.15) and spin glass-charge-ordered antiferromagnet (x≥0.25). The ferromagnetic state is characterized by ordering of the Mn³⁺d _x ²-y orbitals. It is suggested that thespin glass state originates from local static Jahn-Teller distortions. The antiferromagnetic charge-ordered and the spin-glass disordered phases coexist in samples with 0.25<x<0.32, which may be due to the charge order-disorder phase transformation being martensitic in character. The magnetic phase diagram is constructed.     

Superconductivity with two-fold symmetry in topological superconductor Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Topological superconductivity is the quantum condensate of paired electrons with an odd parity of the pairing function. By using a Corbino-shape like electrode configuration, we measure the c-axis resistivity of the recently discovered superconductor Sr _x Bi₂Se₃ with the magnetic field rotating within the basal planes, and find clear evidence of two-fold superconductivity. The Laue diffraction measurements on these samples show that the maximum gap direction is either parallel or perpendicular to the main crystallographic axis. This observation is consistent with the theoretical prediction and strongly suggests that Sr _x Bi₂Se₃ is a topological superconductor.     

Negative thermal expansion coefficient in the high-temperature superconductor Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8 + <Emphasis Type="Italic">x</Emphasis></Subscript>

Powder and single-crystal samples of the high-temperature superconductor Bi₂Sr₂CaCu₂O_{8 + x} are studied by X-ray diffraction. Its thermal expansion coefficient is found to be negative over a wide temperature range (160–260 K). Possible causes of this effect are discussed.     

Effect of KNbO<Subscript>3</Subscript> modification on structural,electrical and magnetic properties of BiFeO<Subscript>3</Subscript>

The polycrystalline samples of (Bi_1?x K _x ) (Fe_1?x Nb _x ) O₃ (BKFN) for x = 0.0, 0.1, 0.2 and 0.3 were synthesized by a solid-state reaction method. The X-ray diffraction patterns of BKFN exhibit that the addition of KNbO₃ in BiFeO₃ gradually changes its structure from rhombohedral to pseudocubic. The analysis of scanning electron micrograph clearly showed that the sintered samples have well-defined and uniformly distributed grains. Addition of KNbO₃ to BiFeO₃ enhances the dielectric, ferroelectric and ferromagnetic properties of BiFeO₃. Detailed studies of impedance and related parameters of BKFN using the complex impedance spectroscopic technique exhibit the significant contributions of grain and grain boundaries in the resistive and transport properties of the materials. Some oxygen vacancies created in the ceramic samples during high-temperature processing play an important role in the conduction mechanism. The leakage current or tangent loss of BiFeO₃ is greatly reduced on addition of KNbO₃ to the parent compound BiFeO₃. Preliminary studies of ferroelectric and magnetic characteristics of the samples reveal the existence of ferroelectric, and weak ferromagnetic ordered ceramics.     

Effect of cation substitution on the lattice dynamics and ferroelectric instability of cubic BaTiO<Subscript>3</Subscript> and BaZrO<Subscript>3</Subscript> doped with Bi and La ions

The spectra of lattice vibration frequencies of solid solutions Ba_{1 ? x} Bi_2x/3? _x/3Ti(Zr)O₃ and Ba_{1 ? x} La _x Ti(Zr)_{1 ? x/4}? _x/4O₃ are calculated in terms of a generalized Gordon-Kim model with inclusion of the dipole and quadrupole polarizabilities. Over the entire concentration range, the calculated phonon spectra contain a ferroelectric soft mode. The effect of various interactions on the ferroelectric instability of these solid solutions is studied. It is shown that the character of ferroelectric instability is largely determined by the mechanism of charge compensation.